Fragmentation dynamics of ionized neon trimer inside helium nanodroplets: a theoretical study.

PubMed

Bonhommeau, David; Viel, Alexandra; Halberstadt, Nadine

2004-06-22

We report a theoretical study of the fragmentation dynamics of Ne(3) (+) inside helium nanodroplets, following vertical ionization of the neutral neon trimer. The motion of the neon atoms is treated classically, while transitions between the electronic states of the ionic cluster are treated quantum mechanically. A diatomics-in-molecules description of the potential energy surfaces is used, in a minimal basis set consisting of three effective p orbitals on each neon atom for the missing electron. The helium environment is modeled by a friction force acting on the neon atoms when their speed exceeds the Landau velocity. A reasonable range of values for the corresponding friction coefficient is obtained by comparison with existing experimental measurements. (c) 2004 American Institute of Physics.

Enhanced Ionization of Embedded Clusters by Electron-Transfer-Mediated Decay in Helium Nanodroplets.

PubMed

LaForge, A C; Stumpf, V; Gokhberg, K; von Vangerow, J; Stienkemeier, F; Kryzhevoi, N V; O'Keeffe, P; Ciavardini, A; Krishnan, S R; Coreno, M; Prince, K C; Richter, R; Moshammer, R; Pfeifer, T; Cederbaum, L S; Mudrich, M

2016-05-20

We report the observation of electron-transfer-mediated decay (ETMD) involving magnesium (Mg) clusters embedded in helium (He) nanodroplets. ETMD is initiated by the ionization of He followed by removal of two electrons from the Mg clusters of which one is transferred to the He ion while the other electron is emitted into the continuum. The process is shown to be the dominant ionization mechanism for embedded clusters for photon energies above the ionization potential of He. For Mg clusters larger than five atoms we observe stable doubly ionized clusters. Thus, ETMD provides an efficient pathway to the formation of doubly ionized cold species in doped nanodroplets.

Insights into geometries, stabilities, electronic structures, reactivity descriptors, and magnetic properties of bimetallic Nim Cun-m (m = 1, 2; n = 3-13) clusters: Comparison with pure copper clusters.

PubMed

Singh, Raman K; Iwasa, Takeshi; Taketsugu, Tetsuya

2018-05-25

A long-range corrected density functional theory (LC-DFT) was applied to study the geometric structures, relative stabilities, electronic structures, reactivity descriptors and magnetic properties of the bimetallic NiCu n -1 and Ni 2 Cu n -2 (n = 3-13) clusters, obtained by doping one or two Ni atoms to the lowest energy structures of Cu n , followed by geometry optimizations. The optimized geometries revealed that the lowest energy structures of the NiCu n -1 and Ni 2 Cu n -2 clusters favor the Ni atom(s) situated at the most highly coordinated position of the host copper clusters. The averaged binding energy, the fragmentation energies and the second-order energy differences signified that the Ni doped clusters can continue to gain an energy during the growth process. The electronic structures revealed that the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies of the LC-DFT are reliable and can be used to predict the vertical ionization potential and the vertical electron affinity of the systems. The reactivity descriptors such as the chemical potential, chemical hardness and electrophilic power, and the reactivity principle such as the minimum polarizability principle are operative for characterizing and rationalizing the electronic structures of these clusters. Moreover, doping of Ni atoms into the copper clusters carry most of the total spin magnetic moment. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Structure and stability of clusters of β-alanine in the gas phase: importance of the nature of intermolecular interactions.

PubMed

Piekarski, Dariusz Grzegorz; Díaz-Tendero, Sergio

2017-02-15

We present a theoretical study of neutral clusters of β-alanine molecules in the gas phase, (β-ala) n n ≤ 5. Classical molecular dynamics simulations carried out with different internal excitation energies provide information on the clusters formation and their thermal decomposition limits. We also present an assessment study performed with different families of density functionals using the dimer, (β-ala) 2 , as a benchmark system. The M06-2X functional provides the best agreement in geometries and relative energies in comparison with the reference values computed with the MP2 and CCSD(T) methods. The structure, stability, dissociation energies and vertical ionization potentials of the studied clusters have been investigated using this functional in combination with the 6-311++G(d,p) basis set. An exhaustive analysis of intermolecular interactions is also presented. These results provide new insights into the stability, interaction nature and formation mechanisms of clusters of amino acids in the gas phase.

Complexes of DNA bases and Watson-Crick base pairs interaction with neutral silver Agn (n = 8, 10, 12) clusters: a DFT and TDDFT study.

PubMed

Srivastava, Ruby

2018-03-01

We study the binding of the neutral Ag n (n = 8, 10, 12) to the DNA base-adenine (A), guanine (G) and Watson-Crick -adenine-thymine, guanine-cytosine pairs. Geometries of complexes were optimized at the DFT level using the hybrid B3LYP functional. LANL2DZ effective core potential was used for silver and 6-31 + G ** was used for all other atoms. NBO charges were analyzed using the Natural population analysis. The absorption properties of Ag n -A,G/WC complexes were also studied using time-dependent density functional theory. The absorption spectra for these complexes show wavelength in the visible region. It was revealed that silver clusters interact more strongly with WC pairs than with isolated DNA complexes. Furthermore, it was found that the electronic charge transferred from silver to isolated DNA clusters are less than the electronic charge transferred from silver to the Ag n -WC complexes. The vertical ionization potential, vertical electron affinity, hardness, and electrophilicity index of Ag n -DNA/WC complexes have also been discussed.

Density functional study on structure and stability of bimetallic AuNZn (N<=6) clusters and their cations

NASA Astrophysics Data System (ADS)

Tanaka, Hiromasa; Neukermans, Sven; Janssens, Ewald; Silverans, Roger E.; Lievens, Peter

2003-10-01

A systematic study on the structure and stability of zinc doped gold clusters has been performed by density functional theory calculations. All the lowest-energy isomers found have a planar structure and resemble pure gold clusters in shape. Stable isomers tend to equally delocalize valence s electrons of the constituent atoms over the entire structure and maximize the number of Au-Zn bonds in the structure. This is because the Au-Zn bond is stronger than the Au-Au bond and gives an extra σ-bonding interaction by the overlap between vacant Zn 4p and valence Au 6s(5d) orbitals. No three-dimensional isomers were found for Au5Zn+ and Au4Zn clusters containing six delocalized valence electrons. This result reflects that these clusters have a magic number of delocalized electrons for two-dimensional systems. Calculated vertical ionization energies and dissociation energies as a function of the cluster size show odd-even behavior, in agreement with recent mass spectrometric observations [Tanaka et al., J. Am. Chem. Soc. 125, 2862 (2003)].

Extreme ionization of Xe clusters driven by ultraintense laser fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heidenreich, Andreas; Last, Isidore; Jortner, Joshua

We applied theoretical models and molecular dynamics simulations to explore extreme multielectron ionization in Xe{sub n} clusters (n=2-2171, initial cluster radius R{sub 0}=2.16-31.0 A ring ) driven by ultraintense infrared Gaussian laser fields (peak intensity I{sub M}=10{sup 15}-10{sup 20} W cm{sup -2}, temporal pulse length {tau}=10-100 fs, and frequency {nu}=0.35 fs{sup -1}). Cluster compound ionization was described by three processes of inner ionization, nanoplasma formation, and outer ionization. Inner ionization gives rise to high ionization levels (with the formation of (Xe{sup q+}){sub n} with q=2-36), which are amenable to experimental observation. The cluster size and laser intensity dependence of themore » inner ionization levels are induced by a superposition of barrier suppression ionization (BSI) and electron impact ionization (EII). The BSI was induced by a composite field involving the laser field and an inner field of the ions and electrons, which manifests ignition enhancement and screening retardation effects. EII was treated using experimental cross sections, with a proper account of sequential impact ionization. At the highest intensities (I{sub M}=10{sup 18}-10{sup 20} W cm{sup -2}) inner ionization is dominated by BSI. At lower intensities (I{sub M}=10{sup 15}-10{sup 16} W cm{sup -2}), where the nanoplasma is persistent, the EII contribution to the inner ionization yield is substantial. It increases with increasing the cluster size, exerts a marked effect on the increase of the (Xe{sup q+}){sub n} ionization level, is most pronounced in the cluster center, and manifests a marked increase with increasing the pulse length (i.e., becoming the dominant ionization channel (56%) for Xe{sub 2171} at {tau}=100 fs). The EII yield and the ionization level enhancement decrease with increasing the laser intensity. The pulse length dependence of the EII yield at I{sub M}=10{sup 15}-10{sup 16} W cm{sup -2} establishes an ultraintense laser pulse length control mechanism of extreme ionization products.« less

Geometrical, electronic, and magnetic properties of CunFe (n=1-12) clusters: A density functional study

NASA Astrophysics Data System (ADS)

Ling, Wang; Dong, Die; Shi-Jian, Wang; Zheng-Quan, Zhao

2015-01-01

The geometrical, electronic, and magnetic properties of small CunFe (n=1-12) clusters have been investigated by using density functional method B3LYP and LanL2DZ basis set. The structural search reveals that Fe atoms in low-energy CunFe isomers tend to occupy the position with the maximum coordination number. The ground state CunFe clusters possess planar structure for n=2-5 and three-dimensional (3D) structure for n=6-12. The electronic properties of CunFe clusters are analyzed through the averaged binding energy, the second-order energy difference and HOMO-LUMO energy gap. It is found that the magic numbers of stability are 1, 3, 7 and 9 for the ground state CunFe clusters. The energy gap of Fe-encapsulated cage clusters is smaller than that of other configurations. The Cu5Fe and Cu7Fe clusters have a very large energy gap (>2.4 eV). The vertical ionization potential (VIP), electron affinity (EA) and photoelectron spectra are also calculated and simulated theoretically for all the ground-state clusters. The magnetic moment analyses for the ground-state CunFe clusters show that Fe atom can enhance the magnetic moment of the host cluster and carries most of the total magnetic moment.

Density functional study of the structural, electronic, and magnetic properties of Mo n and Mo n S ( n = 1 - 10) clusters

NASA Astrophysics Data System (ADS)

Ziane, M.; Amitouche, F.; Bouarab, S.; Vega, A.

2017-12-01

Structural and electronic properties of pure molybdenum Mo n and molybdenum-sulfide Mo n S ( n = 1 - 10) clusters were investigated in the framework of the density functional theory within the generalized gradient approximation to exchange and correlation with the aim of addressing how doping with a single S atom affects the geometries, magnetic properties, and reactivity of pure molybdenum clusters. These clusters exhibit a less marked tendency to dimerization than their isoelectronic Cr counterparts despite sharing their half-filled valence shell configuration. Doping with a single S impurity is enough to change the structure of the host molybdenum cluster to a large extent, as well as to modify the bonding pattern, the magnetic state and the magnetic moment distribution in the Mo host. Vertical ionization potentials and electron affinities are calculated to determine global reactivity indicators like the electronegativity and the chemical hardness. The results are discussed in terms of the thermodynamical and relative stabilities, charge transfer effects, and spin-polarized densities of electronic states.

Clustered DNA damages induced in human hematopoietic cells by low doses of ionizing radiation

NASA Technical Reports Server (NTRS)

Sutherland, Betsy M.; Bennett, Paula V.; Cintron-Torres, Nela; Hada, Megumi; Trunk, John; Monteleone, Denise; Sutherland, John C.; Laval, Jacques; Stanislaus, Marisha; Gewirtz, Alan

2002-01-01

Ionizing radiation induces clusters of DNA damages--oxidized bases, abasic sites and strand breaks--on opposing strands within a few helical turns. Such damages have been postulated to be difficult to repair, as are double strand breaks (one type of cluster). We have shown that low doses of low and high linear energy transfer (LET) radiation induce such damage clusters in human cells. In human cells, DSB are about 30% of the total of complex damages, and the levels of DSBs and oxidized pyrimidine clusters are similar. The dose responses for cluster induction in cells can be described by a linear relationship, implying that even low doses of ionizing radiation can produce clustered damages. Studies are in progress to determine whether clusters can be produced by mechanisms other than ionizing radiation, as well as the levels of various cluster types formed by low and high LET radiation.

Clustered DNA damages induced in isolated DNA and in human cells by low doses of ionizing radiation

NASA Technical Reports Server (NTRS)

Sutherland, B. M.; Bennett, P. V.; Sidorkina, O.; Laval, J.; Lowenstein, D. I. (Principal Investigator)

2000-01-01

Clustered DNA damages-two or more closely spaced damages (strand breaks, abasic sites, or oxidized bases) on opposing strands-are suspects as critical lesions producing lethal and mutagenic effects of ionizing radiation. However, as a result of the lack of methods for measuring damage clusters induced by ionizing radiation in genomic DNA, neither the frequencies of their production by physiological doses of radiation, nor their repairability, nor their biological effects are known. On the basis of methods that we developed for quantitating damages in large DNAs, we have devised and validated a way of measuring ionizing radiation-induced clustered lesions in genomic DNA, including DNA from human cells. DNA is treated with an endonuclease that induces a single-strand cleavage at an oxidized base or abasic site. If there are two closely spaced damages on opposing strands, such cleavage will reduce the size of the DNA on a nondenaturing gel. We show that ionizing radiation does induce clustered DNA damages containing abasic sites, oxidized purines, or oxidized pyrimidines. Further, the frequency of each of these cluster classes is comparable to that of frank double-strand breaks; among all complex damages induced by ionizing radiation, double-strand breaks are only about 20%, with other clustered damage constituting some 80%. We also show that even low doses (0.1-1 Gy) of high linear energy transfer ionizing radiation induce clustered damages in human cells.

Tailoring Ion Charge State Distribution in Tetramethyltin Clusters under Influence of Moderate Intensity Picosecond Laser Pulse: Role of Laser Wavelength and Rate of Energy Deposition

NASA Astrophysics Data System (ADS)

Sharma, Pramod; Das, Soumitra; Vatsa, Rajesh K.

2017-07-01

Systematic manipulation of ionic-outcome in laser-cluster interaction process has been realized for studies carried out on tetramethyltin (TMT) clusters under picosecond laser conditions, determined by choice of laser wavelength and intensity. As a function of laser intensity, TMT clusters exhibit gradual enhancement in overall ionization of its cluster constituents, up to a saturation level of ionization, which was distinct for different wavelengths (266, 355, and 532 nm). Simultaneously, systematic appearance of higher multiply charged atomic ions and shift in relative abundance of multiply charged atomic ions towards higher charge state was observed, using time-of-flight mass spectrometer. At saturation level, multiply charged atomic ions up to (C2+, Sn2+) at 266 nm, (C4+, Sn4+) at 355 nm, and (C4+, Sn6+) at 532 nm were detected. In addition, at 355 nm intra-cluster ion chemistry within the ionized cluster leads to generation of molecular hydrogen ion (H2 +) and triatomic molecular hydrogen ion (H3 +). Generation of multiply charged atomic ions is ascribed to efficient coupling of laser pulse with the cluster media, facilitated by inner-ionized electrons produced within the cluster, at the leading edge of laser pulse. Role of inner-ionized electrons is authenticated by measuring kinetic energy distribution of electrons liberated upon disintegration of excessively ionized cluster, under the influence of picosecond laser pulse.

Improvements in Ionized Cluster-Beam Deposition

NASA Technical Reports Server (NTRS)

Fitzgerald, D. J.; Compton, L. E.; Pawlik, E. V.

1986-01-01

Lower temperatures result in higher purity and fewer equipment problems. In cluster-beam deposition, clusters of atoms formed by adiabatic expansion nozzle and with proper nozzle design, expanding vapor cools sufficiently to become supersaturated and form clusters of material deposited. Clusters are ionized and accelerated in electric field and then impacted on substrate where films form. Improved cluster-beam technique useful for deposition of refractory metals.

Endohedral metallofullerene Sc3NC@C84: a theoretical prediction.

PubMed

Wang, Dong-Lai; Xu, Hong-Liang; Su, Zhong-Min; Xin, Guang

2012-11-21

Very recently, two novel Sc(3)NC-based cluster fullerenes Sc(3)NC@C(80) (Wang et. al. J. Am. Chem. Soc. 2010, 132, 16362) and Sc(3)NC@C(78) (Wu et. al. J. Phys. Chem. C 2011, 115, 23755) were prepared and characterized, respectively. Inspired by these findings, the possibility of encapsulating Sc(3)NC cluster in the C(84) fullerene is performed using density functional theory (DFT). Firstly, the isolated pentagon rule (IPR) D(2d) (23) C(84) fullerene is employed to encase the Sc(3)NC cluster: four possible endohedral metallofullerene isomers a-d are designed. The large binding energies (ranging from 163.7 to 210.0 kcal mol(-1)) indicate that the planar quinary cluster Sc(3)NC can be stably encapsulated in the C(84) (isomer 23) cage. Further, we consider the incorporation of Sc(3)NC into the non-IPR C(s) (51365) C(84) cage leading to isomer e and show the high stability of isomer e, which has a larger binding energy, larger HOMO-LUMO gap, higher adiabatic (vertical) ionization potential, and lower adiabatic (vertical) electron affinity than the former four Sc(3)NC@C(84) (isomer 23). Significantly, the predicted binding energy (294.2 kcal mol(-1)) of isomer e is even larger than that (289.2 and 277.7 kcal mol(-1), respectively) of the synthesized Sc(3)NC@C(80) and Sc(3)NC@C(78,) suggesting a considerable possibility for experimental realization. The (13)C NMR chemical shifts and Raman spectra of this a new endofullerene have been explored to assist future experimental characterization.

Study of Electron Ionization and Fragmentation of Non-hydrated and Hydrated Tetrahydrofuran Clusters

NASA Astrophysics Data System (ADS)

Neustetter, Michael; Mahmoodi-Darian, Masoomeh; Denifl, Stephan

2017-05-01

Mass spectroscopic investigations on tetrahydrofuran (THF, C4H8O), a common model molecule of the DNA-backbone, have been carried out. We irradiated isolated THF and (hydrated) THF clusters with low energy electrons (electron energy 70 eV) in order to study electron ionization and ionic fragmentation. For elucidation of fragmentation pathways, deuterated TDF (C4D8O) was investigated as well. One major observation is that the cluster environment shows overall a protective behavior on THF. However, also new fragmentation channels open in the cluster. In this context, we were able to solve a discrepancy in the literature about the fragment ion peak at mass 55 u in the electron ionization mass spectrum of THF. We ascribe this ion yield to the fragmentation of ionized THF clusters.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, H.B.; Hu, Y.J.; Bernstein, E.R.

Small methanol clusters are formed by expanding a mixture of methanol vapor seeded in helium and are detected using vacuum UV (vuv) (118 nm) single-photon ionization/linear time-of-flight mass spectrometer (TOFMS). Protonated cluster ions, (CH{sub 3}OH){sub n-1}H{sup +} (n=2-8), formed through intracluster ion-molecule reactions following ionization, essentially correlate to the neutral clusters, (CH{sub 3}OH){sub n}, in the present study using 118 nm light as the ionization source. Both experimental and Born-Haber calculational results clarify that not enough excess energy is released into protonated cluster ions to initiate further fragmentation in the time scale appropriate for linear TOFMS. Size-specific spectra for (CH{submore » 3}OH){sub n} (n=4 to 8) clusters in the OH stretch fundamental region are recorded by IR+vuv (118 nm) nonresonant ion-dip spectroscopy through the detection chain of IR multiphoton predissociation and subsequent vuv single-photon ionization. The general structures and gross features of these cluster spectra are consistent with previous theoretical calculations. The lowest-energy peak contributed to each cluster spectrum is redshifted with increasing cluster size from n=4 to 8, and limits near {approx}3220 cm{sup -1} in the heptamer and octamer. Moreover, IR+vuv nonresonant ionization detected spectroscopy is employed to study the OH stretch first overtone of the methanol monomer. The rotational temperature of the clusters is estimated to be at least 50 K based on the simulation of the monomer rotational envelope under clustering conditions.« less

Ground and excited states of the Rydberg radical H3O: Electron propagator and quantum defect analysis

NASA Astrophysics Data System (ADS)

Melin, Junia; Ortiz, J. V.; Martín, I.; Velasco, A. M.; Lavín, C.

2005-06-01

Vertical excitation energies of the Rydberg radical H3O are inferred from ab initio electron propagator calculations on the electron affinities of H3O+. The adiabatic ionization energy of H3O is evaluated with coupled-cluster calculations. These predictions provide optimal parameters for the molecular-adapted quantum defect orbital method, which is used to determine oscillator strengths. Given that the experimental spectrum of H3O does not seem to be available, comparisons with previous calculations are discussed. A simple model Hamiltonian, suitable for the study of bound states with arbitrarily high energies is generated by these means.

Structural, electronic and vibrational properties of small GaxNy (x+y = 2 5) nanoclusters: a B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Yadav, P. S.; Yadav, R. K.; Agrawal, B. K.

2007-02-01

An ab initio study of the stability, structural and electronic properties has been made for 49 gallium nitride nanoclusters, GaxNy (x+y = 2-5). Among the various configurations corresponding to a fixed x+y = n value, the configuration possessing the maximum value of binding energy (BE) is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize the geometries of the nanoclusters fully. The binding energies (BEs), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and the bond lengths have been obtained for all the clusters. We have considered the zero-point energy (ZPE) corrections ignored by the earlier workers. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have been investigated for the most stable structures. The configurations containing the N atoms in majority are seen to be the most stable structures. The strong N-N bond has an important role in stabilizing the clusters. For clusters containing one Ga atom and all the others as N atoms, the BE increases monotonically with the number of the N atoms. The HOMO-LUMO gap and IP fluctuate with the cluster size n, having larger values for the clusters containing odd number of N atoms. On the other hand, the EA decreases with the cluster size up to n = 3, and shows slow fluctuations thereafter for the larger clusters. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA) because of the lower energies of the most stable ground state of the cationic (anionic) clusters. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in experiments.

Optimizing the ionization and energy absorption of laser-irradiated clusters

NASA Astrophysics Data System (ADS)

Kundu, M.; Bauer, D.

2008-03-01

It is known that rare-gas or metal clusters absorb incident laser energy very efficiently. However, due to the intricate dependencies on all the laser and cluster parameters, it is difficult to predict under which circumstances ionization and energy absorption are optimal. With the help of three-dimensional particle-in-cell simulations of xenon clusters (up to 17256 atoms), it is shown that for a given laser pulse energy and cluster, an optimum wavelength exists that corresponds to the approximate wavelength of the transient, linear Mie-resonance of the ionizing cluster at an early stage of negligible expansion. In a single ultrashort laser pulse, the linear resonance at this optimum wavelength yields much higher absorption efficiency than in the conventional, dual-pulse pump-probe setup of linear resonance during cluster expansion.

Blue emitting undecaplatinum clusters

NASA Astrophysics Data System (ADS)

Chakraborty, Indranath; Bhuin, Radha Gobinda; Bhat, Shridevi; Pradeep, T.

2014-07-01

A blue luminescent 11-atom platinum cluster showing step-like optical features and the absence of plasmon absorption was synthesized. The cluster was purified using high performance liquid chromatography (HPLC). Electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) suggest a composition, Pt11(BBS)8, which was confirmed by a range of other experimental tools. The cluster is highly stable and compatible with many organic solvents.A blue luminescent 11-atom platinum cluster showing step-like optical features and the absence of plasmon absorption was synthesized. The cluster was purified using high performance liquid chromatography (HPLC). Electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) suggest a composition, Pt11(BBS)8, which was confirmed by a range of other experimental tools. The cluster is highly stable and compatible with many organic solvents. Electronic supplementary information (ESI) available: Details of experimental procedures, instrumentation, chromatogram of the crude cluster; SEM/EDAX, DLS, PXRD, TEM, FT-IR, and XPS of the isolated Pt11 cluster; UV/Vis, MALDI MS and SEM/EDAX of isolated 2 and 3; and 195Pt NMR of the K2PtCl6 standard. See DOI: 10.1039/c4nr02778g

Ionization energies of aqueous nucleic acids: photoelectron spectroscopy of pyrimidine nucleosides and ab initio calculations.

PubMed

Slavícek, Petr; Winter, Bernd; Faubel, Manfred; Bradforth, Stephen E; Jungwirth, Pavel

2009-05-13

Vertical ionization energies of the nucleosides cytidine and deoxythymidine in water, the lowest ones amounting in both cases to 8.3 eV, are obtained from photoelectron spectroscopy measurements in aqueous microjets. Ab initio calculations employing a nonequilibrium polarizable continuum model quantitatively reproduce the experimental spectra and provide molecular interpretation of the individual peaks of the photoelectron spectrum, showing also that lowest ionization originates from the base. Comparison of calculated vertical ionization potentials of pyrimidine bases, nucleosides, and nucleotides in water and in the gas phase underlines the dramatic effect of bulk hydration on the electronic structure. In the gas phase, the presence of sugar and, in particular, of phosphate has a strong effect on the energetics of ionization of the base. Upon bulk hydration, the ionization potential of the base in contrast becomes rather insensitive to the presence of the sugar and phosphate, which indicates a remarkable screening ability of the aqueous solvent. Accurate aqueous-phase vertical ionization potentials provide a significant improvement to the corrected gas-phase values used in the literature and represent important information in assessing the threshold energies for photooxidation and oxidation free energies of solvent-exposed DNA components. Likewise, such energetic data should allow improved assessment of delocalization and charge-hopping mechanisms in DNA ionized by radiation.

Penning ionization electron spectroscopy of CO 2 clusters in collision with metastable rare gas atoms

NASA Astrophysics Data System (ADS)

Maruyama, Ryo; Tanaka, Hideyasu; Yamakita, Yoshihiro; Misaizu, Fuminori; Ohno, Koichi

2000-09-01

Penning ionization electron spectra (PIES) of CO 2 clusters have been observed for the first time. An unusually fast electron band with excess kinetic energies of 1.4-2.9 eV with respect to the monomer band for the ionic X state was observed for CO 2 clusters in collision with He*(2 3S) atoms. While for PIES with Ne*(3 3P), no such unusual band was observed. The unusual band is ascribed to autoionization into stable structures of ionic clusters to which direct ionization processes are almost impossible due to very small Franck-Condon overlaps associated with a very large geometry difference between the ionic and neutral clusters.

Early stages of styrene-isoprene copolymerization in gas phase clusters probed by resonance enhanced multiphoton ionization.

PubMed

Mahmoud, Hatem; Germanenko, Igor N; El-Shall, M Samy

2006-04-06

We present direct evidence for the formation of the covalent bonded styrene (isoprene)(2) oligomer and the isoprene dimer ions following resonance ionization of the gas phase styrene-isoprene binary clusters. The application of resonance ionization to study polymerization reactions in clusters provides new information on the structure and mechanism of formation of the early stages of polymerization and holds considerable promise for the discovery of new initiation mechanisms and for the development of novel materials with unique properties.

Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

NASA Astrophysics Data System (ADS)

Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For vanadium oxide clusters, the oxygen-deficient clusters are detected for every family, indicating a stable structure of (VO2)x(V2O5)y. The stoichiometry of oxygen-rich clusters can be expressed as (MO2)0,1(M2O5)yO1-3 and their structures are consistent with chemically bonded species.

Observation of novel photochemistry in the multiphoton ionization of Mo(CO) sub 6 van der Waals clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peifer, W.R.; Garvey, J.F.

1989-07-27

van der Waals clusters of Mo(CO){sub 6} generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization and the product ions analyzed by quadrupole mass spectrometry. Oxomolybdenum and dioxomolybdenum ions are observed to be produced with high efficiency. This behavior is in striking contrast to that of metal carbonyl monomers and covalently bound cluster carbonyls, which under complete ligand loss prior to ionization. The observed photochemistry is ascribed to reactions between a photoproduced molybdenum atom and the ligands of neighboring Mo(CO){sub 6} solvent molecules within the van der Waals cluster.

Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

DOE PAGES

Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; ...

2016-04-05

Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through amore » combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated ( R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

Revealing isomerism in sodium-water clusters: Photoionization spectra of Na(H2O)n (n = 2-90)

NASA Astrophysics Data System (ADS)

Dierking, Christoph W.; Zurheide, Florian; Zeuch, Thomas; Med, Jakub; Parez, Stanislav; Slavíček, Petr

2017-06-01

Soft ionization of sodium tagged polar clusters is increasingly used as a powerful technique for sizing and characterization of small aerosols with possible application, e.g., in atmospheric chemistry or combustion science. Understanding the structure and photoionization of the sodium doped clusters is critical for such applications. In this work, we report on measurements of photoionization spectra for sodium doped water clusters containing 2-90 water molecules. While most of the previous studies focused on the ionization threshold of the Na(H2O)n clusters, we provide for the first time full photoionization spectra, including the high-energy region, which are used as reference for a comparison with theory. As reported in previous work, we have seen an initial drop of the appearance ionization energy with cluster size to values of about 3.2 eV for n <5 . In the size range from n = 5 to n = 15, broad ion yield curves emerge; for larger clusters, a constant range between signal appearance (˜2.8 eV) and signal saturation (˜4.1 eV) has been observed. The measurements are interpreted with ab initio calculations and ab initio molecular dynamics simulations for selected cluster sizes (n ≤ 15). The simulations revealed theory shortfalls when aiming at quantitative agreement but allowed us identifying structural motifs consistent with the observed ionization energy distributions. We found a decrease in the ionization energy with increasing coordination of the Na atom and increasing delocalization of the Na 3s electron cloud. The appearance ionization energy is determined by isomers with fully solvated sodium and a highly delocalized electron cloud, while both fully and incompletely solvated isomers with localized electron clouds can contribute to the high energy part of the photoionization spectrum. Simulations at elevated temperatures show an increased abundance of isomers with low ionization energies, an entropic effect enabling size selective infrared action spectroscopy, based on near threshold photoionization of Na(H2O)n clusters. In addition, simulations of the sodium pick-up process were carried out to study the gradual formation of the hydrated electron which is the basis of the sodium-tagging sizing.

Revealing isomerism in sodium-water clusters: Photoionization spectra of Na(H2O)n (n = 2-90).

PubMed

Dierking, Christoph W; Zurheide, Florian; Zeuch, Thomas; Med, Jakub; Parez, Stanislav; Slavíček, Petr

2017-06-28

Soft ionization of sodium tagged polar clusters is increasingly used as a powerful technique for sizing and characterization of small aerosols with possible application, e.g., in atmospheric chemistry or combustion science. Understanding the structure and photoionization of the sodium doped clusters is critical for such applications. In this work, we report on measurements of photoionization spectra for sodium doped water clusters containing 2-90 water molecules. While most of the previous studies focused on the ionization threshold of the Na(H 2 O) n clusters, we provide for the first time full photoionization spectra, including the high-energy region, which are used as reference for a comparison with theory. As reported in previous work, we have seen an initial drop of the appearance ionization energy with cluster size to values of about 3.2 eV for n<5. In the size range from n = 5 to n = 15, broad ion yield curves emerge; for larger clusters, a constant range between signal appearance (∼2.8 eV) and signal saturation (∼4.1 eV) has been observed. The measurements are interpreted with ab initio calculations and ab initio molecular dynamics simulations for selected cluster sizes (n≤ 15). The simulations revealed theory shortfalls when aiming at quantitative agreement but allowed us identifying structural motifs consistent with the observed ionization energy distributions. We found a decrease in the ionization energy with increasing coordination of the Na atom and increasing delocalization of the Na 3s electron cloud. The appearance ionization energy is determined by isomers with fully solvated sodium and a highly delocalized electron cloud, while both fully and incompletely solvated isomers with localized electron clouds can contribute to the high energy part of the photoionization spectrum. Simulations at elevated temperatures show an increased abundance of isomers with low ionization energies, an entropic effect enabling size selective infrared action spectroscopy, based on near threshold photoionization of Na(H 2 O) n clusters. In addition, simulations of the sodium pick-up process were carried out to study the gradual formation of the hydrated electron which is the basis of the sodium-tagging sizing.

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization.

PubMed

Neustetter, M; Jabbour Al Maalouf, E; Limão-Vieira, P; Denifl, S

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n (+) (0 ≤ n ≤ 6) and W2(CO)n (+) (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n (+) (0 ≤ n ≤ 3) and W2C(CO)n (+) (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.

Formation of positive cluster ions Li(n) Br (n = 2-7) and ionization energies studied by thermal ionization mass spectrometry.

PubMed

Veličković, S R; Đustebek, J B; Veljković, F M; Veljković, M V

2012-05-01

Clusters of the type Li(n)X (X = halides) can be considered as potential building blocks of cluster-assembly materials. In this work, Li(n)Br (n = 2-7) clusters were obtained by a thermal ionization source of modified design and selected by a magnetic sector mass spectrometer. Positive ions of the Li(n)Br (n = 4-7) cluster were detected for the first time. The order of ion intensities was Li(2)Br(+) > Li(4)Br(+) > Li(5)Br(+) > Li(6)Br(+) > Li(3)Br(+). The ionization energies (IEs) were measured and found to be 3.95 ± 0.20 eV for Li(2)Br, 3.92 ± 0.20 eV for Li(3)Br, 3.93 ± 0.20 eV for Li(4)Br, 4.08 ± 0.20 eV for Li(5)Br, 4.14 ± 0.20 eV for Li(6)Br and 4.19 ± 0.20 eV for Li(7)Br. All of these clusters have a much lower ionization potential than that of the lithium atom, so they belong to the superalkali class. The IEs of Li(n)Br (n = 2-4) are slightly lower than those in the corresponding small Li(n) or Li(n)H clusters, whereas the IEs of Li(n)Br are very similar to those of Li(n) or Li(n)H for n = 5 and 6. The thermal ionization source of modified design is an important means for simultaneously obtaining and measuring the IEs of Li(n)Br (n = 2-7) clusters (because their ions are hermodynamically stable with respect to the loss of lithium atoms in the gas phase) and increasingly contributes toward the development of clusters for practical applications. Copyright © 2012 John Wiley & Sons, Ltd.

Nanosecond laser-cluster interactions at 109-1012 W/cm 2

NASA Astrophysics Data System (ADS)

Singh, Rohtash; Tripathi, V. K.; Vatsa, R. K.; Das, D.

2017-08-01

An analytical model and a numerical code are developed to study the evolution of multiple charge states of ions by irradiating clusters of atoms of a high atomic number (e.g., Xe) by 1.06 μm and 0.53 μm nanosecond laser pulses of an intensity in the range of 109-1012 W/cm 2 . The laser turns clusters into plasma nanoballs. Initially, the momentum randomizing collisions of electrons are with neutrals, but soon these are taken over by collisions with ions. The ionization of an ion to the next higher state of ionization is taken to be caused by an energetic free electron impact, and the rates of impact ionization are suitably modelled by having an inverse exponential dependence of ionizing collision frequency on the ratio of ionization potential to electron temperature. Cluster expansion led adiabatic cooling is a major limiting mechanism on electron temperature. In the intensity range considered, ionization states up to 7 are expected with nanosecond pulses. Another possible mechanism, filamentation of the laser, has also been considered to account for the observation of higher charged states. However, filamentation is seen to be insufficient to cause substantial local enhancement in the intensity to affect electron heating rates.

Matrix Assisted and/or Laser Desorption Ionization Quadrupole Ion Trap Time-of-Flight Mass Spectrometry of WO3 Clusters Formation in Gas Phase. Nanodiamonds, Fullerene, and Graphene Oxide Matrices

NASA Astrophysics Data System (ADS)

Ausekar, Mayuri Vilas; Mawale, Ravi Madhukar; Pazdera, Pavel; Havel, Josef

2018-03-01

The formation of W x O y +●/-● clusters in the gas phase was studied by laser desorption ionization (LDI) and matrix assisted laser desorption ionization (MALDI) of solid WO3. LDI produced (WO3) n + ●/- ● ( n = 1-7) clusters. In MALDI, when using nano-diamonds (NDs), graphene oxide (GO), or fullerene (C60) matrices, higher mass clusters were generated. In addition to (WO3) n -● clusters, oxygen-rich or -deficient species were found in both LDI and MALDI (with the total number of clusters exceeding one hundred ≈ 137). This is the first time that such matrices have been used for the generation of(WO3) n + ●/-● clusters in the gas phase, while new high mass clusters (WO3) n -● ( n = 12-19) were also detected. [Figure not available: see fulltext.

Influence of the geometrical detail in the description of DNA and the scoring method of ionization clustering on nanodosimetric parameters of track structure: a Monte Carlo study using Geant4-DNA

NASA Astrophysics Data System (ADS)

Bueno, M.; Schulte, R.; Meylan, S.; Villagrasa, C.

2015-11-01

The aim of this study was to evaluate the influence of the geometrical detail of the DNA on nanodosimetric parameters of track structure induced by protons and alpha particles of different energies (LET values ranging from 1 to 162.5~\\text{keV}~μ {{\\text{m}}-1} ) as calculated by Geant4-DNA Monte Carlo simulations. The first geometry considered consisted of a well-structured placement of a realistic description of the DNA double helix wrapped around cylindrical histones (GeomHist) forming a 18 kbp-long chromatin fiber. In the second geometry considered, the DNA was modeled as a total of 1800 ten bp-long homogeneous cylinders (2.3 nm diameter and 3.4 nm height) placed in random positions and orientations (GeomCyl). As for GeomHist, GeomCyl contained a DNA material equivalent to 18 kbp. Geant4-DNA track structure simulations were performed and ionizations were counted in the scoring volumes. For GeomCyl, clusters were defined as the number of ionizations (ν) scored in each 10 bp-long cylinder. For GeomHist, clusters of ionizations scored in the sugar-phosphate groups of the double-helix were revealed by the DBSCAN clustering algorithm according to a proximity criteria among ionizations separated by less than 10 bp. The topology of the ionization clusters formed using GeomHist and GeomCyl geometries were compared in terms of biologically relevant nanodosimetric quantities. The discontinuous modeling of the DNA for GeomCyl led to smaller cluster sizes than for GeomHist. The continuous modeling of the DNA molecule for GeomHist allowed the merging of ionization points by the DBSCAN algorithm giving rise to larger clusters, which were not detectable within the GeomCyl geometry. Mean cluster size (m1) was found to be of the order of 10% higher for GeomHist compared to GeomCyl for LET <15~\\text{keV}~μ {{\\text{m}}-1} . For higher LETs, the difference increased with LET similarly for protons and alpha particles. Both geometries showed the same relationship between m1 and the cumulative relative frequency of clusters with ν ≥slant 3 (f3) within statistical variations, independently of particle type. In order to obtain ionization cluster size distributions relevant for biological DNA lesions, the complex DNA geometry and a scoring method without fixed boundaries should be preferred to the simple cylindrical geometry with a fixed scoring volume.

Effects of the nanoplasma on the energetics of Coulomb explosion of molecular clusters in ultraintense laser fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Last, Isidore; Jortner, Joshua

We report on theoretical and computational studies of electron and nuclear energies in the Coulomb explosion of (D{sub 2}){sub n/2} clusters (n=250-33 000, cluster radius R{sub 0}=11 A-55 A) coupled to ultraintense Gaussian laser fields (laser peak intensities I{sub M}=10{sup 15}-10{sup 18} W cm{sup -2}, pulse widths {tau}=25-50 fs, and frequency {nu}=0.35 fs{sup -1}). Molecular dynamics simulations were fit by semiempirical relations for the average E{sub av} and maximal E{sub M} ion energies and for their dependence on the cluster radius (R{sub 0}) and on the laser parameters. This revealed two kinds of Coulomb explosion domains separated by the bordermore » radius R{sub 0}{sup (I)}, which marks complete cluster outer ionization and which depends on I{sub M} and {tau}, (i) the cluster vertical ionization (CVI) domain (R{sub 0}R{sub 0}{sup (I)}), which prevails at lower laser intensities over a broad region of cluster sizes (i.e., at I{sub M}=10{sup 15} W cm{sup -2}, R{sub 0}>R{sub 0}{sup (I)}=6.2 A for {tau}=25 fs, and R{sub 0}>R{sub 0}{sup (I)}=9.5 A for {tau}=50 fs). The effects of the persistent nanoplasma on Coulomb explosion in the non-CVI domain are manifested by a distinct cluster size dependence, i.e., E{sub av}{proportional_to}R{sub 0}{sup {eta}} ({eta}=0) and E{sub M}{proportional_to}R{sub 0}{sup {eta}} ({eta}=1) for R{sub 0}>(2.0-2.5)R{sub 0}{sup (I)}, and by a bimodal distribution of the ion kinetic energies. The energetics of Coulomb explosion in the non-CVI domain and its dependence (or independence) on the cluster size and laser parameters was semiquantitatively described by a cold nanoplasma model, which is based on a lychee configuration of the cluster charge, and which induces Coulomb explosion in the presence of the persistent nanoplasma. The results of our analyses are general for the cluster size dependence of the energetics of Coulomb explosion of multicharged elemental and molecular Xe{sub n}, (CH{sub 4}){sub n}, and (DI){sub n} clusters in the non-CVI domain.« less

Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters.

PubMed

West, Adam H C; Yoder, Bruce L; Luckhaus, David; Saak, Clara-Magdalena; Doppelbauer, Maximilian; Signorell, Ruth

2015-04-16

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem to be mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes but decrease slightly with increasing cluster size.

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neustetter, M.; Jabbour Al Maalouf, E.; Denifl, S., E-mail: Stephan.Denifl@uibk.ac.at, E-mail: plimaovieira@fct.unl.pt

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO){sub 6}) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO){sub 6} clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO){sub n}{sup +} (0 ≤ n ≤ 6) and W{sub 2}(CO){sub n}{sup +} (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO){sub n}{sup +} (0 ≤more » n ≤ 3) and W{sub 2}C(CO){sub n}{sup +} (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.« less

Calculation of Hammett Equation parameters for some N,N‧-bis (substituted-phenyl)-1,4-quinonediimines by density functional theory

NASA Astrophysics Data System (ADS)

Sein, Lawrence T.

2011-08-01

Hammett parameters σ' were determined from vertical ionization potentials, vertical electron affinities, adiabatic ionization potentials, adiabatic electron affinities, HOMO, and LUMO energies of a series of N, N' -bis (3',4'-substituted-phenyl)-1,4-quinonediimines computed at the B3LYP/6-311+G(2d,p) level on B3LYP/6-31G ∗ molecular geometries. These parameters were then least squares fit as a function of literature Hammett parameters. For N, N' -bis (4'-substituted-phenyl)-1,4-quinonediimines, the least squares fits demonstrated excellent linearity, with the square of Pearson's correlation coefficient ( r2) greater than 0.98 for all isomers. For N, N' -bis (3'-substituted-3'-aminophenyl)-1,4-quinonediimines, the least squares fits were less nearly linear, with r2 approximately 0.70 for all isomers when derived from calculated vertical ionization potentials, but those from calculated vertical electron affinities usually greater than 0.90.

Multistep Ionization of Argon Clusters in Intense Femtosecond Extreme Ultraviolet Pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bostedt, C.; Thomas, H.; Hoener, M.

The interaction of intense extreme ultraviolet femtosecond laser pulses ({lambda}=32.8 nm) from the FLASH free electron laser (FEL) with clusters has been investigated by means of photoelectron spectroscopy and modeled by Monte Carlo simulations. For laser intensities up to 5x10{sup 13} W/cm{sup 2}, we find that the cluster ionization process is a sequence of direct electron emission events in a developing Coulomb field. A nanoplasma is formed only at the highest investigated power densities where ionization is frustrated due to the deep cluster potential. In contrast with earlier studies in the IR and vacuum ultraviolet spectral regime, we find nomore » evidence for electron emission from plasma heating processes.« less

Water cluster fragmentation probed by pickup experiments

NASA Astrophysics Data System (ADS)

Huang, Chuanfu; Kresin, Vitaly V.; Pysanenko, Andriy; Fárník, Michal

2016-09-01

Electron ionization is a common tool for the mass spectrometry of atomic and molecular clusters. Any cluster can be ionized efficiently by sufficiently energetic electrons, but concomitant fragmentation can seriously obstruct the goal of size-resolved detection. We present a new general method to assess the original neutral population of the cluster beam. Clusters undergo a sticking collision with a molecule from a crossed beam, and the velocities of neat and doped cluster ion peaks are measured and compared. By making use of longitudinal momentum conservation, one can reconstruct the sizes of the neutral precursors. Here this method is applied to H2O and D2O clusters in the detected ion size range of 3-10. It is found that water clusters do fragment significantly upon electron impact: the deduced neutral precursor size is ˜3-5 times larger than the observed cluster ions. This conclusion agrees with beam size characterization by another experimental technique: photoionization after Na-doping. Abundant post-ionization fragmentation of water clusters must therefore be an important factor in the interpretation of experimental data; interestingly, there is at present no detailed microscopic understanding of the underlying fragmentation dynamics.

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters.

PubMed

Mahtout, Sofiane; Siouani, Chaouki; Rabilloud, Franck

2018-01-18

Structures, energetics, and electronic properties of noble metal-doped germanium (MGe n with M = Cu, Ag, Au; n = 1-19) clusters are systematically investigated by using the density functional theory (DFT) approach. The endohedral structures in which the metal atom is encapsulated inside of a germanium cage appear at n = 10 when the dopant is Cu and n = 12 for M = Ag and Au. While Cu doping enhances the stability of the corresponding germanium frame, the binding energies of AgGe n and AuGe n are always lower than those of pure germanium clusters. Our results highlight the great stability of the CuGe 10 cluster in a D 4d structure and, to a lesser extent, that of AgGe 15 and AuGe 15 , which exhibits a hollow cage-like geometry. The sphere-type geometries obtained for n = 10-15 present a peculiar electronic structure in which the valence electrons of the noble metal and Ge atoms are delocalized and exhibit a shell structure associated with the quasi-spherical geometry. It is found that the coinage metal is able to give both s- and d-type electrons to be reorganized together with the valence electrons of Ge atoms through a pooling of electrons. The cluster size dependence of the stability, the frontier orbital energy gap, the vertical ionization potentials, and electron affinities are given.

Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Wucher, Andreas; Winograd, Nicholas

2016-02-01

Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

Multiconfiguration Pair-Density Functional Theory Is Free From Delocalization Error.

PubMed

Bao, Junwei Lucas; Wang, Ying; He, Xiao; Gagliardi, Laura; Truhlar, Donald G

2017-11-16

Delocalization error has been singled out by Yang and co-workers as the dominant error in Kohn-Sham density functional theory (KS-DFT) with conventional approximate functionals. In this Letter, by computing the vertical first ionization energy for well separated He clusters, we show that multiconfiguration pair-density functional theory (MC-PDFT) is free from delocalization error. To put MC-PDFT in perspective, we also compare it with some Kohn-Sham density functionals, including both traditional and modern functionals. Whereas large delocalization errors are almost universal in KS-DFT (the only exception being the very recent corrected functionals of Yang and co-workers), delocalization error is removed by MC-PDFT, which bodes well for its future as a step forward from KS-DFT.

Rare-gas-cluster explosions under irradiation by intense short XUV pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, K.; Murphy, B.; Kandadai, N.

High-intensity, extreme-ultraviolet (XUV) femtosecond interactions with large rare-gas clusters of xenon and argon have been studied at a wavelength of 38 nm. Pulses of XUV radiation with nJ energy are produced by high-order harmonic conversion from a 35-fs, near-infrared, terawatt laser. Mass resolved ion spectra show charge states up to Xe{sup 8+} and Ar{sup 4+}. Kinetic-energy measurements of ions and electrons indicate that a nanoplasma is formed and a hydrodynamic cluster explosion ensues after heating by the short wavelength pulse. It appears that the observed charge states and electron temperatures are consistent with sequential, single-photon ionization and collisional ionization ofmore » ions that have had their ionization potential depressed by plasma continuum lowering in the cluster nanoplasma.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.

Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through amore » combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated ( R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

PubMed

Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

2014-08-01

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

Coupled-cluster treatment of molecular strong-field ionization

NASA Astrophysics Data System (ADS)

Jagau, Thomas-C.

2018-05-01

Ionization rates and Stark shifts of H2, CO, O2, H2O, and CH4 in static electric fields have been computed with coupled-cluster methods in a basis set of atom-centered Gaussian functions with a complex-scaled exponent. Consideration of electron correlation is found to be of great importance even for a qualitatively correct description of the dependence of ionization rates and Stark shifts on the strength and orientation of the external field. The analysis of the second moments of the molecular charge distribution suggests a simple criterion for distinguishing tunnel and barrier suppression ionization in polyatomic molecules.

Peas in a Pod: Environment and Ionization in Green Pea Galaxies

NASA Astrophysics Data System (ADS)

Kurtz, Heather; Jaskot, Anne; Drew, Patrick; Pare, Dylan; Griffin, Jon; Petersen, Michael

2016-01-01

The Green Peas are extreme, highly ionized, starburst galaxies with strong [OIII] 5007 emission. Using the Sloan Digital Sky Survey, we present statistics on the environment of Green Peas and investigate its effects on their ionized gas properties. Although most dwarf starburst galaxies are in low-density environments, we identify a sample of Green Peas in dense environments. Emission line observations with the WIYN 0.9-meter telescope at Kitt Peak reveal that one cluster Green Pea is more highly ionized in the direction of the cluster center. Ram pressure stripping likely generates this ionization gradient. We explore the role of the environment in enhancing star formation rates and ionization, and we compare the nebular properties of Green Peas in high-density environments to those in low-density environments.

Correlated electronic decay in expanding clusters triggered by intense XUV pulses from a Free-Electron-Laser

PubMed Central

Oelze, Tim; Schütte, Bernd; Müller, Maria; Müller, Jan P.; Wieland, Marek; Frühling, Ulrike; Drescher, Markus; Al-Shemmary, Alaa; Golz, Torsten; Stojanovic, Nikola; Krikunova, Maria

2017-01-01

Irradiation of nanoscale clusters and large molecules with intense laser pulses transforms them into highly-excited non- equilibrium states. The dynamics of intense laser-cluster interaction is encoded in electron kinetic energy spectra, which contain signatures of direct photoelectron emission as well as emission of thermalized nanoplasma electrons. In this work we report on a so far not observed spectrally narrow bound state signature in the electron kinetic energy spectra from mixed Xe core - Ar shell clusters ionized by intense extreme-ultraviolet (XUV) pulses from a free-electron-laser. This signature is attributed to the correlated electronic decay (CED) process, in which an excited atom relaxes and the excess energy is used to ionize the same or another excited atom or a nanoplasma electron. By applying the terahertz field streaking principle we demonstrate that CED-electrons are emitted at least a few picoseconds after the ionizing XUV pulse has ended. Following the recent finding of CED in clusters ionized by intense near-infrared laser pulses, our observation of CED in the XUV range suggests that this process is of general relevance for the relaxation dynamics in laser produced nanoplasmas. PMID:28098175

Structural, electronic and vibrational properties of GexCy (x+y=2-5) nanoclusters: A B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Goswami, Sohini; Saha, Sushmita; Yadav, R. K.

2015-11-01

An ab-initio study of the stability, structural and electronic properties has been made for 84 germanium carbide nanoclusters, GexCy (x+y=2-5). The configuration possessing the maximum value of final binding energy (FBE), among the various configurations corresponding to a fixed x+y=n value, is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize fully the geometries of the nanoclusters. The binding energies (BE), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps have been obtained for all the clusters and the bond lengths have been reported for the most stable clusters. We have considered the zero point energy (ZPE) corrections. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have also been investigated for the most stable structures. The configurations containing the carbon atoms in majority are seen to be the most stable structures. The strong C-C bond has important role in stabilizing the clusters. For the clusters containing one germanium atom and all the other as carbon atoms, the BE increases monotonically with the number of the carbon atoms. The HOMO-LUMO gap, IPs and EAs fluctuates with increase in the number of atoms. The nanoclusters containing even number of carbon atoms have large HOMO-LUMO gaps and IPs, whereas the nanoclusters containing even number of carbon atoms have small EAs. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA). The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in the experiments.

On star formation in stellar systems. I - Photoionization effects in protoglobular clusters

NASA Technical Reports Server (NTRS)

Tenorio-Tagle, G.; Bodenheimer, P.; Lin, D. N. C.; Noriega-Crespo, A.

1986-01-01

The progressive ionization and subsequent dynamical evolution of nonhomogeneously distributed low-metal-abundance diffuse gas after star formation in globular clusters are investigated analytically, taking the gravitational acceleration due to the stars into account. The basic equations are derived; the underlying assumptions, input parameters, and solution methods are explained; and numerical results for three standard cases (ionization during star formation, ionization during expansion, and evolution resulting in a stable H II region at its equilibrium Stromgren radius) are presented in graphs and characterized in detail. The time scale of residual-gas loss in typical clusters is found to be about the same as the lifetime of a massive star on the main sequence.

Direct evidence for radiative charge transfer after inner-shell excitation and ionization of large clusters

NASA Astrophysics Data System (ADS)

Hans, Andreas; Stumpf, Vasili; Holzapfel, Xaver; Wiegandt, Florian; Schmidt, Philipp; Ozga, Christian; Reiß, Philipp; Ben Ltaief, Ltaief; Küstner-Wetekam, Catmarna; Jahnke, Till; Ehresmann, Arno; Demekhin, Philipp V.; Gokhberg, Kirill; Knie, André

2018-01-01

We directly observe radiative charge transfer (RCT) in Ne clusters by dispersed vacuum-ultraviolet photon detection. The doubly ionized Ne2+-{{{N}}{{e}}}n-1 initial states of RCT are populated after resonant 1s-3p photoexcitation or 1s photoionization of Ne n clusters with < n> ≈ 2800. These states relax further producing Ne+-Ne+-{{{N}}{{e}}}n-2 final states, and the RCT photon is emitted. Ab initio calculations assign the observed RCT signal to the{}{{{N}}{{e}}}2+(2{{{p}}}-2{[}1{{D}}]){--}{{{N}}{{e}}}n-1 initial state, while transitions from other possible initial states are proposed to be quenched by competing relaxation processes. The present results are in agreement with the commonly discussed scenario, where the doubly ionized atom in a noble gas cluster forms a dimer which dissipates its vibrational energy on a picosecond timescale. Our study complements the picture of the RCT process in weakly bound clusters, providing information which is inaccessible by charged particle detection techniques.

Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

NASA Technical Reports Server (NTRS)

Padial, N.; Csanak, G.; Mckoy, B. V.; Langhoff, P. W.

1981-01-01

Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

Energy and charge transfer in ionized argon coated water clusters.

PubMed

Kočišek, J; Lengyel, J; Fárník, M; Slavíček, P

2013-12-07

We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H2O)n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar(+) and water occurs above the threshold; at higher electron energies above ~28 eV, an excitonic transfer process between Ar(+)* and water opens leading to new products Ar(n)H(+) and (H2O)(n)H(+). On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H2O)(n)H2(2+) and (H2O)(n)(2+) ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

PubMed Central

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; Fang, Yigang; Kostko, Oleg

2017-01-01

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion–molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C2H2)n+, just like ionized acetylene clusters. The fragmentation products result from reactive ion–molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C4H4+ and C6H6+ structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C2H2)n+ isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C6H6+ isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM. PMID:28484019

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

PubMed

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P; Fang, Yigang; Kostko, Oleg; Ahmed, Musahid; Head-Gordon, Martin

2017-05-23

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE PAGES

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; ...

2017-05-08

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Direct Standard-Free Quantitation of Tamiflu® and Other Pharmaceutical Tablets using Clustering Agents with Electrospray Ionization Mass Spectrometry

PubMed Central

Flick, Tawnya G.; Leib, Ryan D.; Williams, Evan R.

2010-01-01

Accurate and rapid quantitation is advantageous to identify counterfeit and substandard pharmaceutical drugs. A standard-free electrospray ionization mass spectrometry method is used to directly determine the dosage in the prescription and over-the-counter drugs, Tamiflu®, Sudafed®, and Dramamine®. A tablet of each drug was dissolved in aqueous solution, filtered, and introduced into solutions containing a known concentration of either L-tryptophan, L-phenylalanine or prednisone as clustering agents. The active ingredient(s) incorporates statistically into large clusters of the clustering agent where effects of differential ionization/detection are substantially reduced. From the abundances of large clusters, the dosages of the active ingredients in each of the tablets were determined to typically better than 20% accuracy even when the ionization/detection efficiency of the individual components differed by over 100×. Although this unorthodox method for quantitation is not as accurate as using conventional standards, it has the advantages that it is fast, it can be applied to mixtures where the identities of the analytes are unknown, and it can be used when suitable standards may not be readily available, such as schedule I or II controlled substances or new designer drugs that have not previously been identified. PMID:20092258

On the calculation of the energies of dissociation, cohesion, vacancy formation, electron attachment, and the ionization potential of small metallic clusters containing a monovacancy

NASA Astrophysics Data System (ADS)

Pogosov, V. V.; Reva, V. I.

2017-09-01

In terms of the model of stable jellium, self-consistent calculations of spatial distributions of electrons and potentials, as well as of energies of dissociation, cohesion, vacancy formation, electron attachment, and ionization potentials of solid clusters of Mg N , Li N (with N ≤ 254 ) and of clusters containing a vacancy ( N ≥ 12) have been performed. The contribution of a monovacancy to the energy of the cluster and size dependences of its characteristics and of asymptotics have been discussed. Calculations have been performed using a SKIT-3 cluster at Glushkov Institute of Cybernetics, National Academy of Sciences, Ukraine (Rpeak = 7.4 Tflops).

Maximum density echogram analysis : a novel approach to study the characteristics of oblique echoes observed by MARSIS/Mars Express

NASA Astrophysics Data System (ADS)

P, M.; Narukull, V. R.; Rao, S. V. B.

2017-12-01

The ionograms of the Mars Advance Radar for Subsurface and Ionospheric Sounding (MARSIS) instrument aboard Mars Express spacecraft show vertical and oblique echoes from the Martian ionosphere. The vertical echoes are from the normal ionosphere while the oblique echoes are believed to be from ionization bulges that occur in regions of strong vertical magnetic fields. These oblique echoes appear as downward facing hyperbolas when plotted as radargram (at 1.9 MHz), which is a color coded plot of apparent altitude as a function of time at a single frequency. In order to extract further information from these ionization bulges, we considered the peak density of the oblique echoes and plotted them in a format similar to a radargram and called it as a 'maximum density radargram' (MDR). Thus, an MDR shows the peak densities in entire ionization bulge. This analysis revealed several new aspects of the ionization bulges. We found that there is an asymmetry in the ionization bulge so that the density on one side of the hyperbola is different than the other side. In some cases, the density on the same side of the hyperbola, between the edge and apex, changes. Occasionally, the radargrams show only one side of the hyperbola, while the MDRs show a full hyperbola. When the density structures are repeatedly observed over the same location with a few days interval, the MDR analysis shows that the density inside the bulge varies from one pass to another. Finally, the ionization bulges in the MDR displays are clearly observed on several nights. Several of these nighttime bulges were not apparent in radargram analysis. These observations are discussed in the light of current understanding on the ionization bulges.

Color gradients in cooling flow cluster central galaxies and the ionization of cluster emission line systems

NASA Technical Reports Server (NTRS)

Romanishin, W.

1988-01-01

Preliminary results are given for a program to measure color gradients in the central galaxies in clusters with a variety of cooling flow rates. The objectives are to search for extended blue continuum regions indicative of star formation, to study the spatial distribution of star formation, and to make a quantitative measure of the amount of light from young stars, which can lead to a measure of the star formation rate (for an assumed initial mass function). Four clusters with large masses and large cluster H-alpha emission fluxes are found to have an excess of blue light concentrated to the centers of the cluster central galaxy. Assumption of a disk IMF leads to the conclusion that the starlight might play a major role in ionizing the emission line gas in these clusters.

A sampling device for counting insect egg clusters and measuring vertical distribution of vegetation

Treesearch

Robert L. Talerico; Robert W., Jr. Wilson

1978-01-01

The use of a vertical sampling pole that delineates known volumes and position is illustrated and demonstrated for counting egg clusters of N. sertifer. The pole can also be used to estimate vertical and horizontal coverage, distribution or damage of vegetation or foliage.

ON THE IONIZATION OF LUMINOUS WMAP SOURCES IN THE GALAXY: CONSTRAINTS FROM He RECOMBINATION LINE OBSERVATIONS WITH THE GBT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roshi, D. Anish; Plunkett, Adele; Rosero, Viviana

2012-04-10

Murray and Raham used the Wilkinson Microwave Anisotropy Probe (WMAP) free-free foreground emission map to identify diffuse ionized regions (DIRs) in the Galaxy. It has been found that the 18 most luminous WMAP sources produce more than half of the total ionizing luminosity of the Galaxy. We observed radio recombination lines (RRLs) toward the luminous WMAP source G49.75-0.45 with the Green Bank Telescope near 1.4 GHz. Hydrogen RRL is detected toward the source but no helium line is detected, implying that n{sub He{sup +}}/n{sub H{sup +}}< 0.024. This limit puts severe constraint on the ionizing spectrum. The total ionizing luminositymore » of G49 (3.05 Multiplication-Sign 10{sup 51} s{sup -1}) is {approx}2.8 times the luminosity of all radio H II regions within this DIR and this is generally the case for other WMAP sources. Murray and Rahman propose that the additional ionization is due to massive clusters ({approx}7.5 Multiplication-Sign 10{sup 3} M{sub Sun} for G49) embedded in the WMAP sources. Such clusters should produce enough photons with energy {>=}24.6 eV to fully ionize helium in the DIR. Our observations rule out a simple model with G49 ionized by a massive cluster. We also considered 'leaky' H II region models for the ionization of the DIR, suggested by Lockman and Anantharamaiah, but these models also cannot explain our observations. We estimate that the helium ionizing photons need to be attenuated by {approx}>10 times to explain the observations. If selective absorption of He ionizing photons by dust is causing this additional attenuation, then the ratio of dust absorption cross sections for He and H ionizing photons should be {approx}>6.« less

Observation of fullerenes (C60-C70) associated with LDEF crater number 31

NASA Technical Reports Server (NTRS)

Radicatidibrozolo, Filippo; Fleming, R. H.; Bunch, T. E.

1992-01-01

The presence of fullerenes in and around the LDEF crater number 31 is reported. This crater has a high C level associated with it, and is interpreted as having been produced by the impact of a C-rich micrometeoroid. Fullerenes are large 3-D C structures, among which the species C sub 60 (MW 720) and C sub 70 (MW 840) are preeminent. Fullerenes have several UV absorption bands, hence fullerenes should be detectable using UV laser ionization time-of-flight mass spectrometry. We use a LIMA-2A instrument with pulsed UV laser (266 nm) to search for high mass C species associated with LDEF crater number 31. The mass range was 0 to 1200 amu. Low ablating laser power levels were used (less than or = 5 x 10 exp 7 W/sq. cm); 200 mass spectra were acquired and summed. We observed high mass signals near m/z 720, exhibiting 24 amu separation, which is characteristic of fullerenes. Alkali ion signals were also observed. Little or no C clusters of intermediate mass were observed. We interpret the signals around m/z 720 as fullerenes, mainly C sub 60+ with lower levels of C sub 70+. We propose that the mechanism that produces these signals is resonant multiphoton ionization (REMPI). This selective mechanism explains why low mass C cluster ions are not observed along with the fullerenes, since they have much higher ionization potentials. This finding is unexpected, since up to now the search for fullerenes in extraterrestrial materials has not been successful. We conclude that the fullerenes became associated with crater number 31 in space. Two alternative (and exciting) scenarios are being considered at this time: either the fullerenes were carried by the C-rich projectile that formed crater number 31, or the fullerenes formed upon impact with the LDEF. We show the results of experiments at the ARC Vertical Gun Facility, which may establish some constraints on the origin of the fullerenes.

Delayed Ionization in Transition Metal Carbon Clusters

NASA Astrophysics Data System (ADS)

Kooi, S. E.; Castleman, A. W., Jr.

1997-03-01

Mass spectrometric studies of several single and binary transition metal carbon cluster systems, produced in a laser vaporization source, reveal several species that undergo delayed ionization. Pulsed extraction and blocking electric fields, in a time-of-flight mass spectrometer, allow the study of delayed ionization over a time window after excitation with a pulsed laser. In systems where metallocarbohedrenes (Met-Cars) are produced, the Met-Cars are the dominate delayed species. Delayed ionization of binary metal Met-Cars Ti_xM_yC_12 (M=Zr,Nb,Y; x+y=8) is dependent on the ratio of the two metals. Delayed behavior is investigated over a range of photoionization wavelengths and fluences. In order to determine the degree to which the delayed ionization is thermionic in character, the experimental data have been compared to Klots's model for thermionic emission from small particles.

An all-electron density functional theory study of the structure and properties of the neutral and singly charged M12 and M13 clusters: M = Sc-Zn.

PubMed

Gutsev, G L; Weatherford, C W; Belay, K G; Ramachandran, B R; Jena, P

2013-04-28

The electronic and geometrical structures of the M12 and M13 clusters where M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn along with their singly negatively and positively charged ions are studied using all-electron density functional theory within the generalized gradient approximation. The geometries corresponding to the lowest total energy states of singly and negatively charged ions of V13, Mn12, Co12, Ni13, Cu13, Zn12, and Zn13 are found to be different from the geometries of the corresponding neutral parents. The computed ionization energies of the neutrals, vertical electron detachment energies from the anions, and energies required to remove a single atom from the M13 and M13(+) clusters are in good agreement with experiment. The change in a total spin magnetic moment of the cation or anion with respect to a total spin magnetic moment of the corresponding neutral is consistent with the one-electron model in most cases, i.e., they differ by ±1.0 μ(B). Exceptions are found only for Sc12(-), Ti12(+), Mn12(-), Mn12(+), Fe12(-), Fe13(+), and Co12(+).

HOW TO FIND YOUNG MASSIVE CLUSTER PROGENITORS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bressert, E.; Longmore, S.; Testi, L.

2012-10-20

We propose that bound, young massive stellar clusters form from dense clouds that have escape speeds greater than the sound speed in photo-ionized gas. In these clumps, radiative feedback in the form of gas ionization is bottled up, enabling star formation to proceed to sufficiently high efficiency so that the resulting star cluster remains bound even after gas removal. We estimate the observable properties of the massive proto-clusters (MPCs) for existing Galactic plane surveys and suggest how they may be sought in recent and upcoming extragalactic observations. These surveys will potentially provide a significant sample of MPC candidates that willmore » allow us to better understand extreme star-formation and massive cluster formation in the Local Universe.« less

STAR CLUSTER FORMATION WITH STELLAR FEEDBACK AND LARGE-SCALE INFLOW

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matzner, Christopher D.; Jumper, Peter H., E-mail: matzner@astro.utoronto.ca

2015-12-10

During star cluster formation, ongoing mass accretion is resisted by stellar feedback in the form of protostellar outflows from the low-mass stars and photo-ionization and radiation pressure feedback from the massive stars. We model the evolution of cluster-forming regions during a phase in which both accretion and feedback are present and use these models to investigate how star cluster formation might terminate. Protostellar outflows are the strongest form of feedback in low-mass regions, but these cannot stop cluster formation if matter continues to flow in. In more massive clusters, radiation pressure and photo-ionization rapidly clear the cluster-forming gas when itsmore » column density is too small. We assess the rates of dynamical mass ejection and of evaporation, while accounting for the important effect of dust opacity on photo-ionization. Our models are consistent with the census of protostellar outflows in NGC 1333 and Serpens South and with the dust temperatures observed in regions of massive star formation. Comparing observations of massive cluster-forming regions against our model parameter space, and against our expectations for accretion-driven evolution, we infer that massive-star feedback is a likely cause of gas disruption in regions with velocity dispersions less than a few kilometers per second, but that more massive and more turbulent regions are too strongly bound for stellar feedback to be disruptive.« less

Clusters of primordial black holes and reionization problem

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belotsky, K. M., E-mail: k-belotsky@yandex.ru; Kirillov, A. A., E-mail: kirillov-aa@yandex.ru; Rubin, S. G., E-mail: sergeirubin@list.ru

2015-05-15

Clusters of primordial black holes may cause the formation of quasars in the early Universe. In turn, radiation from these quasars may lead to the reionization of the Universe. However, the evaporation of primordial black holes via Hawking’s mechanism may also contribute to the ionization of matter. The possibility of matter ionization via the evaporation of primordial black holes with allowance for existing constraints on their density is discussed. The contribution to ionization from the evaporation of primordial black holes characterized by their preset mass spectrum can roughly be estimated at about 10{sup −3}.

Nuclear microprobe investigation of the effects of ionization and displacement damage in vertical, high voltage GaN diodes

DOE PAGES

Vizkelethy, G.; King, M. P.; Aktas, O.; ...

2016-12-02

Radiation responses of high-voltage, vertical gallium-nitride (GaN) diodes were investigated using Sandia National Laboratories’ nuclear microprobe. Effects of the ionization and the displacement damage were studied using various ion beams. We found that the devices show avalanche effect for heavy ions operated under bias well below the breakdown voltage. Here, the displacement damage experiments showed a surprising effect for moderate damage: the charge collection efficiency demonstrated an increase instead of a decrease for higher bias voltages.

Nuclear microprobe investigation of the effects of ionization and displacement damage in vertical, high voltage GaN diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vizkelethy, G.; King, M. P.; Aktas, O.

Radiation responses of high-voltage, vertical gallium-nitride (GaN) diodes were investigated using Sandia National Laboratories’ nuclear microprobe. Effects of the ionization and the displacement damage were studied using various ion beams. We found that the devices show avalanche effect for heavy ions operated under bias well below the breakdown voltage. Here, the displacement damage experiments showed a surprising effect for moderate damage: the charge collection efficiency demonstrated an increase instead of a decrease for higher bias voltages.

Vertical lifting of ionization during geomagnetic storms from satellite measurements of ion composition

NASA Technical Reports Server (NTRS)

Goel, M. K.; Rao, B. C. N.; Chandra, S.; Maier, E. J.

1977-01-01

Magnetic-storm phenomena at low latitudes are discussed based on ion-composition /O(+), H(+), He(+)/ and electron- and ion-temperature measurements from the OGO-4 and Isis-2 satellites. For the moderately severe storms considered, the effects of changes in the neutral composition and in the neutral and plasma temperatures are discussed, and it is shown that these changes would not produce the observed O(+) increase during storms at low latitudes. It is suggested that the observed increase in O(+) in the topside region is a manifestation of the vertical lifting of ionization of the F-layer. The argument in favor of vertical lifting is further substantiated by the observed changes in the F-region critical frequency and the height parameters.

Clustered DNA damages induced by high and low LET radiation, including heavy ions

NASA Technical Reports Server (NTRS)

Sutherland, B. M.; Bennett, P. V.; Schenk, H.; Sidorkina, O.; Laval, J.; Trunk, J.; Monteleone, D.; Sutherland, J.; Lowenstein, D. I. (Principal Investigator)

2001-01-01

Clustered DNA damages--here defined as two or more lesions (strand breaks, oxidized purines, oxidized pyrimidines or abasic sites) within a few helical turns--have been postulated as difficult to repair accurately, and thus highly significant biological lesions. Further, attempted repair of clusters may produce double strand breaks (DSBs). However, until recently, there was no way to measure ionizing radiation-induced clustered damages, except DSB. We recently described an approach for measuring classes of clustered damages (oxidized purine clusters, oxidized pyrimidine clusters, abasic clusters, along with DSB). We showed that ionizing radiation (gamma rays and Fe ions, 1 GeV/amu) does induce such clusters in genomic DNA in solution and in human cells. These studies also showed that each damage cluster results from one radiation hit (and its track), thus indicating that they can be induced by very low doses of radiation, i.e. two independent hits are not required for cluster induction. Further, among all complex damages, double strand breaks comprise--at most-- 20%, with the other clustered damages being at least 80%.

Magnetic switching in Crx (x = 2-8) and its oxide cluster series

NASA Astrophysics Data System (ADS)

Shah, Esha V.; Roy, Debesh R.

2018-04-01

First principle studies on the magnetic ground state structure, noncollinearity, binding energy and various electronic properties of a series of Crx (x = 2-8) clusters are performed. In order to investigate the effect of ionization and oxidation on the clusters, the anionic (Crx-) and oxidized (CrxO2) analogues of those clusters are also studied in detail. To calculate adiabatic electron affinity of CrxO2 clusters, additionally CrxO2- analogues are also included in the present work. An interesting even (non-magnetic) - odd (magnetic) feature in the considered cluster series has been noticed. The similar behavior is also reflected from their electronic properties as even (less reactive) - odd (more reactive). The most of the neutral and ionized chromium clusters, viz., Crx and Crx- are found to be noncollinear in their ground states, whereas oxidation stabilized those clusters into the collinear spin alignments. The bond distances of Cr clusters are found to be close with available experimental studies.

Novel size-dependent chemistry within ionized van der Waals clusters of 1,1-difluoroethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coolbaugh, M.T.; Peifer, W.R.; Garvey, J.F.

1990-02-22

The authors present in this paper evidence for size-dependent cluster chemistry occurring in van der Waals clusters of 1,1-difluoroethane. Clusters of C{sub 2}H{sub 4}F{sub 2} are produced from a neat adiabatic expansion and are ionized via electron impact. In addition to the anticipated fragment ions, we observe ions with the general empirical formula of M{sub n}H{sup +} (where n {ge} 4). The reactive process that generates this species cannot be rationalized in terms of intramolecular analogues of known gas-phase bimolecular ion-molecular reactions. Hence, we fell the production of this product cluster ion represents an additional example of a brand newmore » class of ion-molecule reactions that can only occur within the unique solvated environment of the cluster.« less

Liquid argon TPC signal formation, signal processing and reconstruction techniques

NASA Astrophysics Data System (ADS)

Baller, B.

2017-07-01

This document describes a reconstruction chain that was developed for the ArgoNeuT and MicroBooNE experiments at Fermilab. These experiments study accelerator neutrino interactions that occur in a Liquid Argon Time Projection Chamber. Reconstructing the properties of particles produced in these interactions benefits from the knowledge of the micro-physics processes that affect the creation and transport of ionization electrons to the readout system. A wire signal deconvolution technique was developed to convert wire signals to a standard form for hit reconstruction, to remove artifacts in the electronics chain and to remove coherent noise. A unique clustering algorithm reconstructs line-like trajectories and vertices in two dimensions which are then matched to create of 3D objects. These techniques and algorithms are available to all experiments that use the LArSoft suite of software.

Real-time analysis of self-assembled nucleobases by Venturi easy ambient sonic-spray ionization mass spectrometry.

PubMed

Na, Na; Shi, Ruixia; Long, Zi; Lu, Xin; Jiang, Fubin; Ouyang, Jin

2014-10-01

In this study, the real-time analysis of self-assembled nucleobases was employed by Venturi easy ambient sonic-spray ionization mass spectrometry (V-EASI-MS). With the analysis of three nucleobases including 6-methyluracil (6MU), uracil (U) and thymine (T) as examples, different orders of clusters centered with different metal ions were recorded in both positive and negative modes. Compared with the results obtained by traditional electrospray ionization mass spectrometry (ESI-MS) under the same condition, more clusters with high orders, such as [6MU7+Na](+), [6MU15+2NH4](2+), [6MU10+Na](+), [T7+Na](+), and [T15+2NH4](2+) were detected by V-EASI-MS, which demonstrated the soft ionization ability of V-EASI for studying the non-covalent interaction in a self-assembly process. Furthermore, with the injection of K(+) to the system by a syringe pumping, the real-time monitoring of the formation of nucleobases clusters was achieved by the direct extraction of samples from the system under the Venturi effect. Therefore, the effect of cations on the formation of clusters during self-assembly of nucleobases was demonstrated, which was in accordance with the reports. Free of high voltage, heating or radiation during the ionization, this technique is much soft and suitable for obtaining the real-time information of the self-assembly system, which also makes it quite convenient for extraction samples from the reaction system. This "easy and soft" ionization technique has provided a potential pathway for monitoring and controlling the self-assembly processes. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of Ion Atomic Number on Single-Event Gate Rupture (SEGR) Susceptibility of Power MOSFETs

NASA Technical Reports Server (NTRS)

Lauenstein, Jean-Marie; Goldsman, Neil; Liu, Sandra; Titus, Jeffrey L.; Ladbury, Raymond L.; Kim, Hak S.; Phan, Anthony M.; LaBel, Kenneth A.; Zafrani, Max; Sherman, Phillip

2012-01-01

The relative importance of heavy-ion interaction with the oxide, charge ionized in the epilayer, and charge ionized in the drain substrate, on the bias for SEGR failure in vertical power MOSFETs is experimentally investigated. The results indicate that both the charge ionized in the epilayer and the ion atomic number are important parameters of SEGR failure. Implications on SEGR hardness assurance are discussed.

Valence ionized states of iron pentacarbonyl and eta5-cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy.

PubMed

Fukuda, Ryoichi; Ehara, Masahiro; Nakatsuji, Hiroshi; Kishimoto, Naoki; Ohno, Koichi

2010-02-28

Valence ionized states of iron pentacarbonyl Fe(CO)(5) and eta(5)-cyclopentadienyl cobalt dicarbonyl Co(eta(5)-C(5)H(5))(CO)(2) have been studied by ultraviolet photoelectron spectroscopy, two-dimensional Penning ionization electron spectroscopy (2D-PIES), and symmetry-adapted cluster-configuration interaction calculations. Theory provided reliable assignments for the complex ionization spectra of these molecules, which have metal-carbonyl bonds. Theoretical ionization energies agreed well with experimental observations and the calculated wave functions could explain the relative intensities of PIES spectra. The collision-energy dependence of partial ionization cross sections (CEDPICS) was obtained by 2D-PIES. To interpret these CEDPICS, the interaction potentials between the molecules and a Li atom were examined in several coordinates by calculations. The relation between the slope of the CEDPICS and the electronic structure of the ionized states, such as molecular symmetry and the spatial distribution of ionizing orbitals, was analyzed. In Fe(CO)(5), an attractive interaction was obtained for the equatorial CO, while the interaction for the axial CO direction was repulsive. For Co(eta(5)-C(5)H(5))(CO)(2), the interaction potential in the direction of both Co-C-O and Co-Cp ring was attractive. These anisotropic interactions and ionizing orbital distributions consistently explain the relative slopes of the CEDPICS.

Ionization of pyridine: Interplay of orbital relaxation and electron correlation.

PubMed

Trofimov, A B; Holland, D M P; Powis, I; Menzies, R C; Potts, A W; Karlsson, L; Gromov, E V; Badsyuk, I L; Schirmer, J

2017-06-28

The valence shell ionization spectrum of pyridine was studied using the third-order algebraic-diagrammatic construction approximation scheme for the one-particle Green's function and the outer-valence Green's function method. The results were used to interpret angle resolved photoelectron spectra recorded with synchrotron radiation in the photon energy range of 17-120 eV. The lowest four states of the pyridine radical cation, namely, 2 A 2 (1a 2 -1 ), 2 A 1 (7a 1 -1 ), 2 B 1 (2b 1 -1 ), and 2 B 2 (5b 2 -1 ), were studied in detail using various high-level electronic structure calculation methods. The vertical ionization energies were established using the equation-of-motion coupled-cluster approach with single, double, and triple excitations (EOM-IP-CCSDT) and the complete basis set extrapolation technique. Further interpretation of the electronic structure results was accomplished using Dyson orbitals, electron density difference plots, and a second-order perturbation theory treatment for the relaxation energy. Strong orbital relaxation and electron correlation effects were shown to accompany ionization of the 7a 1 orbital, which formally represents the nonbonding σ-type nitrogen lone-pair (nσ) orbital. The theoretical work establishes the important roles of the π-system (π-π* excitations) in the screening of the nσ-hole and of the relaxation of the molecular orbitals in the formation of the 7a 1 (nσ) -1 state. Equilibrium geometric parameters were computed using the MP2 (second-order Møller-Plesset perturbation theory) and CCSD methods, and the harmonic vibrational frequencies were obtained at the MP2 level of theory for the lowest three cation states. The results were used to estimate the adiabatic 0-0 ionization energies, which were then compared to the available experimental and theoretical data. Photoelectron anisotropy parameters and photoionization partial cross sections, derived from the experimental spectra, were compared to predictions obtained with the continuum multiple scattering approach.

Structure and Electronic Properties of Ionized PAH Clusters

NASA Astrophysics Data System (ADS)

Joblin, Christine; Kokkin, Damian L.; Sabbah, Hassan; Bonnamy, Anthony; Dontot, Leo; Rapacioli, Mathias; Simon, Aude; Spiegelman, Fernand; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Falvo, Cyril; Gamboa, Antonio; Brechignac, Philippe; Garcia, Gustavo A.; Nahon, Laurent

2014-06-01

Polycyclic aromatic hydrocarbon (PAH) clusters have been proposed as candidates for evaporating very small grains that are revealed by their mid-IR emission at the surface of UV-irradiated clouds in interstellar space. This suggestion is a motivation for further characterization of the properties of these clusters in particular when they are ionized. We have used a molecular beam coupled to the photoelectron-photoion coincidence spectrometer DELICIOUS II/ III at the VUV beamline DESIRS of the synchrotron SOLEIL to characterize the electronic properties of cationic coronene (C24H12) and pyrene (C16H10) clusters up to the pentamer and heptamer, respectively. These experimental results are analysed in the light of electronic structure calculations. Simulations of the properties of ionized PAH clusters are faced with the difficulty of describing charge delocalization in these large systems. We will show that recent developments combining a Density Functional Tight Binding method with Configuration Interaction scheme is successful in simulating the ionization potential, which gives strong confidence into the predicted structures for these PAH clusters. We will also present current effort to study charge transfer states by performing complementary measurements with the PIRENEA ion trap set-up. Joint ANR project GASPARIM, ANR-10-BLAN-501 M. Rapacioli, C. Joblin and P. Boissel Astron. & Astrophys., 429 (2005), 193-204. G. Garcia, H. Soldi-Lose and L. Nahon Rev. Sci. Instrum., 80 (2009), 023102; G. Garcia, B. Cunha de Miranda, M. Tia, S. Daly, L. Nahon, Rev. Sci. Instrum., 84 (2013), 053112 M. Rapacioli, A. Simon, L. Dontot and F. Spiegelman Phys. Status Solidi B, 249 (2) (2012), 245-258; L. Dontot, M. Rapacioli and F. Spiegelman (2014) submitted

Using reflection time-of-flight mass spectrometer techniques to investigate cluster dynamics and bonding

NASA Astrophysics Data System (ADS)

Wei, Shiqing; Castleman, A. W., Jr.

1994-02-01

Lase based time-of-flight mass spectrometer systems affixed with reflectrons are valuable tools for investigating cluster dynamics and reactions, spectroscopy and structures. Utilizing the reflectron time-of-flight mass spectrometer techniques, both decay fractions and kinetic energy releases of metastable cluster ions can be measured with high precision. By applying related theoretical models, the desired thermochemical values of metastable species can be deduced, which are otherwise very difficult to obtain. Several examples are discussed with attention focused on ammonia as a test case for hydrogen bond systems, and xenon for weaker van der Waals clusters. A brief overview of applications to investigating solvation effects on reactions and structures, delayed electron transfer and ionization through intracluster Penning ionization is also given.

Interstellar gas in the Gum Nebula

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallerstein, G.; Silk, J.; Jenkins, E.B.

1980-09-15

We have surveyed the interstellar gas in and around the Gum Nebula by optically observing 67 stars at Ca II, 42 stars at Na I, and 14 stars in the ultraviolet with the Copernicus satellite. Velocity dispersions for gas in the Gum Nebula, excluding the region of Vela remnant filaments, are not significantly larger than in the general interstellar medium. The ionization structure is predominantly that of an H II region with moderately high ionization, i.e., strong Si III and S III, in clouds with Vertical BarV/sub LSR/Vertical Bar> or approx. =10 km s/sup -1/. Furthermore, we find an increasemore » in fine-structure excitation with increasing component LSR velocity, suggestive of ram-pressure confinement for the intermediate-velocity clouds. These denser, more highly ionized clouds appear to be concentrated toward the inner Gum Nebula, where a somewhat higher velocity dispersion is found than in the outer regions. Clouds in the Gum Nebula do not show the anomalously high ionization seen in the Vela remnant clouds. The observational data are generally consistent with a model of the Gum Nebula as an H II region ionized by OB stars and stirred up by multiple stellar winds.« less

Ultraviolet gas absorption and dust extinction toward M8

NASA Technical Reports Server (NTRS)

Boggs, Don; Bohm-Vitense, Erika

1990-01-01

Interstellar absorption lines are analyzed using high-resolution IUE spectra of 11 stars in the young cluster NGC 6530 located in the M8 region. High-velocity clouds at -35 km/s and -60 km/s are seen toward all cluster stars. The components arise in gases that are part of large interstellar bubbles centered on the cluster and driven by stellar winds of the most luminous members. Absorption lines of species of different ionization states are separated in velocity. The velocity stratification is best explained as a 'champagne' flow of ionized gas away from the cluster. The C IV/Si IV ratios toward the hotter cluster members are consistent with simple photoionization models if the gas-phase C/Si ratio is increased by preferential accretion onto dust grains. High ion column densities in the central cluster decline with distance from W93, suggesting that radiation from a hot source near W93 has photoionized gas in the central cluster.

Kinetic energy distribution of multiply charged ions in Coulomb explosion of Xe clusters.

PubMed

Heidenreich, Andreas; Jortner, Joshua

2011-02-21

We report on the calculations of kinetic energy distribution (KED) functions of multiply charged, high-energy ions in Coulomb explosion (CE) of an assembly of elemental Xe(n) clusters (average size (n) = 200-2171) driven by ultra-intense, near-infrared, Gaussian laser fields (peak intensities 10(15) - 4 × 10(16) W cm(-2), pulse lengths 65-230 fs). In this cluster size and pulse parameter domain, outer ionization is incomplete∕vertical, incomplete∕nonvertical, or complete∕nonvertical, with CE occurring in the presence of nanoplasma electrons. The KEDs were obtained from double averaging of single-trajectory molecular dynamics simulation ion kinetic energies. The KEDs were doubly averaged over a log-normal cluster size distribution and over the laser intensity distribution of a spatial Gaussian beam, which constitutes either a two-dimensional (2D) or a three-dimensional (3D) profile, with the 3D profile (when the cluster beam radius is larger than the Rayleigh length) usually being experimentally realized. The general features of the doubly averaged KEDs manifest the smearing out of the structure corresponding to the distribution of ion charges, a marked increase of the KEDs at very low energies due to the contribution from the persistent nanoplasma, a distortion of the KEDs and of the average energies toward lower energy values, and the appearance of long low-intensity high-energy tails caused by the admixture of contributions from large clusters by size averaging. The doubly averaged simulation results account reasonably well (within 30%) for the experimental data for the cluster-size dependence of the CE energetics and for its dependence on the laser pulse parameters, as well as for the anisotropy in the angular distribution of the energies of the Xe(q+) ions. Possible applications of this computational study include a control of the ion kinetic energies by the choice of the laser intensity profile (2D∕3D) in the laser-cluster interaction volume.

Compact cosmic ray detector for unattended atmospheric ionization monitoring

NASA Astrophysics Data System (ADS)

Aplin, K. L.; Harrison, R. G.

2010-12-01

Two vertical cosmic ray telescopes for atmospheric cosmic ray ionization event detection are compared. Counter A, designed for low power remote use, was deployed in the Welsh mountains; its event rate increased with altitude as expected from atmospheric cosmic ray absorption. Independently, Counter B's event rate was found to vary with incoming particle acceptance angle. Simultaneous co-located comparison of both telescopes exposed to atmospheric ionization showed a linear relationship between their event rates.

Ionization-induced star formation - IV. Triggering in bound clusters

NASA Astrophysics Data System (ADS)

Dale, J. E.; Ercolano, B.; Bonnell, I. A.

2012-12-01

We present a detailed study of star formation occurring in bound star-forming clouds under the influence of internal ionizing feedback from massive stars across a spectrum of cloud properties. We infer which objects are triggered by comparing our feedback simulations with control simulations in which no feedback was present. We find that feedback always results in a lower star formation efficiency and usually but not always results in a larger number of stars or clusters. Cluster mass functions are not strongly affected by feedback, but stellar mass functions are biased towards lower masses. Ionization also affects the geometrical distribution of stars in ways that are robust against projection effects, but may make the stellar associations more or less subclustered depending on the background cloud environment. We observe a prominent pillar in one simulation which is the remains of an accretion flow feeding the central ionizing cluster of its host cloud and suggest that this may be a general formation mechanism for pillars such as those observed in M16. We find that the association of stars with structures in the gas such as shells or pillars is a good but by no means foolproof indication that those stars have been triggered and we conclude overall that it is very difficult to deduce which objects have been induced to form and which formed spontaneously simply from observing the system at a single time.

Energetics of charged metal clusters containing vacancies

NASA Astrophysics Data System (ADS)

Pogosov, Valentin V.; Reva, Vitalii I.

2018-01-01

We study theoretically large metal clusters containing vacancies. We propose an approach, which combines the Kohn-Sham results for monovacancy in a bulk of metal and analytical expansions in small parameters cv (relative concentration of vacancies) and RN,v -1, RN ,v being cluster radii. We obtain expressions of the ionization potential and electron affinity in the form of corrections to electron work function, which require only the characteristics of 3D defect-free metal. The Kohn-Sham method is used to calculate the electron profiles, ionization potential, electron affinity, electrical capacitance; dissociation, cohesion, and monovacancy-formation energies of the small perfect clusters NaN, MgN, AlN (N ≤ 270) and the clusters containing a monovacancy (N ≥ 12) in the stabilized-jellium model. The quantum-sized dependences for monovacancy-formation energies are calculated for the Schottky scenario and the "bubble blowing" scenario, and their asymptotic behavior is also determined. It is shown that the asymptotical behaviors of size dependences for these two mechanisms differ from each other and weakly depend on the number of atoms in the cluster. The contribution of monovacancy to energetics of charged clusters and the size dependences of their characteristics and asymptotics are discussed. It is shown that the difference between the characteristics for the neutral and charged clusters is entirely determined by size dependences of ionization potential and electron affinity. Obtained analytical dependences may be useful for the analysis of the results of photoionization experiments and for the estimation of the size dependences of the vacancy concentration including the vicinity of the melting point.

Photoelectron Spectroscopy of Free Polyoxoanions Mo6O19 2- and W6O19 2- in the Gas Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Infante, Ivan A.; Visscher, Lucas; Wang, Xue B.

2004-09-22

Two doubly charged polyoxoanions, Mo6O19 2- and W6O19 2-, were observed in the gas phase using electrospray ionization. Their electronic structures were investigated using photoelectron spectroscopy and quasi-relativistic density functional calculations. Each dianion was found to be highly stable despite the presence of strong intramolecular coulomb repulsion, estimated to be about 2 eV for each system. The valence detachment features were all shown to originate from electronic excitations involving oxygen lone-pair type orbitals. Their observed energies were in excellent agreement with the theoretical vertical detachment energies calculated using time-dependent density functional theory. Despite being multiply charged, polyoxometalate oxide clusters canmore » be studied in the gas phase, providing the opportunity for detailed benchmark theoretical studies on the electronic structures of these important transition-metal oxide systems.« less

Zero kinetic energy photoelectron spectroscopy of tryptamine and the dissociation pathway of the singly hydrated cation cluster.

PubMed

Gu, Quanli; Knee, J L

2012-09-14

The relative ionization energies of tryptamine conformations are determined by zero kinetic energy photoelectron spectroscopy and photoionization efficiency measurements. The relative cationic conformational stabilities are compared to the published results for the neutral molecule. In the cation, the interaction strength changes significantly between amino group and either the phenyl or the pyrrole moiety of the indole chromophore where most of the positive charge is located, leading to different conformational structures and relative conformer energies in the cation. In particular, the measured adiabatic ionization potential of isomer B is 60,928 ± 5 cm(-1), at least 400 cm(-1) higher than any of the 6 other tryptamine isomers which all have ionization potentials within 200 cm(-1) of each other. In addition to the monomer, measurements were made on the A conformer of the tryptamine(+)-H(2)O complex including the ionization threshold and cation dissociation energy measured using a threshold photoionization fragmentation method. The water cluster exhibits an unexpectedly high ionization potential of 60,307 ± 100 cm(-1), close to the conformer A monomer of 60 320 ± 100 cm(-1). It also exhibits surprisingly low dissociation energy of 1750 ± 150 cm(-1) compared to other H-bonding involved cation-H(2)O complexes which are typically several thousands of wavenumbers higher. Quantum chemical calculations indicate that upon ionization the structure of the parent molecule in the water complex remains mostly unchanged due to the rigid intermolecular double hydrogen bonded water molecule bridging the monomer backbone and its side chain thus leading to the high ionization potential in the water cluster. The surprisingly low dissociation energy measured in the cationic water complex is attributed to the formation of a much more stable structural isomer H(+) in the exit channel.

Optimal control of the strong-field ionization of silver clusters in helium droplets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truong, N. X.; Goede, S.; Przystawik, A.

Optimal control techniques combined with femtosecond laser pulse shaping are applied to steer and enhance the strong-field induced emission of highly charged atomic ions from silver clusters embedded in helium nanodroplets. With light fields shaped in amplitude and phase we observe a substantial increase of the Ag{sup q+} yield for q>10 when compared to bandwidth-limited and optimally stretched pulses. A remarkably simple double-pulse structure, containing a low-intensity prepulse and a stronger main pulse, turns out to produce the highest atomic charge states up to Ag{sup 20+}. A negative chirp during the main pulse hints at dynamic frequency locking to themore » cluster plasmon. A numerical optimal control study on pure silver clusters with a nanoplasma model converges to a similar pulse structure and corroborates that the optimal light field adapts to the resonant excitation of cluster surface plasmons for efficient ionization.« less

Generation of CsI cluster ions for mass calibration in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Lou, Xianwen; van Dongen, Joost L J; Meijer, E W

2010-07-01

A simple method was developed for the generation of cesium iodide (CsI) cluster ions up to m/z over 20,000 in matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Calibration ions in both positive and negative ion modes can readily be generated from a single MALDI spot of CsI(3) with 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) matrix. The major cluster ion series observed in the positive ion mode is [(CsI)(n)Cs](+), and in the negative ion mode is [(CsI)(n)I](-). In both cluster series, ions spread evenly every 259.81 units. The easy method described here for the production of CsI cluster ions should be useful for MALDI MS calibrations. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Generation of strongly coupled Xe cluster nanoplasmas by low intensive soft x-ray laser irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Namba, S.; Hasegawa, N.; Kishimoto, M.

A seeding gas jet including Xe clusters was irradiated with a laser-driven plasma soft x-ray laser pulse ({lambda}=13.9 nm, {approx}7 ps, {<=}5 Multiplication-Sign 10{sup 9} W/cm{sup 2}), where the laser photon energy is high enough to ionize 4d core electrons. In order to clarify how the innershell ionization followed by the Auger electron emission is affected under the intense laser irradiation, the electron energy distribution was measured. Photoelectron spectra showed that the peak position attributed to 4d hole shifted to lower energy and the spectral width was broadened with increasing cluster size. Moreover, the energy distribution exhibited that a stronglymore » coupled cluster nanoplasma with several eV was generated.« less

Target Plate Material Influence on Fullerene-C60 Laser Desorption/Ionization Efficiency

NASA Astrophysics Data System (ADS)

Zeegers, Guido P.; Günthardt, Barbara F.; Zenobi, Renato

2016-04-01

Systematic laser desorption/ionization (LDI) experiments of fullerene-C60 on a wide range of target plate materials were conducted to gain insight into the initial ion formation in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The positive and negative ion signal intensities of precursor, fragment, and cluster ions were monitored, varying both the laser fluence (0-3.53 Jcm-2) and the ion extraction delay time (0-950 ns). The resulting species-specific ion signal intensities are an indication for the ionization mechanisms that contribute to LDI and the time frames in which they operate, providing insight in the (MA)LDI primary ionization. An increasing electrical resistivity of the target plate material increases the fullerene-C60 precursor and fragment anion signal intensity. Inconel 625 and Ti90/Al6/V4, both highly electrically resistive, provide the highest anion signal intensities, exceeding the cation signal intensity by a factor ~1.4 for the latter. We present a mechanism based on transient electrical field strength reduction to explain this trend. Fullerene-C60 cluster anion formation is negligible, which could be due to the high extraction potential. Cluster cations, however, are readily formed, although for high laser fluences, the preferred channel is formation of precursor and fragment cations. Ion signal intensity depends greatly on the choice of substrate material, and careful substrate selection could, therefore, allow for more sensitive (MA)LDI measurements.

Density functional study of structural and electronic properties of bimetallic silver-gold clusters: Comparison with pure gold and silver clusters

NASA Astrophysics Data System (ADS)

Bonacic-Koutecky, Vlasta; Burda, Jaroslav; Mitric, Roland; Ge, Maofa; Zampella, Giuseppe; Fantucci, Piercarlo

2002-08-01

Bimetallic silver-gold clusters offer an excellent opportunity to study changes in metallic versus "ionic" properties involving charge transfer as a function of the size and the composition, particularly when compared to pure silver and gold clusters. We have determined structures, ionization potentials, and vertical detachment energies for neutral and charged bimetallic AgmAun 3[less-than-or-equal](m+n)[less-than-or-equal]5 clusters. Calculated VDE values compare well with available experimental data. In the stable structures of these clusters Au atoms assume positions which favor the charge transfer from Ag atoms. Heteronuclear bonding is usually preferred to homonuclear bonding in clusters with equal numbers of hetero atoms. In fact, stable structures of neutral Ag2Au2, Ag3Au3, and Ag4Au4 clusters are characterized by the maximum number of hetero bonds and peripheral positions of Au atoms. Bimetallic tetramer as well as hexamer are planar and have common structural properties with corresponding one-component systems, while Ag4Au4 and Ag8 have 3D forms in contrast to Au8 which assumes planar structure. At the density functional level of theory we have shown that this is due to participation of d electrons in bonding of pure Aun clusters while s electrons dominate bonding in pure Agm as well as in bimetallic clusters. In fact, Aun clusters remain planar for larger sizes than Agm and AgnAun clusters. Segregation between two components in bimetallic systems is not favorable, as shown in the example of Ag5Au5 cluster. We have found that the structures of bimetallic clusters with 20 atoms Ag10Au10 and Ag12Au8 are characterized by negatively charged Au subunits embedded in Ag environment. In the latter case, the shape of Au8 is related to a pentagonal bipyramid capped by one atom and contains three exposed negatively charged Au atoms. They might be suitable for activating reactions relevant to catalysis. According to our findings the charge transfer in bimetallic clusters is responsible for formation of negatively charged gold subunits which are expected to be reactive, a situation similar to that of gold clusters supported on metal oxides.

Generation of gas-phase ions from charged clusters: an important ionization step causing suppression of matrix and analyte ions in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Lou, Xianwen; van Dongen, Joost L J; Milroy, Lech-Gustav; Meijer, E W

2016-12-30

Ionization in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a very complicated process. It has been reported that quaternary ammonium salts show extremely strong matrix and analyte suppression effects which cannot satisfactorily be explained by charge transfer reactions. Further investigation of the reasons causing these effects can be useful to improve our understanding of the MALDI process. The dried-droplet and modified thin-layer methods were used as sample preparation methods. In the dried-droplet method, analytes were co-crystallized with matrix, whereas in the modified thin-layer method analytes were deposited on the surface of matrix crystals. Model compounds, tetrabutylammonium iodide ([N(Bu) 4 ]I), cesium iodide (CsI), trihexylamine (THA) and polyethylene glycol 600 (PEG 600), were selected as the test analytes given their ability to generate exclusively pre-formed ions, protonated ions and metal ion adducts respectively in MALDI. The strong matrix suppression effect (MSE) observed using the dried-droplet method might disappear using the modified thin-layer method, which suggests that the incorporation of analytes in matrix crystals contributes to the MSE. By depositing analytes on the matrix surface instead of incorporating in the matrix crystals, the competition for evaporation/ionization from charged matrix/analyte clusters could be weakened resulting in reduced MSE. Further supporting evidence for this inference was found by studying the analyte suppression effect using the same two sample deposition methods. By comparing differences between the mass spectra obtained via the two sample preparation methods, we present evidence suggesting that the generation of gas-phase ions from charged matrix/analyte clusters may induce significant suppression of matrix and analyte ions. The results suggest that the generation of gas-phase ions from charged matrix/analyte clusters is an important ionization step in MALDI-MS. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Communication: Strong laser alignment of solvent-solute aggregates in the gas-phase

NASA Astrophysics Data System (ADS)

Trippel, Sebastian; Wiese, Joss; Mullins, Terry; Küpper, Jochen

2018-03-01

Strong quasi-adiabatic laser alignment of the indole-water-dimer clusters, an amino-acid chromophore bound to a single water molecule through a hydrogen bond, was experimentally realized. The alignment was visualized through ion and electron imaging following strong-field ionization. Molecular-frame photoelectron angular distributions showed a clear suppression of the electron yield in the plane of the ionizing laser's polarization, which was analyzed as strong alignment of the molecular cluster with ⟨cos2 θ2D⟩ ≥ 0.9.

A local search for a graph clustering problem

NASA Astrophysics Data System (ADS)

Navrotskaya, Anna; Il'ev, Victor

2016-10-01

In the clustering problems one has to partition a given set of objects (a data set) into some subsets (called clusters) taking into consideration only similarity of the objects. One of most visual formalizations of clustering is graph clustering, that is grouping the vertices of a graph into clusters taking into consideration the edge structure of the graph whose vertices are objects and edges represent similarities between the objects. In the graph k-clustering problem the number of clusters does not exceed k and the goal is to minimize the number of edges between clusters and the number of missing edges within clusters. This problem is NP-hard for any k ≥ 2. We propose a polynomial time (2k-1)-approximation algorithm for graph k-clustering. Then we apply a local search procedure to the feasible solution found by this algorithm and hold experimental research of obtained heuristics.

Size dependent fragmentation of argon clusters in the soft x-ray ionization regime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gisselbrecht, Mathieu; Lindgren, Andreas; Burmeister, Florian

Photofragmentation of argon clusters of average size ranging from 10 up to 1000 atoms is studied using soft x-ray radiation below the 2p threshold and multicoincidence mass spectroscopy technique. For small clusters (=10), ionization induces fast fragmentation with neutral emission imparting a large amount of energy. While the primary dissociation takes place on a picosecond time scale, the fragments undergo slow degradation in the spectrometer on a microsecond time scale. For larger clusters ({>=}100) we believe that we observe the fragmentation pattern of multiply charged species on a time-scale which lasts a few hundred nanoseconds. The reason for these slowermore » processes is the large number of neutral atoms which act as an efficient cooling bath where the excess energy ('heat') dissipates among all degrees of freedom. Further degradation of the photoionic cluster in spectrometer then takes place on the microsecond time scale, similar to small clusters.« less

Probing the early stages of salt nucleation—experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Shihu; Kong, Xiangyu; Wang, Xue B.

2015-01-14

Due to fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford formation of supersaturated droplets and generating various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M x(SCN)⁻ x+1, doubly charged M y(SCN)²⁻ y+2 (M = Na, K), and triply charged K z(SCN)³⁻ z+3 anion clusters were producedmore » via electrospray of the corresponding salt solutions, and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M x(SCN)⁻ x+1 (M = Na and K) demonstrate they are superhalogen anions. The existence of doubly charged anions M y (SCN)²⁻ y+2 (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K z(SCN)³⁻ z+3 (z = 3x, x ≥ 6) were initially discovered from the photoelectron spectra for those singly charged anions of Msub>x(SCN)⁻ x+1 with the same mass-to-charge ratio (m/z), and later independently confirmed by observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters are found to become preferred, but at higher temperatures those multiply charged clusters are suppressed. The series of anion clusters investigated here range from molecular-like M₁(SCN)⁻ 2 to nano-sized K₂₂(SCN)³⁻ 25, providing a vivid molecular-level growth pattern reflecting the initial salt nucleation process.« less

Observation of correlated electronic decay in expanding clusters triggered by near-infrared fields

PubMed Central

Schütte, B.; Arbeiter, M.; Fennel, T.; Jabbari, G.; Kuleff, A.I.; Vrakking, M.J.J.; Rouzée, A.

2015-01-01

When an excited atom is embedded into an environment, novel relaxation pathways can emerge that are absent for isolated atoms. A well-known example is interatomic Coulombic decay, where an excited atom relaxes by transferring its excess energy to another atom in the environment, leading to its ionization. Such processes have been observed in clusters ionized by extreme-ultraviolet and X-ray lasers. Here, we report on a correlated electronic decay process that occurs following nanoplasma formation and Rydberg atom generation in the ionization of clusters by intense, non-resonant infrared laser fields. Relaxation of the Rydberg states and transfer of the available electronic energy to adjacent electrons in Rydberg states or quasifree electrons in the expanding nanoplasma leaves a distinct signature in the electron kinetic energy spectrum. These so far unobserved electron-correlation-driven energy transfer processes may play a significant role in the response of any nano-scale system to intense laser light. PMID:26469997

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry. Singly as well as multiply charged clusters were formed with the general formulae, (HCOOLi)nLi+, (HCOOLi)nLimm+, (HCOOLi)nHCOO- and (HCOOLi)n(HCOO)mm-. Several magic number cluster ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi)3Li+ being the most abundant and stable cluster ions. Fragmentations of singly charged clusters proceed first by the loss of a dimer unit ((HCOOLi)2) followed by sequential loss of monomer units (HCOOLi). In the case ofmore » positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi)3Li+ at higher collision energies which later fragments to dimer and monomer ions in lower abundance. Quantum mechanical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Hierarchical Velocity Structure in the Core of Abell 2597

NASA Technical Reports Server (NTRS)

Still, Martin; Mushotzky, Richard

2004-01-01

We present XMM-Newton RGS and EPIC data of the putative cooling flow cluster Abell 2597. Velocities of the low-ionization emission lines in the spectrum are blue shifted with respect to the high-ionization lines by 1320 (sup +660) (sub -210) kilometers per second, which is consistent with the difference in the two peaks of the galaxy velocity distribution and may be the signature of bulk turbulence, infall, rotation or damped oscillation in the cluster. A hierarchical velocity structure such as this could be the direct result of galaxy mergers in the cluster core, or the injection of power into the cluster gas from a central engine. The uniform X-ray morphology of the cluster, the absence of fine scale temperature structure and the random distribution of the the galaxy positions, independent of velocity, suggests that our line of sight is close to the direction of motion. These results have strong implications for cooling flow models of the cluster Abell 2597. They give impetus to those models which account for the observed temperature structure of some clusters using mergers instead of cooling flows.

Vibrational spectra and structures of neutral Si(m)C(n) clusters (m + n = 6): sequential doping of silicon clusters with carbon atoms.

PubMed

Savoca, Marco; Lagutschenkov, Anita; Langer, Judith; Harding, Dan J; Fielicke, André; Dopfer, Otto

2013-02-14

Vibrational spectra of mixed silicon carbide clusters Si(m)C(n) with m + n = 6 in the gas phase are obtained by resonant infrared-vacuum-ultraviolet two-color ionization (IR-UV2CI for n ≤ 2) and density functional theory (DFT) calculations. Si(m)C(n) clusters are produced in a laser vaporization source, in which the silicon plasma reacts with methane. Subsequently, they are irradiated with tunable IR light from an IR free electron laser before they are ionized with UV photons from an F(2) laser. Resonant absorption of one or more IR photons leads to an enhanced ionization efficiency for Si(m)C(n) and provides the size-specific IR spectra. IR spectra measured for Si(6), Si(5)C, and Si(4)C(2) are assigned to their most stable isomers by comparison with calculated linear absorption spectra. The preferred Si(m)C(n) structures with m + n = 6 illustrate the systematic transition from chain-like geometries for bare C(6) to three-dimensional structures for bare Si(6). In contrast to bulk SiC, carbon atom segregation is observed already for the smallest n (n = 2).

Effects of molecular weight and cationization agent on the sensitivity of Bi cluster secondary ion mass spectrometry.

PubMed

Fujii, Makiko; Shishido, Rie; Satoh, Takaya; Suzuki, Shigeru; Matsuo, Jiro

2016-07-30

Bi cluster secondary ion mass spectrometry (SIMS) is one of the most promising tools for precise analysis of synthetic polymers. However, the sensitivity in the high-mass region is still insufficient compared with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Accordingly, the effects of metal assistance (cationization agents) were investigated in this study. To investigate the effects caused by varying the ionization agent, three different polyethylene glycol (PEG) samples were prepared, one with an Ag-deposited film, and two others mixed with Ag and Na, respectively. The measurements were performed by using a commercial Bi cluster SIMS and MALDI-TOFMS systems. The mass spectrum obtained with MALDI-TOFMS was used as a reference molecular weight distribution to evaluate the effects of molecular weight and primary ion species (Bi + , Bi 3 + , Bi 3 2 + ) on the sensitivity of Bi cluster SIMS. The intensity of each secondary ion was the highest in Bi 3 2 + irradiation, and the lowest in Bi + irradiation. Regarding the cationization agents, the secondary ion yield was the highest for the sample mixed with Ag, while the degree of decay of sensitivity along with the increase in molecular weight was the smallest for the sample mixed with Na. It was suggested that the cationization mechanism consists of pre-formed ionization and gas-phase ionization processes. The sensitivity of Bi cluster SIMS decreases to approximately one-fiftieth in every 1000 u. These results might help in understanding the mechanism of cationization and further enhancement of secondary ion yields of polymers. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

A Gemini view of the galaxy cluster RXC J1504-0248: insights on the nature of the central gaseous filaments

NASA Astrophysics Data System (ADS)

Soja, A. C.; Sodré, L.; Monteiro-Oliveira, R.; Cypriano, E. S.; Lima Neto, G. B.

2018-07-01

We revisit the galaxy cluster RXC J1504-0248, a remarkable example of a structure with a strong cool core in a near redshift (z = 0.216). We performed a combined analysis using photometric and spectroscopic data obtained at Gemini South Telescope. We estimated the cluster mass through gravitational lensing, obtaining M200 = 5.3 ± 0.4 × 1014 h_{70}^{-1} M⊙ within R200 = 1.56 ± 0.04 h^{-1}_{70} Mpc, in agreement with a virial mass estimate. This cluster presents a prominent filamentary structure associated with its brightest cluster galaxy, located mainly along its major axis and aligned with the X-ray emission. A combined study of three emission line diagnostic diagrams has shown that the filament emission falls in the so-called transition region of these diagrams. Consequently, several ionizing sources should be playing a meaningful role. We have argued that old stars, often invoked to explain low-ionization nuclear emission-line region emission, should not be the major source of ionization. We have noticed that most of the filamentary emission has line ratios consistent with the shock excitation limits obtained from shock models. We also found that line fluxes are related to gas velocities (here estimated from line widths) by power laws with slopes in the range expected from shock models. These models also show, however, that only ˜10 per cent of H α luminosity can be explained by shocks. We conclude that shocks probably associated with the cooling of the intracluster gas in a filamentary structure may indeed be contributing to the filament nebular emission, but cannot be the major source of ionizing photons.

Comprehensive Biothreat Cluster Identification by PCR/Electrospray-Ionization Mass Spectrometry

PubMed Central

Sampath, Rangarajan; Mulholland, Niveen; Blyn, Lawrence B.; Massire, Christian; Whitehouse, Chris A.; Waybright, Nicole; Harter, Courtney; Bogan, Joseph; Miranda, Mary Sue; Smith, David; Baldwin, Carson; Wolcott, Mark; Norwood, David; Kreft, Rachael; Frinder, Mark; Lovari, Robert; Yasuda, Irene; Matthews, Heather; Toleno, Donna; Housley, Roberta; Duncan, David; Li, Feng; Warren, Robin; Eshoo, Mark W.; Hall, Thomas A.; Hofstadler, Steven A.; Ecker, David J.

2012-01-01

Technology for comprehensive identification of biothreats in environmental and clinical specimens is needed to protect citizens in the case of a biological attack. This is a challenge because there are dozens of bacterial and viral species that might be used in a biological attack and many have closely related near-neighbor organisms that are harmless. The biothreat agent, along with its near neighbors, can be thought of as a biothreat cluster or a biocluster for short. The ability to comprehensively detect the important biothreat clusters with resolution sufficient to distinguish the near neighbors with an extremely low false positive rate is required. A technological solution to this problem can be achieved by coupling biothreat group-specific PCR with electrospray ionization mass spectrometry (PCR/ESI-MS). The biothreat assay described here detects ten bacterial and four viral biothreat clusters on the NIAID priority pathogen and HHS/USDA select agent lists. Detection of each of the biothreat clusters was validated by analysis of a broad collection of biothreat organisms and near neighbors prepared by spiking biothreat nucleic acids into nucleic acids extracted from filtered environmental air. Analytical experiments were carried out to determine breadth of coverage, limits of detection, linearity, sensitivity, and specificity. Further, the assay breadth was demonstrated by testing a diverse collection of organisms from each biothreat cluster. The biothreat assay as configured was able to detect all the target organism clusters and did not misidentify any of the near-neighbor organisms as threats. Coupling biothreat cluster-specific PCR to electrospray ionization mass spectrometry simultaneously provides the breadth of coverage, discrimination of near neighbors, and an extremely low false positive rate due to the requirement that an amplicon with a precise base composition of a biothreat agent be detected by mass spectrometry. PMID:22768032

Metal-cluster ionization energy: A profile-insensitive exact expression for the size effect

NASA Astrophysics Data System (ADS)

Seidl, Michael; Perdew, John P.; Brajczewska, Marta; Fiolhais, Carlos

1997-05-01

The ionization energy of a large spherical metal cluster of radius R is I(R)=W+(+c)/R, where W is the bulk work function and c~-0.1 is a material-dependent quantum correction to the electrostatic size effect. We present 'Koopmans' and 'displaced-profile change-in-self-consistent-field' expressions for W and c within the ordinary and stabilized-jellium models. These expressions are shown to be exact and equivalent when the exact density profile of a large neutral cluster is employed; these equivalences generalize the Budd-Vannimenus theorem. With an approximate profile obtained from a restricted variational calculation, the 'displaced-profile' expressions are the more accurate ones. This profile insensitivity is important, because it is not practical to extract c from solutions of the Kohn-Sham equations for small metal clusters.

A screened independent atom model for the description of ion collisions from atomic and molecular clusters

NASA Astrophysics Data System (ADS)

Lüdde, Hans Jürgen; Horbatsch, Marko; Kirchner, Tom

2018-05-01

We apply a recently introduced model for an independent-atom-like calculation of ion-impact electron transfer and ionization cross sections to proton collisions from water, neon, and carbon clusters. The model is based on a geometrical interpretation of the cluster cross section as an effective area composed of overlapping circular disks that are representative of the atomic contributions. The latter are calculated using a time-dependent density-functional-theory-based single-particle description with accurate exchange-only ground-state potentials. We find that the net capture and ionization cross sections in p-X n collisions are proportional to n α with 2/3 ≤ α ≤ 1. For capture from water clusters at 100 keV impact energy α is close to one, which is substantially different from the value α = 2/3 predicted by a previous theoretical work based on the simplest-level electron nuclear dynamics method. For ionization at 100 keV and for capture at lower energies we find smaller α values than for capture at 100 keV. This can be understood by considering the magnitude of the atomic cross sections and the resulting overlaps of the circular disks that make up the cluster cross section in our model. Results for neon and carbon clusters confirm these trends. Simple parametrizations are found which fit the cross sections remarkably well and suggest that they depend on the relevant bond lengths.

Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

PubMed

Bianchi, Federico; Praplan, Arnaud P; Sarnela, Nina; Dommen, Josef; Kürten, Andreas; Ortega, Ismael K; Schobesberger, Siegfried; Junninen, Heikki; Simon, Mario; Tröstl, Jasmin; Jokinen, Tuija; Sipilä, Mikko; Adamov, Alexey; Amorim, Antonio; Almeida, Joao; Breitenlechner, Martin; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Keskinen, Helmi; Kim, Jaeseok; Kirkby, Jasper; Laaksonen, Ari; Lawler, Michael J; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Tomé, António; Virtanen, Annele; Viisanen, Yrjö; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Curtius, Joachim; Kulmala, Markku; Worsnop, Douglas R; Donahue, Neil M; Baltensperger, Urs

2014-12-02

We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

Delayed repair of radiation induced clustered DNA damage: Friend or foe?

PubMed Central

Eccles, Laura J.; O’Neill, Peter; Lomax, Martine E.

2011-01-01

A signature of ionizing radiation exposure is the induction of DNA clustered damaged sites, defined as two or more lesions within one to two helical turns of DNA by passage of a single radiation track. Clustered damage is made up of double strand breaks (DSB) with associated base lesions or abasic (AP) sites, and non-DSB clusters comprised of base lesions, AP sites and single strand breaks. This review will concentrate on the experimental findings of the processing of non-DSB clustered damaged sites. It has been shown that non-DSB clustered damaged sites compromise the base excision repair pathway leading to the lifetime extension of the lesions within the cluster, compared to isolated lesions, thus the likelihood that the lesions persist to replication and induce mutation is increased. In addition certain non-DSB clustered damaged sites are processed within the cell to form additional DSB. The use of E. coli to demonstrate that clustering of DNA lesions is the major cause of the detrimental consequences of ionizing radiation is also discussed. The delayed repair of non-DSB clustered damaged sites in humans can be seen as a “friend”, leading to cell killing in tumour cells or as a “foe”, resulting in the formation of mutations and genetic instability in normal tissue. PMID:21130102

Infrared absorption of methanethiol clusters (CH3SH)n, n = 2-5, recorded with a time-of-flight mass spectrometer using IR depletion and VUV ionization

NASA Astrophysics Data System (ADS)

Fu, Lung; Han, Hui-Ling; Lee, Yuan-Pern

2012-12-01

We investigated IR spectra in the CH- and SH-stretching regions of size-selected methanethiol clusters, (CH3SH)n with n = 2-5, in a pulsed supersonic jet using infrared (IR)-vacuum ultraviolet (VUV) ionization. VUV emission at 132.50 nm served as the source of ionization in a time-of-flight mass spectrometer. Clusters were dissociated with light from a tunable IR laser before ionization. The variations in intensity of methanethiol cluster ions (CH3SH)n+ were monitored as the IR laser light was tuned across the range 2470-3100 cm-1. In the SH-stretching region, the spectrum of (CH3SH)2 shows a weak band near 2601 cm-1, red-shifted only 7 cm-1 from that of the monomer. In contrast, all spectra of (CH3SH)n, n = 3-5, show a broad band near 2567 cm-1 with much greater intensity. In the CH-stretching region, absorption bands of (CH3SH)2 are located near 2865, 2890, 2944, and 3010 cm-1, red-shifted by 3-5 cm-1 from those of CH3SH. These red shifts increase slightly for larger clusters and bands near 2856, 2884, 2938, and 3005 cm-1 were observed for (CH3SH)5. These spectral results indicate that the S-H...S hydrogen bond plays an important role in clusters with n = 3-5, but not in (CH3SH)2, in agreement with theoretical predictions. The absence of a band near 2608 cm-1 that corresponds to absorption of the non-hydrogen-bonded SH moiety and the large width of observed feature near 2567 cm-1 indicate that the dominant stable structures of (CH3SH)n, n = 3-5, have a cyclic hydrogen-bonded framework.

Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ligare, Marshall R.; Baker, Erin S.; Laskin, Julia

Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

Catalog of open clusters and associated interstellar matter

NASA Technical Reports Server (NTRS)

Leisawitz, David

1988-01-01

The Catalog of Open Clusters and Associated Interstellar Matter summarizes observations of 128 open clusters and their associated ionized, atomic, and molecular iinterstellar matter. Cluster sizes, distances, radial velocities, ages, and masses, and the radial velocities and masses of associated interstellar medium components, are given. The database contains information from approximately 400 references published in the scientific literature before 1988.

A Systematic Approach for Determining Vertical Pile Depth of Embedment in Cohensionless Soils to Withstand Lateral Barge Train Impact Loads

DTIC Science & Technology

2017-01-30

dynamic structural time- history response analysis of flexible approach walls founded on clustered pile groups using Impact_Deck. In Preparation, ERDC...research (Ebeling et al. 2012) has developed simplified analysis procedures for flexible approach wall systems founded on clustered groups of vertical...history response analysis of flexible approach walls founded on clustered pile groups using Impact_Deck. In Preparation, ERDC/ITL TR-16-X. Vicksburg, MS

Target Plate Material Influence on Fullerene-C60 Laser Desorption/Ionization Efficiency.

PubMed

Zeegers, Guido P; Günthardt, Barbara F; Zenobi, Renato

2016-04-01

Systematic laser desorption/ionization (LDI) experiments of fullerene-C60 on a wide range of target plate materials were conducted to gain insight into the initial ion formation in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The positive and negative ion signal intensities of precursor, fragment, and cluster ions were monitored, varying both the laser fluence (0-3.53 Jcm(-2)) and the ion extraction delay time (0-950 ns). The resulting species-specific ion signal intensities are an indication for the ionization mechanisms that contribute to LDI and the time frames in which they operate, providing insight in the (MA)LDI primary ionization. An increasing electrical resistivity of the target plate material increases the fullerene-C60 precursor and fragment anion signal intensity. Inconel 625 and Ti90/Al6/V4, both highly electrically resistive, provide the highest anion signal intensities, exceeding the cation signal intensity by a factor ~1.4 for the latter. We present a mechanism based on transient electrical field strength reduction to explain this trend. Fullerene-C60 cluster anion formation is negligible, which could be due to the high extraction potential. Cluster cations, however, are readily formed, although for high laser fluences, the preferred channel is formation of precursor and fragment cations. Ion signal intensity depends greatly on the choice of substrate material, and careful substrate selection could, therefore, allow for more sensitive (MA)LDI measurements. Graphical Abstract ᅟ.

Study of BenW (n = 1-12) clusters: An electron collision perspective

NASA Astrophysics Data System (ADS)

Modak, Paresh; Kaur, Jaspreet; Antony, Bobby

2017-08-01

This article explores electron scattering cross sections by Beryllium-Tungsten clusters (BenW). Beryllium and tungsten are important elements for plasma facing wall components, especially for the deuterium/tritium phase of ITER and in the recently installed JET. The present study focuses on different electron impact interactions in terms of elastic cross section (Qel), inelastic cross section (Qinel), ionization cross section (Qion), and momentum transfer cross section (Qmtcs) for the first twelve clusters belonging to the BenW family. It also predicts the evolution of the cross section with the size of the cluster. These cross sections are used as an input to model processes in plasma. The ionization cross section presented here is compared with the available reported data. This is the first comprehensive report on cross section data for all the above-mentioned scattering channels, to the best of our knowledge. Such broad analysis of cross section data gives vital insight into the study of local chemistry of electron interactions with BenW (n = 1-12) clusters in plasma.

Far-infrared image restoration analysis of the protostellar cluster in S140

NASA Technical Reports Server (NTRS)

Lester, D. F.; Harvey, P. M.; Joy, M.; Ellis, H. B., Jr.

1986-01-01

Image restoration techniques are applied to one-dimensional scans at 50 and 100 microns of the protostellar cluster in S140. These measurements resolve the surrounding nebula clearly, and Fourier methods are used to match the effective beam profiles at these wavelengths. This allows the radial distribution of temperature and dust column density to be derived at a diffraction limited spatial resolution of 23 arcsec (0.1 pc). Evidence for heating of the S140 molecular cloud by a nearby ionization front is established, and the dissociation of molecules inside the ionization front is spatially well correlated with the heating of the dust. The far-infrared spectral distribution of the three near-infrared sources within 10 arcsesc of the cluster center is presented.

Formation of multiply charged ions from large molecules using massive-cluster impact.

PubMed

Mahoney, J F; Cornett, D S; Lee, T D

1994-05-01

Massive-cluster impact is demonstrated to be an effective ionization technique for the mass analysis of proteins as large as 17 kDa. The design of the cluster source permits coupling to both magnetic-sector and quadrupole mass spectrometers. Mass spectra are characterized by the almost total absence of chemical background and a predominance of multiply charged ions formed from 100% glycerol matrix. The number of charge states produced by the technique is observed to range from +3 to +9 for chicken egg lysozyme (14,310 Da). The lower m/z values provided by higher charge states increase the effective mass range of analyses performed with conventional ionization by fast-atom bombardment or liquid secondary ion mass spectrometry.

Tip-Enhanced Photoinduced Electron Transfer and Ionization on Vertical Silicon Nanowires.

PubMed

Chen, Xiaoming; Wang, Tao; Lin, Leimiao; Wo, Fangjie; Liu, Yaqin; Liang, Xiao; Ye, Hui; Wu, Jianmin

2018-05-02

Nanostructured semiconductors are one of the most potent candidates for matrix-free laser desorption/ionization mass spectrometric (LDI-MS) analysis of low-molecular-weight molecules. Herein, the enhanced photoinduced electron transfer and LDI on the tip of a vertical silicon nanowire (SiNW) array were investigated. Theoretical simulation and LDI detection of indigo and isatin molecules in negative ion mode revealed that the electric field can be enhanced on the tip end of SiNWs, thereby promoting the energy and electron transfer to the analytes adsorbed on the tip of SiNWs. On the basis of this finding, a tip-contact sampling method coupled with LDI-MS detection was established. In this strategy, the tip of SiNWs can be regarded as microextraction heads for the sampling of molecules when they come in contact with analytes. Impression of skin, tissue, and pericarp on the vertical SiNW array can effectively transfer endogenous metabolites or exogenous substances onto the tip. Upon laser irradiation, the adsorbed molecules on the SiNW tip can be efficiently ionized and detected in negative ion mode because of the tip-enhanced electron transfer and LDI effect. We believe this work may significantly expand the application of LDI-MS in various fields.

Production of low kinetic energy electrons and energetic ion pairs by Intermolecular Coulombic Decay.

PubMed

Hergenhahn, Uwe

2012-12-01

The paper gives an introduction into Interatomic and Intermolecular Coulombic Decay (ICD). ICD is an autoionization process, which contrary to Auger decay involves neighbouring sites of the initial vacancy as an integral part of the decay transition. As a result of ICD, slow electrons are produced which generally are known to be active in radiation damage. The author summarizes the properties of ICD and reviews a number of important experiments performed in recent years. Intermolecular Coulombic Decay can generally take place in weakly bonded aggregates in the presence of ionizing particles or ionizing radiation. Examples collected here mostly use soft X-rays produced by synchrotron radiation to ionize, and use rare-gas clusters, water clusters or solutes in a liquid jet to observe ICD after irradiation. Intermolecular Coulombic Decay is initiated by single ionization into an excited state. The subsequent relaxation proceeds via an ultra-fast energy transfer to a neighbouring site, where a second ionization occurs. Secondary electrons from ICD have clearly been identified in numerous systems. ICD can take place after primary ionization, as the second step of a decay cascade which also involves Auger decay, or after resonant excitation with an energy which exceeds the ionization potential of the system. ICD is expected to play a role whenever particles or radiation with photon energies above the ionization energies for inner valence electrons are present in weakly bonded matter, e.g., biological tissue. The process produces at the same time a slow electron and two charged atomic or molecular fragments, which will lead to structural changes around the ionized site.

Volume shift and charge instability of simple-metal clusters

NASA Astrophysics Data System (ADS)

Brajczewska, M.; Vieira, A.; Fiolhais, C.; Perdew, J. P.

1996-12-01

Experiment indicates that small clusters show changes (mostly contractions) of the bond lengths with respect to bulk values. We use the stabilized jellium model to study the self-expansion and self-compression of spherical clusters (neutral or ionized) of simple metals. Results from Kohn - Sham density functional theory are presented for small clusters of Al and Na, including negatively-charged ones. We also examine the stability of clusters with respect to charging.

Hydrogen bonding in water clusters and their ionized counterparts.

PubMed

Neela, Y Indra; Mahadevi, A Subha; Sastry, G Narahari

2010-12-30

Ab initio and DFT computations were carried out on four distinct hydrogen-bonded arrangements of water clusters (H(2)O)(n), n = 2-20, represented as W1D, W2D, W2DH, and W3D. The variation in the strength of hydrogen bond as a function of the chain length is studied. In all the four cases, there is a substantial cooperative interaction, albeit in different degrees. The effect of basis set superposition error (BSSE) on the complexation energy of water clusters has been analyzed. Atoms in molecules (AIM) analysis performed to evaluate the nature of the hydrogen bonding shows a high correlation between hydrogen bond strength and the trends in complexation energy. Solvated water clusters exhibit lower complexation energies compared to corresponding gas-phase geometries on PCM (polarized continuum model) optimization. The feasibility of stripping an electron or addition of an electron increases dramatically as the cluster size increases. Although W3D caged structures are stable for neutral clusters, the helical W2DH arrangement appeared to be an optimal choice for its ionized counterparts.

Electron-induced chemistry in imidazole clusters embedded in helium nanodroplets

NASA Astrophysics Data System (ADS)

Kuhn, Martin; Raggl, Stefan; Martini, Paul; Gitzl, Norbert; Darian, Masoomeh Mahmoodi; Goulart, Marcelo; Postler, Johannes; Feketeová, Linda; Scheier, Paul

2018-02-01

Electron-induced chemistry in imidazole (IMI) clusters embedded in helium nanodroplets (with an average size of 2 × 105 He atoms) has been investigated with high-resolution time-of-flight mass spectrometry. The formation of both, negative and positive, ions was monitored as a function of the cluster size n. In both ion spectra a clear series of peaks with IMI cluster sizes up to at least 25 are observed. While the anions are formed by collisions of IMI n with He*-, the cations are formed through ionization of IMI n by He+ as the measured onset for the cation formation is observed at 24.6 eV (ionization energy of He). The most abundant series of anions are dehydrogenated anions IMI n-1(IMI-H)-, while other anion series are IMI clusters involving CN and C2H4 moieties. The formation of cations is dominated by the protonated cluster ions IMI n H+, while the intensity of parent cluster cations IMI n + is also observed preferentially for the small cluster size n. The observation of series of cluster cations [IMI n CH3]+ suggests either CH3+ cation to be solvated by n neutral IMI molecules, or the electron-induced chemistry has led to the formation of protonated methyl-imidazole solvated by ( n - 1) neutral IMI molecules.

HST/WFPC2 and VLT/ISAAC Observations of Proplyds in the Giant H II Region NGC 3603

NASA Astrophysics Data System (ADS)

Brandner, Wolfgang; Grebel, Eva K.; Chu, You-Hua; Dottori, Horacio; Brandl, Bernhard; Richling, Sabine; Yorke, Harold W.; Points, Sean D.; Zinnecker, Hans

2000-01-01

We report the discovery of three proplyd-like structures in the giant H II region NGC 3603. The emission nebulae are clearly resolved in narrowband and broadband HST/WFPC2 observations in the optical and broadband VLT/ISAAC observations in the near-infrared. All three nebulae are tadpole shaped, with the bright ionization front at the head facing the central cluster and a fainter ionization front around the tail pointing away from the cluster. Typical sizes are 6000 AUx20,000 AU The nebulae share the overall morphology of the proplyds (PROto PLanetarY DiskS) in Orion, but are 20 to 30 times larger in size. Additional faint filaments located between the nebulae and the central ionizing cluster can be interpreted as bow shocks resulting from the interaction of the fast winds from the high-mass stars in the cluster with the evaporation flow from the proplyds. Low-resolution spectra of the brightest nebula, which is at a projected separation of 1.3 pc from the cluster, reveal that it has the spectral excitation characteristics of an ultra compact H II region with electron densities well in excess of 104 cm-3. The near-infrared data reveal a point source superposed on the ionization front. The striking similarity of the tadpole-shaped emission nebulae in NGC 3603 to the proplyds in Orion suggests that the physical structure of both types of objects might be the same. We present two-dimensional radiation hydrodynamical simulations of an externally illuminated star-disk-envelope system, which was still in its main accretion phase when first exposed to ionizing radiation from the central cluster. The simulations reproduce the overall morphology of the proplyds in NGC 3603 very well, but also indicate that mass-loss rates of up to 10-5 Msolar yr-1 are required in order to explain the size of the proplyds. Due to these high mass-loss rates, the proplyds in NGC 3603 should only survive ~105 yr. Despite this short survival time, we detect three proplyds. This indicates that circumstellar disks must be common around young stars in NGC 3603 and that these particular proplyds have only recently been exposed to their present harsh UV environment.

Different mechanisms of cluster explosion within a unified smooth particle hydrodynamics Thomas-Fermi approach: Optical and short-wavelength regimes compared

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rusek, Marian; Orlowski, Arkadiusz

2005-04-01

The dynamics of small ({<=}55 atoms) argon clusters ionized by an intense femtosecond laser pulse is studied using a time-dependent Thomas-Fermi model. The resulting Bloch-like hydrodynamic equations are solved numerically using the smooth particle hydrodynamics method without the necessity of grid simulations. As follows from recent experiments, absorption of radiation and subsequent ionization of clusters observed in the short-wavelength laser frequency regime (98 nm) differs considerably from that in the optical spectral range (800 nm). Our theoretical approach provides a unified framework for treating these very different frequency regimes and allows for a deeper understanding of the underlying cluster explosionmore » mechanisms. The results of our analysis following from extensive numerical simulations presented in this paper are compared both with experimental findings and with predictions of other theoretical models.« less

Down syndrome and ionizing radiation.

PubMed

Verger, P

1997-12-01

This review examines the epidemiologic and experimental studies into the possible role ionizing radiation might play in Down Syndrome (trisomy 21). It is prompted by a report of a temporal cluster of cases of this chromosomal disorder observed in West Berlin exactly 9 mo after the radioactive cloud from Chernobyl passed. In approximately 90% of cases, Down Syndrome is due to the nondisjunction of chromosome 21, most often in the oocyte, which may be exposed to ionizing radiation during two separate periods: before the completion of the first meiosis or around the time of ovulation. Most epidemiologic studies into trisomies and exposure to ionizing radiation examine only the first period; the Chernobyl cluster is related to the second. Analysis of these epidemiologic results indicates that the possibility that ionizing radiation might be a risk factor in Down Syndrome cannot be excluded. The experimental results, although sometimes contradictory, demonstrate that irradiation may induce nondisjunction in oogenesis and spermatogenesis; they cannot, however, be easily extrapolated to humans. The weaknesses of epidemiologic studies into the risk factors for Down Syndrome at birth (especially the failure to take into account the trisomy cases leading to spontaneous abortion) are discussed. We envisage the utility and feasibility of new studies, in particular among women exposed to prolonged or repeated artificially-produced ionizing radiation.

Electron impact ionization cross sections of beryllium-tungsten clusters*

NASA Astrophysics Data System (ADS)

Sukuba, Ivan; Kaiser, Alexander; Huber, Stefan E.; Urban, Jan; Probst, Michael

2016-01-01

We report calculated electron impact ionization cross sections (EICSs) of beryllium-tungsten clusters, BenW with n = 1,...,12, from the ionization threshold to 10 keV using the Deutsch-Märk (DM) and the binary-encounter-Bethe (BEB) formalisms. The positions of the maxima of DM and BEB cross sections are mostly close to each other. The DM cross sections are more sensitive with respect to the cluster size. For the clusters smaller than Be4W they yield smaller cross sections than BEB and vice versa larger cross sections than BEB for clusters larger than Be6W. The maximum cross section values for the singlet-spin groundstate clusters range from 7.0 × 10-16 cm2 at 28 eV (BeW) to 54.2 × 10-16 cm2 at 43 eV (Be12W) for the DM cross sections and from 13.5 × 10-16 cm2 at 43 eV (BeW) to 38.9 × 10-16 cm2 at 43 eV (Be12W) for the BEB cross sections. Differences of the EICSs in different isomers and between singlet and triplet states are also explored. Both the DM and BEB cross sections could be fitted perfectly to a simple expression used in modeling and simulation codes in the framework of nuclear fusion research. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2015-60583-7

Electron impact ionization of size selected hydrogen clusters (H2)N: ion fragment and neutral size distributions.

PubMed

Kornilov, Oleg; Toennies, J Peter

2008-05-21

Clusters consisting of normal H2 molecules, produced in a free jet expansion, are size selected by diffraction from a transmission nanograting prior to electron impact ionization. For each neutral cluster (H2)(N) (N=2-40), the relative intensities of the ion fragments Hn+ are measured with a mass spectrometer. H3+ is found to be the most abundant fragment up to N=17. With a further increase in N, the abundances of H3+, H5+, H7+, and H9+ first increase and, after passing through a maximum, approach each other. At N=40, they are about the same and more than a factor of 2 and 3 larger than for H11+ and H13+, respectively. For a given neutral cluster size, the intensities of the ion fragments follow a Poisson distribution. The fragmentation probabilities are used to determine the neutral cluster size distribution produced in the expansion at a source temperature of 30.1 K and a source pressure of 1.50 bar. The distribution shows no clear evidence of a magic number N=13 as predicted by theory and found in experiments with pure para-H2 clusters. The ion fragment distributions are also used to extract information on the internal energy distribution of the H3+ ions produced in the reaction H2+ + H2-->H3+ +H, which is initiated upon ionization of the cluster. The internal energy is assumed to be rapidly equilibrated and to determine the number of molecules subsequently evaporated. The internal energy distribution found in this way is in good agreement with data obtained in an earlier independent merged beam scattering experiment.

The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

NASA Technical Reports Server (NTRS)

Eisele, F. L.

1999-01-01

An improved version of a transverse ion source was developed which uses selected ion chemical ionization mass spectrometry techniques inside of a particle nucleation flow tube. These new techniques are very unique, in that the chemical ionization is done inside of the flow tube rather than by having to remove the compounds and clusters of interest which are lost on first contact,with any surfaces. The transverse source is also unique because it allows the ion reaction time to be varied over more than an order of magnitude, which in turn makes possible the separation of ion induced cluster growth from the charging of preexisting molecular clusters. As a result of combining these unique capabilities, the first ever measurements of prenucleation molecular clusters were performed. These clusters are the intermediate stage of growth in the gas-to-particle conversion process. This new technique provides a means of observing clusters containing 2, 3, 4, ... and up to about 8 sulfuric acid molecules, where the critical cluster size under these measurement conditions was about 4 or 5. Thus, the nucleation process can now be directly observed and even growth beyond the critical cluster size can be investigated. The details of this investigation are discussed in a recently submitted paper, which is included as Appendix A. Measurements of the diffusion coefficient of sulfuric acid and sulfuric acid clustered with a water molecule have also been performed. The measurements are also discussed in more detail in another recently submitted paper which is included as Appendix B. The empirical results discussed in both of these papers provide a critical test of present nucleation theories. They also provide new hope for resolving many of the huge discrepancies between field observation and model prediction of particle nucleation. The second part of the research conducted under this project was directed towards the development of new chemical ionization techniques for measuring sulfur oxidation products.

Clusters of Monoisotopic Elements for Calibration in (TOF) Mass Spectrometry

NASA Astrophysics Data System (ADS)

Kolářová, Lenka; Prokeš, Lubomír; Kučera, Lukáš; Hampl, Aleš; Peňa-Méndez, Eladia; Vaňhara, Petr; Havel, Josef

2017-03-01

Precise calibration in TOF MS requires suitable and reliable standards, which are not always available for high masses. We evaluated inorganic clusters of the monoisotopic elements gold and phosphorus (Au n +/Au n - and P n +/P n -) as an alternative to peptides or proteins for the external and internal calibration of mass spectra in various experimental and instrumental scenarios. Monoisotopic gold or phosphorus clusters can be easily generated in situ from suitable precursors by laser desorption/ionization (LDI) or matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Their use offers numerous advantages, including simplicity of preparation, biological inertness, and exact mass determination even at lower mass resolution. We used citrate-stabilized gold nanoparticles to generate gold calibration clusters, and red phosphorus powder to generate phosphorus clusters. Both elements can be added to samples to perform internal calibration up to mass-to-charge ( m/z) 10-15,000 without significantly interfering with the analyte. We demonstrated the use of the gold and phosphorous clusters in the MS analysis of complex biological samples, including microbial standards and total extracts of mouse embryonic fibroblasts. We believe that clusters of monoisotopic elements could be used as generally applicable calibrants for complex biological samples.

IONIZED GAS KINEMATICS AT HIGH RESOLUTION. V. [Ne ii], MULTIPLE CLUSTERS, HIGH EFFICIENCY STAR FORMATION, AND BLUE FLOWS IN HE 2–10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beck, Sara; Turner, Jean; Lacy, John

2015-11-20

We measured the 12.8 μm [Ne ii] line in the dwarf starburst galaxy He 2–10 with the high-resolution spectrometer TEXES on the NASA IRTF. The data cube has a diffraction-limited spatial resolution of ∼1″ and a total velocity resolution, including thermal broadening, of ∼5 km s{sup −1}. This makes it possible to compare the kinematics of individual star-forming clumps and molecular clouds in the three dimensions of space and velocity, and allows us to determine star formation efficiencies. The kinematics of the ionized gas confirm that the starburst contains multiple dense clusters. From the M/R of the clusters and themore » ≃30%–40% star formation efficiencies, the clusters are likely to be bound and long lived, like globulars. Non-gravitational features in the line profiles show how the ionized gas flows through the ambient molecular material, as well as a narrow velocity feature, which we identify with the interface of the H ii region and a cold dense clump. These data offer an unprecedented view of the interaction of embedded H ii regions with their environment.« less

Inclusion of orbital relaxation and correlation through the unitary group adapted open shell coupled cluster theory using non-relativistic and scalar relativistic Hamiltonians to study the core ionization potential of molecules containing light to medium-heavy elements

NASA Astrophysics Data System (ADS)

Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

2018-02-01

The orbital relaxation attendant on ionization is particularly important for the core electron ionization potential (core IP) of molecules. The Unitary Group Adapted State Universal Coupled Cluster (UGA-SUMRCC) theory, recently formulated and implemented by Sen et al. [J. Chem. Phys. 137, 074104 (2012)], is very effective in capturing orbital relaxation accompanying ionization or excitation of both the core and the valence electrons [S. Sen et al., Mol. Phys. 111, 2625 (2013); A. Shee et al., J. Chem. Theory Comput. 9, 2573 (2013)] while preserving the spin-symmetry of the target states and using the neutral closed-shell spatial orbitals of the ground state. Our Ansatz invokes a normal-ordered exponential representation of spin-free cluster-operators. The orbital relaxation induced by a specific set of cluster operators in our Ansatz is good enough to eliminate the need for different sets of orbitals for the ground and the core-ionized states. We call the single configuration state function (CSF) limit of this theory the Unitary Group Adapted Open-Shell Coupled Cluster (UGA-OSCC) theory. The aim of this paper is to comprehensively explore the efficacy of our Ansatz to describe orbital relaxation, using both theoretical analysis and numerical performance. Whenever warranted, we also make appropriate comparisons with other coupled-cluster theories. A physically motivated truncation of the chains of spin-free T-operators is also made possible by the normal-ordering, and the operational resemblance to single reference coupled-cluster theory allows easy implementation. Our test case is the prediction of the 1s core IP of molecules containing a single light- to medium-heavy nucleus and thus, in addition to demonstrating the orbital relaxation, we have addressed the scalar relativistic effects on the accuracy of the IPs by using a hierarchy of spin-free Hamiltonians in conjunction with our theory. Additionally, the contribution of the spin-free component of the two-electron Gaunt term, not usually taken into consideration, has been estimated at the Self-Consistent Field (ΔSCF) level and is found to become increasingly important and eventually quite prominent for molecules with third period atoms and below. The accuracies of the IPs computed using UGA-OSCC are found to be of the same order as the Coupled Cluster Singles Doubles (ΔCCSD) values while being free from spin contamination. Since the UGA-OSCC uses a common set of orbitals for the ground state and the ion, it obviates the need of two N5 AO to MO transformation in contrast to the ΔCCSD method.

Inclusion of orbital relaxation and correlation through the unitary group adapted open shell coupled cluster theory using non-relativistic and scalar relativistic Hamiltonians to study the core ionization potential of molecules containing light to medium-heavy elements.

PubMed

Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

2018-02-07

The orbital relaxation attendant on ionization is particularly important for the core electron ionization potential (core IP) of molecules. The Unitary Group Adapted State Universal Coupled Cluster (UGA-SUMRCC) theory, recently formulated and implemented by Sen et al. [J. Chem. Phys. 137, 074104 (2012)], is very effective in capturing orbital relaxation accompanying ionization or excitation of both the core and the valence electrons [S. Sen et al., Mol. Phys. 111, 2625 (2013); A. Shee et al., J. Chem. Theory Comput. 9, 2573 (2013)] while preserving the spin-symmetry of the target states and using the neutral closed-shell spatial orbitals of the ground state. Our Ansatz invokes a normal-ordered exponential representation of spin-free cluster-operators. The orbital relaxation induced by a specific set of cluster operators in our Ansatz is good enough to eliminate the need for different sets of orbitals for the ground and the core-ionized states. We call the single configuration state function (CSF) limit of this theory the Unitary Group Adapted Open-Shell Coupled Cluster (UGA-OSCC) theory. The aim of this paper is to comprehensively explore the efficacy of our Ansatz to describe orbital relaxation, using both theoretical analysis and numerical performance. Whenever warranted, we also make appropriate comparisons with other coupled-cluster theories. A physically motivated truncation of the chains of spin-free T-operators is also made possible by the normal-ordering, and the operational resemblance to single reference coupled-cluster theory allows easy implementation. Our test case is the prediction of the 1s core IP of molecules containing a single light- to medium-heavy nucleus and thus, in addition to demonstrating the orbital relaxation, we have addressed the scalar relativistic effects on the accuracy of the IPs by using a hierarchy of spin-free Hamiltonians in conjunction with our theory. Additionally, the contribution of the spin-free component of the two-electron Gaunt term, not usually taken into consideration, has been estimated at the Self-Consistent Field (ΔSCF) level and is found to become increasingly important and eventually quite prominent for molecules with third period atoms and below. The accuracies of the IPs computed using UGA-OSCC are found to be of the same order as the Coupled Cluster Singles Doubles (ΔCCSD) values while being free from spin contamination. Since the UGA-OSCC uses a common set of orbitals for the ground state and the ion, it obviates the need of two N 5 AO to MO transformation in contrast to the ΔCCSD method.

High resolution far-infrared observations of the evolved H II region M16

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBreen, B.; Fazio, G.G.; Jaffe, D.T.

1982-03-01

M16 is an evolved, extremely density bounded H II region, which now consists only of a series of ionization fronts at molecular cloud boundaries. The source of ionization is the OB star cluster (NGC 6611) which is about 5 x 10/sup 6/ years old. We used the CFA/UA 102 cm balloon-borne telescope to map this region and detected three far-infrared (far-IR) sources embedded in an extended ridge of emission. Source I is an unresolved far-IR source embedded in a molecular cloud near a sharp ionization front. An H/sub 2/O maser is associated with this source, but no radio continuum emissionmore » has been observed. The other two far-IR sources (II and III) are associated with ionized gas-molecular cloud interfaces, with the far-IR radiation arising from dust at the boundary heated by the OB cluster. Source II is located at the southern prominent neutral intrusion with its associated bright rims and dark ''elephant trunk'' globules that delineate the current progress of the ionization front into the neutral material, and Source III arises at the interface of the northern molecular cloud fragment.« less

Ionization of doped helium nanodroplets: Complexes of C60 with water clusters

NASA Astrophysics Data System (ADS)

Denifl, S.; Zappa, F.; Mähr, I.; Mauracher, A.; Probst, M.; Urban, J.; Mach, P.; Bacher, A.; Bohme, D. K.; Echt, O.; Märk, T. D.; Scheier, P.

2010-06-01

Water clusters are known to undergo an autoprotonation reaction upon ionization by photons or electron impact, resulting in the formation of (H2O)nH3O+. Ejection of OH cannot be quenched by near-threshold ionization; it is only partly quenched when clusters are complexed with inert gas atoms. Mass spectra recorded by electron ionization of water-doped helium droplets show that the helium matrix also fails to quench OH loss. The situation changes drastically when helium droplets are codoped with C60. Charged C60-water complexes are predominantly unprotonated; C60(H2O)4+ and (C60)2(H2O)4+ appear with enhanced abundance. Another intense ion series is due to C60(H2O)nOH+; dehydrogenation is proposed to be initiated by charge transfer between the primary He+ ion and C60. The resulting electronically excited C60+∗ leads to the formation of a doubly charged C60-water complex either via emission of an Auger electron from C60+∗, or internal Penning ionization of the attached water complex, followed by charge separation within {C60(H2O)n}2+. This mechanism would also explain previous observations of dehydrogenation reactions in doped helium droplets. Mass-analyzed ion kinetic energy scans reveal spontaneous (unimolecular) dissociation of C60(H2O)n+. In addition to the loss of single water molecules, a prominent reaction channel yields bare C60+ for sizes n=3, 4, or 6. Ab initio Hartree-Fock calculations for C60-water complexes reveal negligible charge transfer within neutral complexes. Cationic complexes are well described as water clusters weakly bound to C60+. For n=3, 4, or 6, fissionlike desorption of the entire water complex from C60(H2O)n+ energetically competes with the evaporation of a single water molecule.

Interaction of intense ultrashort pulse lasers with clusters.

NASA Astrophysics Data System (ADS)

Petrov, George

2007-11-01

The last ten years have witnessed an explosion of activity involving the interaction of clusters with intense ultrashort pulse lasers. Atomic or molecular clusters are targets with unique properties, as they are halfway between solid and gases. The intense laser radiation creates hot dense plasma, which can provide a compact source of x-rays and energetic particles. The focus of this investigation is to understand the salient features of energy absorption and Coulomb explosion by clusters. The evolution of clusters is modeled with a relativistic time-dependent 3D Molecular Dynamics (MD) model [1]. The Coulomb interaction between particles is handled by a fast tree algorithm, which allows large number of particles to be used in simulations [2]. The time histories of all particles in a cluster are followed in time and space. The model accounts for ionization-ignition effects (enhancement of the laser field in the vicinity of ions) and a variety of elementary processes for free electrons and charged ions, such as optical field and collisional ionization, outer ionization and electron recapture. The MD model was applied to study small clusters (1-20 nm) irradiated by a high-intensity (10^16-10^20 W/cm^2) sub-picosecond laser pulse. We studied fundamental cluster features such as energy absorption, x-ray emission, particle distribution, average charge per atom, and cluster explosion as a function of initial cluster radius, laser peak intensity and wavelength. Simulations of novel applications, such as table-top nuclear fusion from exploding deuterium clusters [3] and high power synchrotron radiation for biological applications and imaging [4] have been performed. The application for nuclear fusion was motivated by the efficient absorption of laser energy (˜100%) and its high conversion efficiency into ion kinetic energy (˜50%), resulting in neutron yield of 10^6 neutrons/Joule laser energy. Contributors: J. Davis and A. L. Velikovich. [1] G. M. Petrov, et al Phys. Plasmas 12 063103 (2005); 13 033106 (2006) [2] G. M. Petrov, J. Davis, European Phys. J. D 41 629 (2007) [3] G. M. Petrov, J. Davis, A. L. Velikovich, Plasma Phys. Contr. Fusion 48 1721 (2006) [4] G. M. Petrov, J. Davis, A. L. Velikovich, J. Phys. B 39 4617 (2006)

Unexpected methyl migrations of ethanol dimer under synchrotron VUV radiation

NASA Astrophysics Data System (ADS)

Xiao, Weizhan; Hu, Yongjun; Li, Weixing; Guan, Jiwen; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

2015-01-01

While methyl transfer is well known to occur in the enzyme- and metal-catalyzed reactions, the methyl transfer in the metal-free organic molecules induced by the photon ionization has been less concerned. Herein, vacuum ultraviolet single photon ionization and dissociation of ethanol dimer are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical methods. Besides the protonated clusters cation (C2H5OH) ṡ H+ (m/z = 47) and the β-carbon-carbon bond cleavage fragment CH2O ṡ (C2H5OH)H+ (m/z = 77), the measured mass spectra revealed that a new fragment (C2H5OH) ṡ (CH3)+ (m/z = 61) appeared at the photon energy of 12.1 and 15.0 eV, where the neutral dimer could be vertically ionized to higher ionic state. Thereafter, the generated carbonium ions are followed by a Wagner-Meerwein rearrangement and then dissociate to produce this new fragment, which is considered to generate after surmounting a few barriers including intra- and inter-molecular methyl migrations by the aid of theoretical calculations. The appearance energy of this new fragment is measured as 11.55 ± 0.05 eV by scanning photoionization efficiency curve. While the signal intensity of fragment m/z = 61 starts to increase, the fragments m/z = 47 and 77 tend to slowly incline around 11.55 eV photon energy. This suggests that the additional fragment channels other than (C2H5OH) ṡ H+ and CH2O ṡ (C2H5OH)H+ have also been opened, which consume some dimer cations. The present report provides a clear description of the photoionization and dissociation processes of the ethanol dimer in the range of the photon energy 12-15 eV.

Advanced carbon-based material C{sub 60} modification using partially ionized cluster and energetic beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du Yuancheng; Ren Zhongmin; Ning Zhifeng

1997-06-20

Two processes have been undertaken using Partially ionized cluster deposition (PICBD) and energetic ion bombardment beams deposition (IBD) respectively. C{sub 60} films deposited by PICBD at V=0 and 65 V, which result in highly textured close-packed structure in orientation (110) and being more polycrystalline respectively, the resistance of C{sub 60} films to oxygen diffusion contamination will be improved. In the case of PICBD, the ionized C{sub 60} soccer-balls molecules in the evaporation beams will be fragmented in collision with the substrate under the elevated accelerating fields Va. As a new synthetic IBD processing, two low energy (400 and 1000 eV)more » nitrogen ion beams have been used to bombard C{sub 60} films to synthesize the carbon nitride films.« less

The Effect of Clustering on Estimations of the UV Ionizing Background from the Proximity Effect

NASA Astrophysics Data System (ADS)

Pascarelle, S. M.; Lanzetta, K. M.; Chen, H. W.

1999-09-01

There have been several determinations of the ionizing background using the proximity effect observed in the distibution of Lyman-alpha absorption lines in the spectra of QSOs at high redshift. It is usually assumed that the distribution of lines should be the same at very small impact parameters to the QSO as it is at large impact parameters, and any decrease in line density at small impact parameters is due to ionizing radiation from the QSO. However, if these Lyman-alpha absorption lines arise in galaxies (Lanzetta et al. 1995, Chen et al. 1998), then the strength of the proximity effect may have been underestimated in previous work, since galaxies are known to cluster around QSOs. Therefore, the UV background estimations have likely been overestimated by the same factor.

The State of the Warm and Cold Gas in the Extreme Starburst at the Core of the Phoenix Galaxy Cluster (SPT-CLJ2344-4243)

NASA Astrophysics Data System (ADS)

McDonald, Michael; Swinbank, Mark; Edge, Alastair C.; Wilner, David J.; Veilleux, Sylvain; Benson, Bradford A.; Hogan, Michael T.; Marrone, Daniel P.; McNamara, Brian R.; Wei, Lisa H.; Bayliss, Matthew B.; Bautz, Marshall W.

2014-03-01

We present new optical integral field spectroscopy (Gemini South) and submillimeter spectroscopy (Submillimeter Array) of the central galaxy in the Phoenix cluster (SPT-CLJ2344-4243). This cluster was previously reported to have a massive starburst (~800 M ⊙ yr-1) in the central, brightest cluster galaxy, most likely fueled by the rapidly cooling intracluster medium. These new data reveal a complex emission-line nebula, extending for >30 kpc from the central galaxy, detected at [O II]λλ3726, 3729, [O III]λλ4959, 5007, Hβ, Hγ, Hδ, [Ne III]λ3869, and He II λ4686. The total Hα luminosity, assuming Hα/Hβ = 2.85, is L Hα = 7.6 ± 0.4 ×1043 erg s-1, making this the most luminous emission-line nebula detected in the center of a cool core cluster. Overall, the relative fluxes of the low-ionization lines (e.g., [O II], Hβ) to the UV continuum are consistent with photoionization by young stars. In both the center of the galaxy and in a newly discovered highly ionized plume to the north of the galaxy, the ionization ratios are consistent with both shocks and active galactic nucleus (AGN) photoionization. We speculate that this extended plume may be a galactic wind, driven and partially photoionized by both the starburst and central AGN. Throughout the cluster we measure elevated high-ionization line ratios (e.g., He II/Hβ, [O III]/Hβ), coupled with an overall high-velocity width (FWHM gsim 500 km s-1), suggesting that shocks are likely important throughout the interstellar medium of the central galaxy. These shocks are most likely driven by a combination of stellar winds from massive young stars, core-collapse supernovae, and the central AGN. In addition to the warm, ionized gas, we detect a substantial amount of cold, molecular gas via the CO(3-2) transition, coincident in position with the galaxy center. We infer a molecular gas mass of M_{H_2} = 2.2 ± 0.6 × 1010 M ⊙, which implies that the starburst will consume its fuel in ~30 Myr if it is not replenished. The L IR/M_{H_2} that we measure for this cluster is consistent with the starburst limit of 500 L ⊙/M ⊙, above which radiation pressure is able to disperse the cold reservoir. The combination of the high level of turbulence in the warm phase and the high L IR/M_{H_2} ratio suggests that this violent starburst may be in the process of quenching itself. We propose that phases of rapid star formation may be common in the cores of galaxy clusters, but so short-lived that their signatures are quickly erased and appear only in a subsample of the most strongly cooling clusters.

The effect of pi-stacking, h-bonding, and electrostatic interactions on the ionization energies of nucleic acid bases: adenine-adenine, thymine-thymine and adenine-thymine dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bravaya, Ksenia B.; Kostko, Oleg; Ahmed, Musahid

A combined theoretical and experimental study of the ionized dimers of thymine and adenine, TT, AA, and AT, is presented. Adiabatic and vertical ionization energies(IEs) for monomers and dimers as well as thresholds for the appearance of the protonated species are reported and analyzed. Non-covalent interactions stronglyaffect the observed IEs. The magnitude and the nature of the effect is different for different isomers of the dimers. The computations reveal that for TT, the largestchanges in vertical IEs (0.4 eV) occur in asymmetric h-bonded and symmetric pi- stacked isomers, whereas in the lowest-energy symmetric h-bonded dimer the shiftin IEs is muchmore » smaller (0.1 eV). The origin of the shift and the character of the ionized states is different in asymmetric h-bonded and symmetric stacked isomers. Inthe former, the initial hole is localized on one of the fragments, and the shift is due to the electrostatic stabilization of the positive charge of the ionized fragment by thedipole moment of the neutral fragment. In the latter, the hole is delocalized, and the change in IE is proportional to the overlap of the fragments' MOs. The shifts in AAare much smaller due to a less effcient overlap and a smaller dipole moment. The ionization of the h-bonded dimers results in barrierless (or nearly barrierless) protontransfer, whereas the pi-stacked dimers relax to structures with the hole stabilized by the delocalization or electrostatic interactions.« less

The Pillars of Creation revisited with MUSE: gas kinematics and high-mass stellar feedback traced by optical spectroscopy

NASA Astrophysics Data System (ADS)

McLeod, A. F.; Dale, J. E.; Ginsburg, A.; Ercolano, B.; Gritschneder, M.; Ramsay, S.; Testi, L.

2015-06-01

Integral field unit (IFU) data of the iconic Pillars of Creation in M16 are presented. The ionization structure of the pillars was studied in great detail over almost the entire visible wavelength range, and maps of the relevant physical parameters, e.g. extinction, electron density, electron temperature, line-of-sight velocity of the ionized and neutral gas are shown. In agreement with previous authors, we find that the pillar tips are being ionized and photoevaporated by the massive members of the nearby cluster NGC 6611. They display a stratified ionization structure where the emission lines peak in a descending order according to their ionization energies. The IFU data allowed us to analyse the kinematics of the photoevaporative flow in terms of the stratified ionization structure, and we find that, in agreement with simulations, the photoevaporative flow is traced by a blueshift in the position-velocity profile. The gas kinematics and ionization structure have allowed us to produce a sketch of the 3D geometry of the Pillars, positioning the pillars with respect to the ionizing cluster stars. We use a novel method to detect a previously unknown bipolar outflow at the tip of the middle pillar and suggest that it has an embedded protostar as its driving source. Furthermore we identify a candidate outflow in the leftmost pillar. With the derived physical parameters and ionic abundances, we estimate a mass-loss rate due to the photoevaporative flow of 70 M⊙ Myr-1 which yields an expected lifetime of approximately 3 Myr.

Ionospheric disturbances in low- and middle-latitudes induced by neutral winds and vertical ExB drift during the 2015 St. Patrick's Day storm

NASA Astrophysics Data System (ADS)

Lee, W. K.; Kil, H.; Krall, J.

2016-12-01

Significant longitudinal and latitudinal modulations in plasma density were observed by satellites during the 17 March 2015 storm. Pronounced equatorial ionization anomaly (EIA) and ionization trough developed in the Indian sector (60°-90°E), whereas those features did not appear in the African sector (20°-40°E). Significant ionospheric uplift was observed in the Indian sector, but the uplift was ignorable in the African sector. The vertical ExB drift is an important factor for the longitudinal variation of the ionospheric morphology, but the observed latitudinal density profiles are not explained satisfactorily by the effect of the vertical ExB drift alone. In this study, we investigate the combined effect of vertical ExB drift and meridional winds by conducting SAMI2 (Sam2 is Another Model of the Ionosphere) model simulations. By comparing the model results with satellite observations, we will assess the ionospheric conditions in the Indian and African sectors. The observations of Defense Meteorological satellite Program, Swarm, and Communication/Navigation Outage Forecasting System satellites will be analyzed for this purpose.

Dynamic Coupling of Quasi-Electrostatic Thundercloud Fields to the Mesosphere and Lower Ionosphere: Sprites and Jets

NASA Technical Reports Server (NTRS)

Pasko, Victor Petrovich

1996-01-01

Red Sprites and Blue Jets are two different types of recently discovered optical flashes ob- served above large thunderstorm systems. Sprites are luminous glows occurring at altitudes typically ranging from approximately 50 to 90 km. In video they exhibit a red color at their top which gradually changes to blue at lower altitudes. Sprites may occur singly or in clusters of two or more. The lateral extent of "unit" sprites is typically 5-10 km and they endure for several milliseconds. Jets are upward moving (approximately 100 km/s) highly collimated beams of luminosity, emanating from the tops of thunderclouds, extending up to approximately 50 km altitude and exhibiting a primarily blue color. We propose that sprites result from large electric field transients capable of causing electron heating, breakdown ionization and excitation of optical emissions at mesospheric altitudes following the removal of thundercloud charge by a cloud-to-ground discharge. Depending on the history of charge accumulation and removal, and the distribution of ambient atmospheric conductivity, the breakdown region may have the shape of vertically oriented ionization column(s). Results of a two-dimensional and self consistent quasi-electrostatic (QE) model indicate that most of the observed features of sprites can be explained in terms of the formation and self-driven propagation of streamer type channels of breakdown ionization. Comparison of the optical emission intensities of the 1st and 2nd positive bands of N2, Meinel and 1st negative bands of N2(+) and the 1st negative band of O2(+) demonstrates that the 1st positive band of N2 is the dominant optical emission in the altitude range approximately 50-90 km, which accounts for the observed red color of sprites. Optical emissions of the 1st and 2nd positive bands of N2 occur in carrot-like vertical structures with typical transverse dimension approximately 5-10 km which can span an altitude range from approximately 80 km to well below approximately 50 km. The appearance of optical emissions associated with sprites can be delayed in time (approximately 1-20 ms) with respect to the causative cloud to ground discharge. Theoretical model results are found to be in good agreement with recent video, photometric and spectral measurements of sprites.

Infrared Absorption of Methanol-Water Clusters Mn(H2O), n = 1-4, Recorded with the Vuv-Ionization Techniques

NASA Astrophysics Data System (ADS)

Lee, Yu-Fang; Lee, Yuan-Pern

2016-06-01

We investigated IR spectra in the CH- and OH-stretching regions of size-selected methanol-water clusters, Mn(H_2O) with M representing CH_3OH and n = 1-4, in a pulsed supersonic jet by using the VUV (vacuum-ultraviolet)-ionization/IR-depletion technique. The VUV light at 118 nm served as the source of ionization in a time-of-flight mass spectrometer. The tunable IR laser served as a source of dissociation for clusters before ionization. Spectra of methanol-water clusters in the OH region show significant variations as the number of methanol molecules increase, whereas spectra in the CH region are similar. For M(H_2O), absorption of a structure with H_2O as a proton donor was observed at 3570, 3682, and 3722 wn, whereas that of methanol as a proton donor was observed at 3611 and 3753 wn. For M2(H_2O), the OH-stretching band of the dangling OH of H_2O was observed at 3721 wn, whereas overlapped bands near 3425, 3472, and 3536 wn correspond to the OH-stretching modes of three hydrogen-bonded OH in a cyclic structure. For M3(H_2O), the dangling OH shifts to 3715 wn, and the hydrogen-bonded OH-stretching bands become much broader, with a band near 3179 wn having the smallest wavenumber. Scaled harmonic vibrational wavenumbers and relative IR intensities predicted for the methanol-water clusters with the M06-2X/aug-cc-pVTZ method are consistent with our experimental results. For M4(H_2O), observed spectrum agree less with theoretical predictions, indicating the presence of isomers other than the most stable cyclic one. Spectra of Mn(H_2O) and Mn+1 are compared and the cooperative hydrogen-bonding is discussed.

Revealing Thermal Instabilities in the Core of the Phoenix Cluster

NASA Astrophysics Data System (ADS)

McDonald, Michael

2017-08-01

The Phoenix cluster is the most relaxed cluster known, and hosts the strongest cool core of any cluster yet discovered. At the center of this cluster is a massive starburst galaxy, with a SFR of 500-1000 Msun/yr, seemingly satisfying the early cooling flow predictions, despite the presence of strong AGN feedback from the central supermassive black hole. Here we propose deep narrow-band imaging of the central 120 kpc of the cluster, to map the warm (10^4K) ionized gas via the [O II] emission line. In low-z clusters, such as Perseus and Abell 1795, the warm, ionized phase is of critical importance to map out thermal instabilities in the hot gas, and maps of Halpha and [O II] have been used for decades to understand how (and how not) cooling proceeds in the intracluster medium. The data proposed for here, combined with deep ALMA data, a recently-approved Large Chandra Program, and recently-approved multi-frequency JVLA data, will allow us to probe the cooling ICM, the cool, filamentary gas, the cold molecular gas, the star-forming population, and the AGN jets all on scales of <10 kpc. This multi-observatory campaign, focusing on the most extreme cooling cluster, will lead to a more complete understanding of how and why thermal instabilities develop in the hot ICM of cool core clusters.

CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J.; Winograd, Nicholas

2016-09-01

The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure.

Infrared absorption of methanol clusters (CH3OH)n with n = 2-6 recorded with a time-of-flight mass spectrometer using infrared depletion and vacuum-ultraviolet ionization.

PubMed

Han, Hui-Ling; Camacho, Cristopher; Witek, Henryk A; Lee, Yuan-Pern

2011-04-14

We investigated IR spectra in the CH- and OH-stretching regions of size-selected methanol clusters, (CH(3)OH)(n) with n = 2-6, in a pulsed supersonic jet by using the IR-VUV (vacuum-ultraviolet) ionization technique. VUV emission at 118 nm served as the source of ionization in a time-of-flight mass spectrometer. The tunable IR laser emission served as a source of predissociation or excitation before ionization. The variations of intensity of protonated methanol cluster ions (CH(3)OH)(n)H(+) and CH(3)OH(+) and (CH(3)OH)(2)(+) were monitored as the IR laser light was tuned across the range 2650-3750 cm(-1). Careful processing of these action spectra based on photoionization efficiencies and the production and loss of each cluster due to photodissociation yielded IR spectra of the size-selected clusters. Spectra of methanol clusters in the OH region have been extensively investigated; our results are consistent with previous reports, except that the band near 3675 cm(-1) is identified as being associated with the proton acceptor of (CH(3)OH)(2). Spectra in the CH region are new. In the region 2800-3050 cm(-1), bands near 2845, 2956, and 3007 cm(-1) for CH(3)OH split into 2823, 2849, 2934, 2955, 2984, and 3006 cm(-1) for (CH(3)OH)(2) that correspond to proton donor and proton acceptor, indicating that the methanol dimer has a preferred open-chain structure. In contrast, for (CH(3)OH)(3), the splitting diminishes and the bands near 2837, 2954, and 2987 cm(-1) become narrower, indicating a preferred cyclic structure. Anharmonic vibrational wavenumbers predicted for the methanol open-chain dimer and the cyclic trimer with the B3LYP∕VPT2∕ANO1 level of theory are consistent with experimental results. For the tetramer and pentamer, the spectral pattern similar to that of the trimer but with greater widths was observed, indicating that the most stable structures are also cyclic.

Hundred Thousand Degree Gas in the Virgo Cluster of Galaxies

NASA Astrophysics Data System (ADS)

Sparks, W. B.; Pringle, J. E.; Carswell, R. F.; Donahue, M.; Martin, R.; Voit, M.; Cracraft, M.; Manset, N.; Hough, J. H.

2012-05-01

The physical relationship between low-excitation gas filaments at ~104 K, seen in optical line emission, and diffuse X-ray emitting coronal gas at ~107 K in the centers of many galaxy clusters is not understood. It is unclear whether the ~104 K filaments have cooled and condensed from the ambient hot (~107 K) medium or have some other origin such as the infall of cold gas in a merger, or the disturbance of an internal cool reservoir of gas by nuclear activity. Observations of gas at intermediate temperatures (~105-106 K) can potentially reveal whether the central massive galaxies are gaining cool gas through condensation or losing it through conductive evaporation and hence identify plausible scenarios for transport processes in galaxy cluster gas. Here we present spectroscopic detection of ~105 K gas spatially associated with the Hα filaments in a central cluster galaxy, M87, in the Virgo Cluster. The measured emission-line fluxes from triply ionized carbon (C IV 1549 Å) and singly ionized helium (He II 1640 Å) are consistent with a model in which thermal conduction determines the interaction between hot and cold phases.

Autoionization following nanoplasma formation in atomic and molecular clusters

NASA Astrophysics Data System (ADS)

Schütte, Bernd; Lahl, Jan; Oelze, Tim; Krikunova, Maria; Vrakking, Marc J. J.; Rouzée, Arnaud

2016-05-01

Nanoplasmas resulting from the ionization of nano-scale particles by intense laser pulses are typically described by quasiclassical models, where electron emission is understood to take place via thermal processes. Recently, we discovered that, following the interaction of intense near-infrared (NIR) laser pulses with molecular oxygen clusters, electron emission from nanoplasmas can also occur from atomic bound states via autoionization [Schütte et al., Phys. Rev. Lett. 114, 123002 (2015)]. Here we extend these studies and demonstrate that the formation and decay of doubly-excited atoms and ions is a very common phenomenon in nanoplasmas. We report on the observation of autoionization involving spin-orbit excited states in molecular oxygen and carbon dioxide clusters as well as in atomic krypton and xenon clusters ionized by intense NIR pulses, for which we find clear bound-state signatures in the electron kinetic energy spectra. By applying terahertz (THz) streaking, we show that the observed autoionization processes take place on a picosecond to nanosecond timescale after the interaction of the NIR laser pulse with the clusters. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.

OPTICAL PHOTOMETRIC AND POLARIMETRIC INVESTIGATION OF NGC 1931

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandey, A. K.; Eswaraiah, C.; Sharma, Saurabh

We present optical photometric and polarimetric observations of stars toward NGC 1931 with the aim of deriving cluster parameters such as distance, reddening, age, and luminosity/mass function as well as understanding dust properties and star formation in the region. The distance to the cluster is found to be 2.3 {+-} 0.3 kpc and the reddening E(B - V) in the region is found to be variable. The stellar density contours reveal two clusters in the region. The observations suggest a differing reddening law within the cluster region. Polarization efficiency of the dust grains toward the direction of the cluster ismore » found to be less than that for the general diffuse interstellar medium (ISM). The slope of the mass function (-0.98 {+-} 0.22) in the southern region in the mass range of 0.8 < M/M {sub Sun} < 9.8 is found to be shallower in comparison to that in the northern region (-1.26 {+-} 0.23), which is comparable to the Salpeter value (-1.35). The K-band luminosity function (KLF) of the region is found to be comparable to the average value of the slope ({approx}0.4) for young clusters obtained by Lada and Lada; however, the slope of the KLF is steeper in the northern region as compared to the southern region. The region is probably ionized by two B2 main-sequence-type stars. The mean age of the young stellar objects (YSOs) is found to be 2 {+-} 1 Myr, which suggests that the identified YSOs could be younger than the ionizing sources of the region. The morphology of the region, the distribution and ages of the YSOs, and ionizing sources indicate a triggered star formation in the region.« less

Al7CX (X=Li-Cs) clusters: Stability and the prospect for cluster materials

NASA Astrophysics Data System (ADS)

Ashman, C.; Khanna, S. N.; Pederson, M. R.; Kortus, J.

2000-12-01

Al7C clusters, recently found to have a high-electron affinity and exceptional stability, are shown to form ionic molecules when combined with alkali-metal atoms. Our studies, based on an ab initio gradient-corrected density-functional scheme, show that Al7CX (X=Li-Cs) clusters have a very low-electron affinity and a high-ionization potential. When combined, the two- and four-atom composite clusters of Al7CLi units leave the Al7C clusters almost intact. Preliminary studies indicate that Al7CLi may be suitable to form cluster-based materials.

Ionization-induced solvent migration in acetanilide-methanol clusters inferred from isomer-selective infrared spectroscopy.

PubMed

Weiler, Martin; Nakamura, Takashi; Sekiya, Hiroshi; Dopfer, Otto; Miyazaki, Mitsuhiko; Fujii, Masaaki

2012-12-07

We present the resonance-enhanced multiphoton ionization, infrared-ultraviolet hole burning (IR-UV HB), and IR dip spectra of the trans-acetanilide-methanol (AA-MeOH) cluster in the S(0), S(1), and cationic ground state (D(0)) in a supersonic jet. The IR-UV HB spectra demonstrate the co-existence of two isomers in S(0,1), in which MeOH binds either to the NH or the CO site of the peptide linkage in AA, denoted as AA(NH)-MeOH and AA(CO)-MeOH. When AA(CO)-MeOH is selectively ionized, its IR spectrum in D(0) is the same as that measured for AA(+) (NH)-MeOH. Thus, photoionization of AA(CO)-MeOH induces migration of MeOH from the CO to the NH site with 100% yield. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computation of Electron Impact Ionization Cross sections of Iron Hydrogen Clusters - Relevance in Fusion Plasmas

NASA Astrophysics Data System (ADS)

Patel, Umang; Joshipura, K. N.

2017-04-01

Plasma-wall interaction (PWI) is one of the key issues in nuclear fusion research. In nuclear fusion devices, such as the JET tokamak or the ITER, first-wall materials will be directly exposed to plasma components. Erosion of first-wall materials is a consequence of the impact of hydrogen and its isotopes as main constituents of the hot plasma. Besides the formation of gas-phase atomic species in various charge states, di- and polyatomic molecular species are expected to be formed via PWI processes. These compounds may profoundly disturb the fusion plasma, may lead to unfavorable re-deposition of materials and composites in other areas of the vessel. Interaction between atoms, molecules as well transport of impurities are of interest for modelling of fusion plasma. Qion by electron impact are such process also important in low temperature plasma processing, astrophysics etc. We reported electron impact Qionfor iron hydrogen clusters, FeHn (n = 1 to 10) from ionization threshold to 2000 eV. A semi empirical approach called Complex Scattering Potential - Ionization Contribution (CSP-ic) has been employed for the reported calculation. In context of fusion relevant species Qion were reported for beryllium and its hydrides, tungsten and its oxides and cluster of beryllium-tungsten by Huber et al.. Iron hydrogen clusters are another such species whose Qion were calculated through DM and BEB formalisms, same has been compared with present calculations.

Electron interaction with nitromethane embedded in helium droplets: attachment and ionization measurements.

PubMed

Ferreira da Silva, F; Ptasińska, S; Denifl, S; Gschliesser, D; Postler, J; Matias, C; Märk, T D; Limão-Vieira, P; Scheier, P

2011-11-07

Results of a detailed study on electron interactions with nitromethane (CH(3)NO(2)) embedded in helium nanodroplets are reported. Anionic and cationic products formed are analysed by mass spectrometry. When the doped helium droplets are irradiated with low-energy electrons of about 2 eV kinetic energy, exclusively parent cluster anions (CH(3)NO(2))(n)(-) are formed. At 8.5 eV, three anion cluster series are observed, i.e., (CH(3)NO(2))(n)(-), [(CH(3)NO(2))(n)-H](-), and (CH(3)NO(2))(n)NO(2)(-), the latter being the most abundant. The results obtained for anions are compared with previous electron attachment studies with bare nitromethane and nitromethane condensed on a surface. The cation chemistry (induced by electron ionization of the helium matrix at 70 eV and subsequent charge transfer from He(+) to the dopant cluster) is dominated by production of methylated and protonated nitromethane clusters, (CH(3)NO(2))(n)CH(3)(+) and (CH(3)NO(2))(n)H(+).

PROPERTIES OF QSO METAL-LINE ABSORPTION SYSTEMS AT HIGH REDSHIFTS: NATURE AND EVOLUTION OF THE ABSORBERS AND NEW EVIDENCE ON ESCAPE OF IONIZING RADIATION FROM GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boksenberg, Alec; Sargent, Wallace L. W., E-mail: boksy@ast.cam.ac.uk

2015-05-15

Using Voigt-profile-fitting procedures on Keck High Resolution Spectrograph spectra of nine QSOs, we identify 1099 C IV absorber components clumped in 201 systems outside the Lyman forest over 1.6 ≲ z ≲ 4.4. With associated Si IV, C II, Si II  and N V where available, we investigate the bulk statistical and ionization properties of the components and systems and find no significant change in redshift for C IV and Si IV while C II, Si II  and N V change substantially. The C IV components exhibit strong clustering, but no clustering is detected for systems on scales from 150 kmmore » s{sup –1} out to 50,000 km s{sup –1}. We conclude that the clustering is due entirely to the peculiar velocities of gas present in the circumgalactic media of galaxies. Using specific combinations of ionic ratios, we compare our observations with model ionization predictions for absorbers exposed to the metagalactic ionizing radiation background augmented by proximity radiation from their associated galaxies and find that the generally accepted means of radiative escape by transparent channels from the internal star-forming sites is spectrally not viable for our stronger absorbers. We develop an active scenario based on runaway stars with resulting changes in the efflux of radiation that naturally enable the needed spectral convergence, and in turn provide empirical indicators of morphological evolution in the associated galaxies. Together with a coexisting population of relatively compact galaxies indicated by the weaker absorbers in our sample, the collective escape of radiation is sufficient to maintain the intergalactic medium ionized over the full range 1.9 < z ≲ 4.4.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

McDonald, Michael; Bautz, Marshall W.; Swinbank, Mark

We present new optical integral field spectroscopy (Gemini South) and submillimeter spectroscopy (Submillimeter Array) of the central galaxy in the Phoenix cluster (SPT-CLJ2344-4243). This cluster was previously reported to have a massive starburst (∼800 M {sub ☉} yr{sup –1}) in the central, brightest cluster galaxy, most likely fueled by the rapidly cooling intracluster medium. These new data reveal a complex emission-line nebula, extending for >30 kpc from the central galaxy, detected at [O II]λλ3726, 3729, [O III]λλ4959, 5007, Hβ, Hγ, Hδ, [Ne III]λ3869, and He II λ4686. The total Hα luminosity, assuming Hα/Hβ = 2.85, is L {sub Hα} =more » 7.6 ± 0.4 ×10{sup 43} erg s{sup –1}, making this the most luminous emission-line nebula detected in the center of a cool core cluster. Overall, the relative fluxes of the low-ionization lines (e.g., [O II], Hβ) to the UV continuum are consistent with photoionization by young stars. In both the center of the galaxy and in a newly discovered highly ionized plume to the north of the galaxy, the ionization ratios are consistent with both shocks and active galactic nucleus (AGN) photoionization. We speculate that this extended plume may be a galactic wind, driven and partially photoionized by both the starburst and central AGN. Throughout the cluster we measure elevated high-ionization line ratios (e.g., He II/Hβ, [O III]/Hβ), coupled with an overall high-velocity width (FWHM ≳ 500 km s{sup –1}), suggesting that shocks are likely important throughout the interstellar medium of the central galaxy. These shocks are most likely driven by a combination of stellar winds from massive young stars, core-collapse supernovae, and the central AGN. In addition to the warm, ionized gas, we detect a substantial amount of cold, molecular gas via the CO(3-2) transition, coincident in position with the galaxy center. We infer a molecular gas mass of M{sub H{sub 2}} = 2.2 ± 0.6 × 10{sup 10} M {sub ☉}, which implies that the starburst will consume its fuel in ∼30 Myr if it is not replenished. The L {sub IR}/M{sub H{sub 2}} that we measure for this cluster is consistent with the starburst limit of 500 L {sub ☉}/M {sub ☉}, above which radiation pressure is able to disperse the cold reservoir. The combination of the high level of turbulence in the warm phase and the high L {sub IR}/M{sub H{sub 2}} ratio suggests that this violent starburst may be in the process of quenching itself. We propose that phases of rapid star formation may be common in the cores of galaxy clusters, but so short-lived that their signatures are quickly erased and appear only in a subsample of the most strongly cooling clusters.« less

Effect of the phenoxy groups on PDIB and its derivatives

NASA Astrophysics Data System (ADS)

Song, Peng; Guan, Baijie; Zhou, Qiao; Zhao, Meiyu; Huang, Jindou; Ma, Fengcai

2016-10-01

The anisotropic hole and electron mobilities in N,N‧-3,4,9,10-perylenediimide-1,7-phenoxy (PDIB-2OPh) and N,Nʹ-3,4,9,10-perylenediimide (PDIB) were theoretically predicted using the Marcus-Hush theory. The substituent effect of phenoxy on their mobility rates, absorption spectra, electron affinities, and ionization potentials was explored. By comparing the simulated hole mobility in PDIB and PDIB-2OPh, it is found that the phenoxy rings act as spacers between adjacent stacking columns in the phenoxy-substituted derivatives. The increasement of the number of benzene oxygen groups leads to the absorption spectra red-shift of these molecular systems. This coincides with their change tendency of the adiabatic ionization potentials, vertical ionization potentials. However, the calculated adiabatic electron affinities and vertical electron affinities of N,N‧-butyl-3,4,9,10-perylenediimide-1,6,7,12-phenoxy (PDIB-4OPh) are larger than those of PDIB;OPh. The steric effect in PDIB-4OPh is expected to cause space reversal and thus to changes in the properties of the molecule.

Effect of the phenoxy groups on PDIB and its derivatives

PubMed Central

Song, Peng; Guan, Baijie; Zhou, Qiao; Zhao, Meiyu; Huang, Jindou; Ma, Fengcai

2016-01-01

The anisotropic hole and electron mobilities in N,N′-3,4,9,10-perylenediimide-1,7-phenoxy (PDIB-2OPh) and N,Nʹ-3,4,9,10-perylenediimide (PDIB) were theoretically predicted using the Marcus–Hush theory. The substituent effect of phenoxy on their mobility rates, absorption spectra, electron affinities, and ionization potentials was explored. By comparing the simulated hole mobility in PDIB and PDIB-2OPh, it is found that the phenoxy rings act as spacers between adjacent stacking columns in the phenoxy-substituted derivatives. The increasement of the number of benzene oxygen groups leads to the absorption spectra red-shift of these molecular systems. This coincides with their change tendency of the adiabatic ionization potentials, vertical ionization potentials. However, the calculated adiabatic electron affinities and vertical electron affinities of N,N′-butyl-3,4,9,10-perylenediimide-1,6,7,12-phenoxy (PDIB-4OPh) are larger than those of PDIB;OPh. The steric effect in PDIB-4OPh is expected to cause space reversal and thus to changes in the properties of the molecule. PMID:27759050

Relaxation channels of multi-photon excited xenon clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serdobintsev, P. Yu.; Melnikov, A. S.; Department of Physics, St. Petersburg State University, Saint Petersburg 198904

2015-09-21

The relaxation processes of the xenon clusters subjected to multi-photon excitation by laser radiation with quantum energies significantly lower than the thresholds of excitation of atoms and ionization of clusters were studied. Results obtained by means of the photoelectron spectroscopy method showed that desorption processes of excited atoms play a significant role in the decay of two-photon excited xenon clusters. A number of excited states of xenon atoms formed during this process were discovered and identified.

Examining the structural evolution of bicarbonate–water clusters: insights from photoelectron spectroscopy, basin-hopping structural search, and comparison with available IR spectral studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, Hui; Hou, Gao-Lei; Liu, Yi-Rong

2016-05-31

Bicarbonate serves a crucial biochemical role in the physiological pH buffering system and also has important atmospheric implications. In the current study, HCO 3 $-$(H 2O) n (n = 0-13) clusters were successfully produced via electrospray ionization of corresponding bulk salt solution, and were characterized by combining negative ion photoelectron spectroscopy and theoretical calculations. The photoelectron spectra reveal that the electron binding energy monotonically increases with the cluster size up to n = 10 and remains largely the same after n > 10. The photo-detaching feature of the solute HCO3$-$itself, which dominates in the small clusters, diminishes with increase ofmore » water coverage. Based on the charge distribution and molecular orbital analyses, the universal high electron binding energy tail that dominates in the larger clusters can be attributed to ionization of water. Thus, the transition of ionization from solute to solvent at the size larger than n=10 has been observed. Extensive theoretical structural search based on the Basin-Hopping unbiased method was carried out, and a plethora of low energy isomers have been obtained for each medium and large size. By comparing the simulated photoelectron spectra and calculated electron binding energies with the experiments, as well as by comparing the simulated infrared spectra with previously reported IR spectra, the probable global minima and the structural evolutionary routes are presented. The nature of bicarbonate-water interactions are mainly electrostatic as implied by the electron localization function (ELF) analysis.« less

Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Aryya; Vaval, Nayana, E-mail: np.vaval@ncl.res.in; Pal, Sourav

2015-07-14

Auger decay is an efficient ultrafast relaxation process of core-shell or inner-shell excited atom or molecule. Generally, it occurs in femto-second or even atto-second time domain. Direct measurement of lifetimes of Auger process of single ionized and double ionized inner-shell state of an atom or molecule is an extremely difficult task. In this paper, we have applied the highly correlated complex absorbing potential-equation-of-motion coupled cluster (CAP-EOMCC) approach which is a combination of CAP and EOMCC approach to calculate the lifetime of the states arising from 2p inner-shell ionization of an Ar atom and 3d inner-shell ionization of Kr atom. Wemore » have also calculated the lifetime of Ar{sup 2+}(2p{sup −1}3p{sup −1}) {sup 1}D, Ar{sup 2+}(2p{sup −1}3p{sup −1}) {sup 1}S, and Ar{sup 2+}(2p{sup −1}3s{sup −1}) {sup 1}P double ionized states. The predicted results are compared with the other theoretical results as well as experimental results available in the literature.« less

Probing the Dragonfish star-forming complex: the ionizing population of the young massive cluster Mercer 30

NASA Astrophysics Data System (ADS)

de la Fuente, D.; Najarro, F.; Borissova, J.; Ramírez Alegría, S.; Hanson, M. M.; Trombley, C.; Figer, D. F.; Davies, B.; Garcia, M.; Kurtev, R.; Urbaneja, M. A.; Smith, L. C.; Lucas, P. W.; Herrero, A.

2016-05-01

It has recently been claimed that the nebula, Dragonfish, is powered by a superluminous but elusive OB association. However, systematic searches in near-infrared photometric surveys have found many other cluster candidates in this region of the sky. Among these, the first confirmed young massive cluster was Mercer 30, where Wolf-Rayet stars were found.We perform a new characterization of Mercer 30 with unprecedented accuracy, combining NICMOS/HST and VVV photometric data with multi-epoch ISAAC/VLT H- and K-band spectra. Stellar parameters for most of spectroscopically observed cluster members are found through precise non-LTE atmosphere modeling with the CMFGEN code. Our spectrophotometric study for this cluster yields a new, revised distance of d = (12.4 ± 1.7) kpc and a total of QHMc30 ≈ 6.70 × 1050 s-1 Lyman ionizing photons. A cluster age of (4.0 ± 0.8) Myr is found through isochrone fitting, and a total mass of (1.6 ± 0.6) × 104M⊙ is estimated, thanks to our extensive knowledge of the post-main-sequence population. As a consequence, membership of Mercer 30 to the Dragonfish star-forming complex is confirmed, allowing us to use this cluster as a probe for the whole complex, which turns out to be extremely large (~400 pc across) and located at the outer edge of the Sagittarius-Carina spiral arm (~11 kpc from the Galactic center). The Dragonfish complex hosts 19 young clusters or cluster candidates (including Mercer 30 and a new candidate presented in this work) and an estimated minimum of nine field Wolf-Rayet stars. All these contributions account for, at least 73% of the ionization of the Dragonfish nebula and leaves little or no room for the alleged superluminous OB association; alternative explanations are discussed. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile, under programs IDs 179.B-2002, 081.D-0471, 083.D-0765, 087.D-0957, and 089.D-0989.

Atomic Cluster Ionization and Attosecond Generation at Long Wavelengths

DTIC Science & Technology

2015-10-31

fellowships for further studies in science, mathematics, engineering or technology fields: Student Metrics This section only applies to graduating...order to investigate this we use a modified Lewenstein quantum model in which the cluster is represented by a 1D Coulomb potential for the parent ion

Large-scale Map of Millimeter-wavelength Hydrogen Radio Recombination Lines around a Young Massive Star Cluster

NASA Astrophysics Data System (ADS)

Nguyen-Luong, Q.; Anderson, L. D.; Motte, F.; Kim, Kee-Tae; Schilke, P.; Carlhoff, P.; Beuther, H.; Schneider, N.; Didelon, P.; Kramer, C.; Louvet, F.; Nony, T.; Bihr, S.; Rugel, M.; Soler, J.; Wang, Y.; Bronfman, L.; Simon, R.; Menten, K. M.; Wyrowski, F.; Walmsley, C. M.

2017-08-01

We report the first map of large-scale (10 pc in length) emission of millimeter-wavelength hydrogen recombination lines (mm-RRLs) toward the giant H II region around the W43-Main young massive star cluster (YMC). Our mm-RRL data come from the IRAM 30 m telescope and are analyzed together with radio continuum and cm-RRL data from the Karl G. Jansky Very Large Array and HCO+ 1-0 line emission data from the IRAM 30 m. The mm-RRLs reveal an expanding wind-blown ionized gas shell with an electron density ˜70-1500 cm-3 driven by the WR/OB cluster, which produces a total Lyα photon flux of 1.5× {10}50 s-1. This shell is interacting with the dense neutral molecular gas in the W43-Main dense cloud. Combining the high spectral and angular resolution mm-RRL and cm-RRL cubes, we derive the two-dimensional relative distributions of dynamical and pressure broadening of the ionized gas emission and find that the RRL line shapes are dominated by pressure broadening (4-55 {km} {{{s}}}-1) near the YMC and by dynamical broadening (8-36 {km} {{{s}}}-1) near the shell’s edge. Ionized gas clumps hosting ultra-compact H II regions found at the edge of the shell suggest that large-scale ionized gas motion triggers the formation of new star generation near the periphery of the shell.

Illustrating the Concepts of Isotopes and Mass Spectrometry in Introductory Courses: A MALDI-TOF Mass Spectrometry Laboratory Experiment

ERIC Educational Resources Information Center

Dopke, Nancy Carter; Lovett, Timothy Neal

2007-01-01

Mass spectrometry is a widely used and versatile tool for scientists in many different fields. Soft ionization techniques such as matrix-assisted laser desorption/ionization (MALDI) allow for the analysis of biomolecules, polymers, and clusters. This article describes a MALDI mass spectrometry experiment designed for students in introductory…

Ionization Efficiency in the Dayside Martian Upper Atmosphere

NASA Astrophysics Data System (ADS)

Cui, J.; Wu, X.-S.; Xu, S.-S.; Wang, X.-D.; Wellbrock, A.; Nordheim, T. A.; Cao, Y.-T.; Wang, W.-R.; Sun, W.-Q.; Wu, S.-Q.; Wei, Y.

2018-04-01

Combining the Mars Atmosphere and Volatile Evolution measurements of neutral atmospheric density, solar EUV/X-ray flux, and differential photoelectron intensity made during 240 nominal orbits, we calculate the ionization efficiency, defined as the ratio of the secondary (photoelectron impact) ionization rate to the primary (photon impact) ionization rate, in the dayside Martian upper atmosphere under a range of solar illumination conditions. Both the CO2 and O ionization efficiencies tend to be constant from 160 km up to 250 km, with respective median values of 0.19 ± 0.03 and 0.27 ± 0.04. These values are useful for fast calculation of the ionization rate in the dayside Martian upper atmosphere, without the need to construct photoelectron transport models. No substantial diurnal and solar cycle variations can be identified, except for a marginal trend of reduced ionization efficiency approaching the terminator. These observations are favorably interpreted by a simple scenario with ionization efficiencies, as a first approximation, determined by a comparison between relevant cross sections. Our analysis further reveals a connection between regions with strong crustal magnetic fields and regions with high ionization efficiencies, which are likely indicative of more efficient vertical transport of photoelectrons near magnetic anomalies.

CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry.

PubMed

Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J; Winograd, Nicholas

2016-09-01

The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure. Graphical Abstract ᅟ.

Mass-Selective Laser Photoionization.

ERIC Educational Resources Information Center

Smalley, R. E.

1982-01-01

Discusses the nature and applications of mass-selective laser photoionization. The ionization can be done with a single intense laser pulse lasting a few billionths of a second with no molecular fragmentation. Applications focus on: (1) benzene clusters, excimers, and exciplexes; (2) metal clusters; and (3) triplet formation and decay. (Author/JN)

Supramolecular clusters between carbohydrates and concave pyridines. Detection in the gas phase by resonance-enhanced multi-photon ionization reflectron time-of-flight mass spectrometer.

PubMed

Liebig, Timo; Lüning, Ulrich; Grotemeyer, Jürgen

2006-01-01

For the first time the formation of supramolecular clusters between concave pyridines and different carbohydrates could be observed in the gas phase. The different clusters have been investigated by means of laser desorption into a supersonic beam followed by resonant multi photon excitation yielding mass spectra with high intensity of the different cluster. These preliminary results open a way for the investigations of the hydrogen bonds in these compounds.

Epicyclic helical channels for parametric resonance ionization cooling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johson, Rolland Paul; Derbenev, Yaroslav

Proposed next-generation muon colliders will require major technical advances to achieve rapid muon beam cooling requirements. Parametric-resonance Ionization Cooling (PIC) is proposed as the final 6D cooling stage of a high-luminosity muon collider. In PIC, a half-integer parametric resonance causes strong focusing of a muon beam at appropriately placed energy absorbers while ionization cooling limits the beam’s angular spread. Combining muon ionization cooling with parametric resonant dynamics in this way should then allow much smaller final transverse muon beam sizes than conventional ionization cooling alone. One of the PIC challenges is compensation of beam aberrations over a sufficiently wide parametermore » range while maintaining the dynamical stability with correlated behavior of the horizontal and vertical betatron motion and dispersion. We explore use of a coupling resonance to reduce the dimensionality of the problem and to shift the dynamics away from non-linear resonances. PIC simulations are presented.« less

Method for Continuous Monitoring of Electrospray Ion Formation

NASA Astrophysics Data System (ADS)

Metzler, Guille; Crathern, Susan; Bachmann, Lorin; Fernández-Metzler, Carmen; King, Richard

2017-10-01

A method for continuously monitoring the performance of electrospray ionization without the addition of hardware or chemistry to the system is demonstrated. In the method, which we refer to as SprayDx, cluster ions with solvent vapor natively formed by electrospray are followed throughout the collection of liquid chromatography-selected reaction monitoring data. The cluster ion extracted ion chromatograms report on the consistency of the ion formation and detection system. The data collected by the SprayDx method resemble the data collected for postcolumn infusion of analyte. The response of the cluster ions monitored reports on changes in the physical parameters of the ion source such as voltage and gas flow. SprayDx is also observed to report on ion suppression in a fashion very similar to a postcolumn infusion of analyte. We anticipate the method finding utility as a continuous readout on the performance of electrospray and other atmospheric pressure ionization processes. [Figure not available: see fulltext.

Desorption electrospray ionization mass spectrometry of DNA nucleobases: implications for a liquid film model.

PubMed

Qiu, Bo; Luo, Hai

2009-05-01

Desorption electrospray ionization (DESI) mass spectrometry has been implemented on a commercial ion-trap mass spectrometer and used to optimize mass spectrometric conditions for DNA nucleobases: adenine, cytosine, thymine, and guanine. Experimental parameters including spray voltage, distance between mass spectrometer inlet and the sampled spot, and nebulizing gas inlet pressure were optimized. Cluster ions including some magic number clusters of nucleobases were observed for the first time using DESI mass spectrometry. The formation of the cluster species was found to vary with the nucleobases, acidification of the spray solvent, and the deposited sample amount. All the experimental results can be explained well using a liquid film model based on the two-step droplet pick-up mechanism. It is further suggested that solubility of the analytes in the spray solvent is an important factor to consider for their studies by using DESI. 2009 John Wiley & Sons, Ltd.

Soft-landing ion mobility of silver clusters for small-molecule matrix-assisted laser desorption ionization mass spectrometry and imaging of latent fingerprints.

PubMed

Walton, Barbara L; Verbeck, Guido F

2014-08-19

Matrix-assisted laser desorption ionization (MALDI) imaging is gaining popularity, but matrix effects such as mass spectral interference and damage to the sample limit its applications. Replacing traditional matrices with silver particles capable of equivalent or increased photon energy absorption from the incoming laser has proven to be beneficial for low mass analysis. Not only can silver clusters be advantageous for low mass compound detection, but they can be used for imaging as well. Conventional matrix application methods can obstruct samples, such as fingerprints, rendering them useless after mass analysis. The ability to image latent fingerprints without causing damage to the ridge pattern is important as it allows for further characterization of the print. The application of silver clusters by soft-landing ion mobility allows for enhanced MALDI and preservation of fingerprint integrity.

1997 Technical Digest Series. Volume 7: Applications of High Field and Short Wavelength Sources VII

DTIC Science & Technology

1997-03-01

clusters irradiated with ultrashort , high intensity laser pulses can exhibit "ionization ig- nition" which leads...8, 9]. 25-atom Ne clusters and 25-atom Ar clusters are modelled as irradiated by a 800 nm, 15 fs (fwhm) laser pulse with peak intensities ranging...Measurements of the spatial and spectral properties of ultrashort , intense laser pulses propagating in underdense plasmas demonstrate

Cluster glass induced exchange biaslike effect in the perovskite cobaltites

NASA Astrophysics Data System (ADS)

Luo, Wanju; Wang, Fangwei

2007-04-01

Exchange biaslike phenomenon is observed in the Ba doped perovskite polycrystalline LaCoO3. The magnetic hysteresis loop shifts in both horizontal and vertical directions at 5K when the samples are cooled down to 5K in a magnetic field. The nature of this magnetic anisotropy is ascribed to the freezing properties of the local anisotropy in the cluster glass system. The magnetic shifts in horizontal and vertical directions can be derived directly under the principle that the spins of a cluster are frozen in random orientations and aligned to the field direction upon zero field and field cooling, respectively.

IONIZED GAS IN THE FIRST 10 kpc OF THE INTERSTELLAR GALACTIC HALO: METAL ION FRACTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howk, J. Christopher; Consiglio, S. Michelle, E-mail: jhowk@nd.edu, E-mail: smconsiglio@ucla.edu

2012-11-10

We present direct measures of the ionization fractions of several sulfur ions in the Galactic warm ionized medium (WIM). We obtained high-resolution ultraviolet absorption-line spectroscopy of post-asymptotic giant branch stars in the globular clusters Messier 3 [(l, b) = (42.{sup 0}2, +78.{sup 0}7), d = 10.2 kpc, and z = 10.0 kpc] and Messier 5 [(l, b) = (3.{sup 0}9, +46.{sup 0}8), d = 7.5 kpc, and z = +5.3 kpc] with the Hubble Space Telescope and Far Ultraviolet Spectroscopic Explorer to measure, or place limits on, the column densities of S I, S II, S III, S IV, Smore » VI, and H I. These clusters also house millisecond pulsars, whose dispersion measures give an electron column density from which we infer the H II column in these directions. We find fractions of S{sup +2} in the WIM for the M 3 and M 5 sight lines x(S{sup +2}) {identical_to} N(S{sup +2})/N(S) = 0.33 {+-} 0.07 and 0.47 {+-} 0.09, respectively, with variations perhaps related to location. With negligible quantities of the higher ionization states, we conclude that S{sup +} and S{sup +2} account for all of the S in the WIM. We extend the methodology to study the ion fractions in the warm and hot ionized gas of the Milky Way, including the high ions Si{sup +3}, C{sup +3}, N{sup +4}, and O{sup +5}. The vast majority of the Galactic ionized gas is warm (T {approx} 10{sup 4} K) and photoionized (the WIM) or very hot (T > 4 Multiplication-Sign 10{sup 5} K) and collisionally ionized. The common tracer of ionized gas beyond the Milky Way, O{sup +5}, traces <1% of the total ionized gas mass of the Milky Way.« less

Improved field emission properties of carbon nanotubes grown on stainless steel substrate and its application in ionization gauge

NASA Astrophysics Data System (ADS)

Li, Detian; Cheng, Yongjun; Wang, Yongjun; Zhang, Huzhong; Dong, Changkun; Li, Da

2016-03-01

Vertically aligned carbon nanotube (CNT) arrays were fabricated by chemical vapor deposition (CVD) technique on different substrates. Microstructures and field emission characteristics of the as-grown CNT arrays were investigated systematically, and its application in ionization gauge was also evaluated preliminarily. The results indicate that the as-grown CNT arrays are vertically well-aligned relating to the substrate surfaces, but the CNTs grown on stainless steel substrate are longer and more crystalline than the ones grown on silicon wafer substrate. The field emission behaviors of the as-grown CNT arrays are strongly dependent upon substrate properties. Namely, the CNT array grown on stainless steel substrate has better field emission properties, including lower turn on and threshold fields, better emission stability and repeatability, compared with the one grown on silicon wafer substrate. The superior field emission properties of the CNT array grown on stainless steel substrate are mainly attributed to low contact resistance, high thermal conductivity, good adhesion strength, etc. In addition, the metrological behaviors of ionization gauge with the CNT array grown on stainless steel substrate as an electron source were investigated, and this novel cathode ionization gauge extends the lower limit of linear pressure measurement to 10-8 Pa, which is one order of magnitude lower than the result reported for the same of gauge with CNT cathode.

The Ordered Clustered Travelling Salesman Problem: A Hybrid Genetic Algorithm

PubMed Central

Ahmed, Zakir Hussain

2014-01-01

The ordered clustered travelling salesman problem is a variation of the usual travelling salesman problem in which a set of vertices (except the starting vertex) of the network is divided into some prespecified clusters. The objective is to find the least cost Hamiltonian tour in which vertices of any cluster are visited contiguously and the clusters are visited in the prespecified order. The problem is NP-hard, and it arises in practical transportation and sequencing problems. This paper develops a hybrid genetic algorithm using sequential constructive crossover, 2-opt search, and a local search for obtaining heuristic solution to the problem. The efficiency of the algorithm has been examined against two existing algorithms for some asymmetric and symmetric TSPLIB instances of various sizes. The computational results show that the proposed algorithm is very effective in terms of solution quality and computational time. Finally, we present solution to some more symmetric TSPLIB instances. PMID:24701148

Identification of multiply charged proteins and amino acid clusters by liquid nitrogen assisted spray ionization mass spectrometry.

PubMed

Kumar Kailasa, Suresh; Hasan, Nazim; Wu, Hui-Fen

2012-08-15

The development of liquid nitrogen assisted spray ionization mass spectrometry (LNASI MS) for the analysis of multiply charged proteins (insulin, ubiquitin, cytochrome c, α-lactalbumin, myoglobin and BSA), peptides (glutathione, HW6, angiotensin-II and valinomycin) and amino acid (arginine) clusters is described. The charged droplets are formed by liquid nitrogen assisted sample spray through a stainless steel nebulizer and transported into mass analyzer for the identification of multiply charged protein ions. The effects of acids and modifier volumes for the efficient ionization of the above analytes in LNASI MS were carefully investigated. Multiply charged proteins and amino acid clusters were effectively identified by LNASI MS. The present approach can effectively detect the multiply charged states of cytochrome c at 400 nM. A comparison between LNASI and ESI, CSI, SSI and V-EASI methods on instrumental conditions, applied temperature and observed charge states for the multiply charged proteins, shows that the LNASI method produces the good quality spectra of amino acid clusters at ambient conditions without applied any electric field and heat. To date, we believe that the LNASI method is the most simple, low cost and provided an alternative paradigm for production of multiply charged ions by LNASI MS, just as ESI-like ions yet no need for applying any electrical field and it could be operated at low temperature for generation of highly charged protein/peptide ions. Copyright © 2012 Elsevier B.V. All rights reserved.

Microhydration and the Enhanced Acidity of Free Radicals.

PubMed

Walton, John C

2018-02-14

Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were obtained for carboxyl, carboxy-ethynyl, carboxy-methyl, and hydroperoxyl radicals. The numbers of water molecules needed to induce spontaneous ionization were determined. The hydration clusters formed primarily round the CO₂ units of the carboxylate-containing radicals. Only 4 or 5 water molecules were needed to induce ionization of carboxyl and carboxy-ethynyl radicals, thus corroborating their large RED-shifts.

Far-infrared observations of the evolved H II region M16

NASA Technical Reports Server (NTRS)

Mcbreen, B.; Fazio, G. G.; Jaffe, D. T.

1982-01-01

The results of far infrared (FIR) observations of the larger H II region M16, associated with the young open star cluster NGC 6611, are discussed. Three FIR sources detected on an extended ridge of FIR emission within the scanned region are described. The observations confirm that M16 is an H II region in a late stage of evolution. The H II region has expanded and is now extremely density bounded, consisting of an extended region of ionized gas and a series of ionization fronts located at the surrounding molecular cloud boundaries nearest to the exciting OB star cluster. The FIR radiation arises from heated dust at these boundaries.

Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle

2011-03-14

The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMsmore » when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.« less

Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, S. H. M.; Kong, Xiang-Yu; Wang, Xue-Bin, E-mail: xuebin.wang@pnnl.gov

2015-01-14

Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M{sub x}(SCN){sub x+1}{sup −}, doubly charged M{sub y}(SCN){sub y+2}{sup 2−} (M = Na, K), and triply charged K{sub z}(SCN){submore » z+3}{sup 3−} anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M{sub x}(SCN){sub x+1}{sup −} (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions M{sub y}(SCN){sub y+2}{sup 2−} (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K{sub z}(SCN){sub z+3}{sup 3−} (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of M{sub x}(SCN){sub x+1}{sup −} with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters were found to become preferred, but at higher temperatures, those multiply charged clusters were suppressed. The series of anion clusters investigated here range from molecular-like M{sub 1}(SCN){sub 2}{sup −} to nano-sized K{sub 22}(SCN){sub 25}{sup 3−}, providing a vivid molecular-level growth pattern reflecting the initial salt nucleation process.« less

The sensitivity of benzene cluster cation chemical ionization mass spectrometry to select biogenic terpenes

NASA Astrophysics Data System (ADS)

Lavi, Avi; Vermeuel, Michael P.; Novak, Gordon A.; Bertram, Timothy H.

2018-06-01

Benzene cluster cations are a sensitive and selective reagent ion for chemical ionization of select biogenic volatile organic compounds. We have previously reported the sensitivity of a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), using benzene cluster cation ion chemistry, for detection of dimethyl sulfide, isoprene and α-pinene. Here, we present laboratory measurements of the sensitivity of the same instrument to a series of terpenes, including isoprene, α-pinene, β-pinene, D-limonene, ocimene, β-myrcene, farnesene, α-humulene, β-caryophyllene, and isolongifolene at atmospherically relevant mixing ratios (< 100 pptv). In addition, we determine the dependence of CI-ToFMS sensitivity on the reagent ion neutral delivery concentration and water vapor concentration. We show that isoprene is primarily detected as an adduct (C5H8 ṡ C6H6+) with a sensitivity ranging between 4 and 10 ncps ppt-1, which depends strongly on the reagent ion precursor concentration, de-clustering voltages, and specific humidity (SH). Monoterpenes are detected primarily as the molecular ion (C10H16+) with an average sensitivity, across the five measured compounds, of 14 ± 3 ncps ppt-1 for SH between 7 and 14 g kg-1, typical of the boreal forest during summer. Sesquiterpenes are detected primarily as the molecular ion (C15H24+) with an average sensitivity, across the four measured compounds, of 9.6 ± 2.3 ncps ppt-1, that is also independent of specific humidity. Comparable sensitivities across broad classes of terpenes (e.g., monoterpenes and sesquiterpenes), coupled to the limited dependence on specific humidity, suggest that benzene cluster cation CI-ToFMS is suitable for field studies of biosphere-atmosphere interactions.

Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y−(HF)n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator

PubMed Central

Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

2017-01-01

Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF)n. The HF molecules were ionized in the form of complex ions associated with the negative core ions Y− produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y−(HF)n (Y=F, O2), where larger clusters with n≥4 were not detected. The mechanisms for the formation of the HF, F−(HF)n, and O2−(HF)n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F−(HF)n (n=1–3), the energies for the loss of HF from F−(HF)3, F−(HF)2, and F−(HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy (ECM). These ECM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O2(HF)n]− (n=1–4) was discussed on the basis of the bond lengths of O2H–F−(HF)n and O2−H–F(HF)n obtained by ab initio calculations. The calculations indicated that [O2(HF)4]− separated into O2H and F−(HF)3. PMID:28966900

Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

PubMed

Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

2017-01-01

Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

PubMed

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil, E-mail: Anil.Shukla@pnnl.gov; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations ofmore » singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Skill transfer, affordances and dexterity in different climbing environments.

PubMed

Seifert, L; Wattebled, L; L'hermette, M; Bideault, G; Herault, R; Davids, K

2013-12-01

This study explored how skills in one region of a perceptual-motor landscape of performance, created in part by previous experience in rock climbing, can shape those that emerge in another region (ice climbing). Ten novices in rock climbing and five intermediate rock climbers were observed climbing an icefall. Locations of right and left ice tools and crampons were videotaped from a frontal camera. Inter-individual variability of upper and lower limb couplings and types of action regarding icefall properties were assessed by cluster hierarchical analysis, distinguishing three clusters. Pelvis vertical displacement, duration and number of pelvis pauses were also analyzed. Experienced rock climbers were grouped in the same cluster and showed the highest range and variability of limb angular locations and coordination patterns, the highest vertical displacement and the shortest pelvis plateaux durations. Non-fluent climbers (clusters 2 and 3) showed low range and variability of limb angular locations and coordination patterns. In particular, climbers of cluster 3 exhibited the lowest vertical displacement, the longest plateaux durations and the greatest ratio between tool swinging and definitive anchorage. Our results exemplified the positive influence of skills in rock climbing on ice climbing performance, facilitated by the detection of affordances from environmental properties. Copyright © 2013 Elsevier B.V. All rights reserved.

Recent Radiation Test Results for Power MOSFETs

NASA Technical Reports Server (NTRS)

Lauenstein, Jean-Marie; Topper, Alyson D.; Casey, Megan C.; Wilcox, Edward P.; Phan, Anthony M.; Kim, Hak S.; LaBel, Kenneth A.

2013-01-01

Single-event effect (SEE) and total ionizing dose (TID) test results are presented for various hardened and commercial power metal-oxide-semiconductor field effect transistors (MOSFETs), including vertical planar, trench, superjunction, and lateral process designs.

Cluster model studies of anion and molecular specificities via electrospray ionization photoelectron spectroscopy

DOE PAGES

Wang, Xue -Bin

2017-01-06

Ion specificity, a widely observed macroscopic phenomenon in condensed phases and at interfaces, is essentially a fundamental chemical physical issue. We have been investigating such effects using cluster models in an “atom-by-atom” and “molecule-by-molecule” fashion not possible with condensed-phase methods. We use electrospray ionization (ESI) to generate molecular and ionic clusters to simulate key molecular entities involved in local binding regions, and characterize them employing negative ion photoelectron spectroscopy (NIPES). Inter- and intramolecular interactions and binding configurations are directly obtained as functions of cluster size and composition, providing insightful molecular-level description and characterization over the local active sites that playmore » crucial roles in determining solution chemistry and condensed phase phenomena. Finally, the topics covered in this article are relevant to a wide scope of research fields ranging from ion specific effects in electrolyte solutions, ion selectivity/recognition in normal functioning of life, to molecular specificity in aerosol particle formation, as well as in rational material design and synthesis.« less

Energy Characteristics of Small Metal Clusters Containing Vacancies

NASA Astrophysics Data System (ADS)

Reva, V. I.; Pogosov, V. V.

2018-02-01

Self-consistent calculations of spatial distributions of electrons, potentials, and energies of dissociation, cohesion, vacancy formation, and electron attachment, as well as the ionization potential of solid Al N , Na N clusters ( N ≥ 254), and clusters containing a vacancy ( N ≥ 12) have been performed using a model of stable jellium. The contribution of a monovacancy to the energy of the cluster, the size dependences of the characteristics, and their asymptotic forms have been considered. The calculations have been performed on the SKIT-3 cluster at the Glushkov Institute of Cybernetics, National Academy of Sciences of Ukraine (Rpeak = 7.4 Tflops).

Nuclear Fusion induced by Coulomb Explosion of Heteronuclear Clusters

NASA Astrophysics Data System (ADS)

Last, Isidore; Jortner, Joshua

2001-07-01

We propose a new mechanism for the production of high-energy ( E>3 keV) deuterons, suitable to induce dd nuclear fusion, based on multielectron ionization and Coulomb explosion of heteronuclear deuterium containing molecular clusters, e.g., (D2O)n, in intense ( 1016-2×1018 W/cm2) laser fields. Cluster size equations for E, in conjunction with molecular dynamics simulations, reveal important advantages of Coulomb explosion of (D2O)n heteronuclear clusters, as compared with (D)n clusters. These involve the considerably increased D+ kinetic energy and a narrow, high-energy distribution of deuterons.

Ionization heating in rare-gas clusters under intense XUV laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arbeiter, Mathias; Fennel, Thomas

The interaction of intense extreme ultraviolet (XUV) laser pulses ({lambda}=32 nm, I=10{sup 11}-10{sup 14} W/cm{sup 2}) with small rare-gas clusters (Ar{sub 147}) is studied by quasiclassical molecular dynamics simulations. Our analysis supports a very general picture of the charging and heating dynamics in finite samples under short-wavelength radiation that is of relevance for several applications of free-electron lasers. First, up to a certain photon flux, ionization proceeds as a series of direct photoemission events producing a jellium-like cluster potential and a characteristic plateau in the photoelectron spectrum as observed in Bostedt et al. [Phys. Rev. Lett. 100, 133401 (2008)]. Second,more » beyond the onset of photoelectron trapping, nanoplasma formation leads to evaporative electron emission with a characteristic thermal tail in the electron spectrum. A detailed analysis of this transition is presented. Third, in contrast to the behavior in the infrared or low vacuum ultraviolet range, the nanoplasma energy capture proceeds via ionization heating, i.e., inner photoionization of localized electrons, whereas collisional heating of conduction electrons is negligible up to high laser intensities. A direct consequence of the latter is a surprising evolution of the mean energy of emitted electrons as function of laser intensity.« less

Equation of motion coupled cluster methods for electron attachment and ionization potential in polyacenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhaskaran-Nair, Kiran; Kowalski, Karol; Jarrell, Mark

2015-11-05

Polyacenes have attracted considerable attention due to their use in organic based optoelectronic materials. Polyacenes are polycyclic aromatic hydrocarbons composed of fused benzene rings. Key to understanding and design of new functional materials is an understanding of their excited state properties starting with their electron affinity (EA) and ionization potential (IP). We have developed a highly accurate and com- putationally e*fficient EA/IP equation of motion coupled cluster singles and doubles (EA/IP-EOMCCSD) method that is capable of treating large systems and large basis set. In this study we employ the EA/IP-EOMCCSD method to calculate the electron affinity and ionization potential ofmore » naphthalene, anthracene, tetracene, pentacene, hex- acene and heptacene. We have compared our results with other previous theoretical studies and experimental data. Our EA/IP results are in very good agreement with experiment and when compared with the other theoretical investigations our results represent the most accurate calculations as compared to experiment.« less

A universal matter-wave interferometer with optical ionization gratings in the time-domain

PubMed Central

Haslinger, Philipp; Dörre, Nadine; Geyer, Philipp; Rodewald, Jonas; Nimmrichter, Stefan; Arndt, Markus

2015-01-01

Matter-wave interferometry with atoms1 and molecules2 has attracted a rapidly growing interest throughout the last two decades both in demonstrations of fundamental quantum phenomena and in quantum-enhanced precision measurements. Such experiments exploit the non-classical superposition of two or more position and momentum states which are coherently split and rejoined to interfere3-11. Here, we present the experimental realization of a universal near-field interferometer built from three short-pulse single-photon ionization gratings12,13. We observe quantum interference of fast molecular clusters, with a composite de Broglie wavelength as small as 275 fm. Optical ionization gratings are largely independent of the specific internal level structure and are therefore universally applicable to different kinds of nanoparticles, ranging from atoms to clusters, molecules and nanospheres. The interferometer is sensitive to fringe shifts as small as a few nanometers and yet robust against velocity-dependent phase shifts, since the gratings exist only for nanoseconds and form an interferometer in the time-domain. PMID:25983851

Temperature structure in the Perseus cluster core observed with Hitomi

NASA Astrophysics Data System (ADS)

Hitomi Collaboration; Aharonian, Felix; Akamatsu, Hiroki; Akimoto, Fumie; Allen, Steven W.; Angelini, Lorella; Audard, Marc; Awaki, Hisamitsu; Axelsson, Magnus; Bamba, Aya; Bautz, Marshall W.; Blandford, Roger; Brenneman, Laura W.; Brown, Gregory V.; Bulbul, Esra; Cackett, Edward M.; Chernyakova, Maria; Chiao, Meng P.; Coppi, Paolo S.; Costantini, Elisa; de Plaa, Jelle; de Vries, Cor P.; den Herder, Jan-Willem; Done, Chris; Dotani, Tadayasu; Ebisawa, Ken; Eckart, Megan E.; Enoto, Teruaki; Ezoe, Yuichiro; Fabian, Andrew C.; Ferrigno, Carlo; Foster, Adam R.; Fujimoto, Ryuichi; Fukazawa, Yasushi; Furukawa, Maki; Furuzawa, Akihiro; Galeazzi, Massimiliano; Gallo, Luigi C.; Gandhi, Poshak; Giustini, Margherita; Goldwurm, Andrea; Gu, Liyi; Guainazzi, Matteo; Haba, Yoshito; Hagino, Kouichi; Hamaguchi, Kenji; Harrus, Ilana M.; Hatsukade, Isamu; Hayashi, Katsuhiro; Hayashi, Takayuki; Hayashida, Kiyoshi; Hiraga, Junko S.; Hornschemeier, Ann; Hoshino, Akio; Hughes, John P.; Ichinohe, Yuto; Iizuka, Ryo; Inoue, Hajime; Inoue, Yoshiyuki; Ishida, Manabu; Ishikawa, Kumi; Ishisaki, Yoshitaka; Iwai, Masachika; Kaastra, Jelle; Kallman, Tim; Kamae, Tsuneyoshi; Kataoka, Jun; Kato, Yuichi; Katsuda, Satoru; Kawai, Nobuyuki; Kelley, Richard L.; Kilbourne, Caroline A.; Kitaguchi, Takao; Kitamoto, Shunji; Kitayama, Tetsu; Kohmura, Takayoshi; Kokubun, Motohide; Koyama, Katsuji; Koyama, Shu; Kretschmar, Peter; Krimm, Hans A.; Kubota, Aya; Kunieda, Hideyo; Laurent, Philippe; Lee, Shiu-Hang; Leutenegger, Maurice A.; Limousin, Olivier; Loewenstein, Michael; Long, Knox S.; Lumb, David; Madejski, Greg; Maeda, Yoshitomo; Maier, Daniel; Makishima, Kazuo; Markevitch, Maxim; Matsumoto, Hironori; Matsushita, Kyoko; McCammon, Dan; McNamara, Brian R.; Mehdipour, Missagh; Miller, Eric D.; Miller, Jon M.; Mineshige, Shin; Mitsuda, Kazuhisa; Mitsuishi, Ikuyuki; Miyazawa, Takuya; Mizuno, Tsunefumi; Mori, Hideyuki; Mori, Koji; Mukai, Koji; Murakami, Hiroshi; Mushotzky, Richard F.; Nakagawa, Takao; Nakajima, Hiroshi; Nakamori, Takeshi; Nakashima, Shinya; Nakazawa, Kazuhiro; Nobukawa, Kumiko K.; Nobukawa, Masayoshi; Noda, Hirofumi; Odaka, Hirokazu; Ohashi, Takaya; Ohno, Masanori; Okajima, Takashi; Ota, Naomi; Ozaki, Masanobu; Paerels, Frits; Paltani, Stéphane; Petre, Robert; Pinto, Ciro; Porter, Frederick S.; Pottschmidt, Katja; Reynolds, Christopher S.; Safi-Harb, Samar; Saito, Shinya; Sakai, Kazuhiro; Sasaki, Toru; Sato, Goro; Sato, Kosuke; Sato, Rie; Sawada, Makoto; Schartel, Norbert; Serlemtsos, Peter J.; Seta, Hiromi; Shidatsu, Megumi; Simionescu, Aurora; Smith, Randall K.; Soong, Yang; Stawarz, Łukasz; Sugawara, Yasuharu; Sugita, Satoshi; Szymkowiak, Andrew; Tajima, Hiroyasu; Takahashi, Hiromitsu; Takahashi, Tadayuki; Takeda, Shiníchiro; Takei, Yoh; Tamagawa, Toru; Tamura, Takayuki; Tanaka, Takaaki; Tanaka, Yasuo; Tanaka, Yasuyuki T.; Tashiro, Makoto S.; Tawara, Yuzuru; Terada, Yukikatsu; Terashima, Yuichi; Tombesi, Francesco; Tomida, Hiroshi; Tsuboi, Yohko; Tsujimoto, Masahiro; Tsunemi, Hiroshi; Tsuru, Takeshi Go; Uchida, Hiroyuki; Uchiyama, Hideki; Uchiyama, Yasunobu; Ueda, Shutaro; Ueda, Yoshihiro; Uno, Shiníchiro; Urry, C. Megan; Ursino, Eugenio; Watanabe, Shin; Werner, Norbert; Wilkins, Dan R.; Williams, Brian J.; Yamada, Shinya; Yamaguchi, Hiroya; Yamaoka, Kazutaka; Yamasaki, Noriko Y.; Yamauchi, Makoto; Yamauchi, Shigeo; Yaqoob, Tahir; Yatsu, Yoichi; Yonetoku, Daisuke; Zhuravleva, Irina; Zoghbi, Abderahmen

2018-03-01

The present paper explains the temperature structure of X-ray emitting plasma in the core of the Perseus cluster based on 1.8-20.0 keV data obtained with the Soft X-ray Spectrometer (SXS) on board the Hitomi Observatory. A series of four observations was carried out, with a total effective exposure time of 338 ks that covered a central region of ˜7΄ in diameter. SXS was operated with an energy resolution of ˜5 eV (full width at half maximum) at 5.9 keV. Not only fine structures of K-shell lines in He-like ions, but also transitions from higher principal quantum numbers were clearly resolved from Si through Fe. That enabled us to perform temperature diagnostics using the line ratios of Si, S, Ar, Ca, and Fe, and to provide the first direct measurement of the excitation temperature and ionization temperature in the Perseus cluster. The observed spectrum is roughly reproduced by a single-temperature thermal plasma model in collisional ionization equilibrium, but detailed line-ratio diagnostics reveal slight deviations from this approximation. In particular, the data exhibit an apparent trend of increasing ionization temperature with the atomic mass, as well as small differences between the ionization and excitation temperatures for Fe, the only element for which both temperatures could be measured. The best-fit two-temperature models suggest a combination of 3 and 5 keV gas, which is consistent with the idea that the observed small deviations from a single-temperature approximation are due to the effects of projecting the known radial temperature gradient in the cluster core along the line of sight. A comparison with the Chandra/ACIS and the XMM-Newton/RGS results, on the other hand, suggests that additional lower-temperature components are present in the intracluster medium (ICM), but not detectable with Hitomi/SXS giving its 1.8-20 keV energy band.

Star-like superalkali cations featuring planar pentacoordinate carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Jin-Chang; Tian, Wen-Juan; Zhao, Xue-Feng

Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe{sub 5} can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F,more » Cl, Br, Li, Na, K) cations containing a CBe{sub 5} moiety. Polyhalogenation and polyalkalination on the CBe{sub 5} unit may help eliminate the high reactivity of bare CBe{sub 5} molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe{sub 5}X{sub 5}{sup +} range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12–2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76–11.07 eV for X = F, Cl, Br and 4.99–6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be–X–Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe{sub 5} motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and highly reactive, the superalkali cation characters of these ppC species should be highlighted, which may be suitable for experimental realization.« less

Ionized-Cluster Beam/Partially Ionized Beam Deposition of Electro- Optical and Nonlinear Optical Organic Materials and Device Development

DTIC Science & Technology

1993-08-29

4’- CH3 O--\\\\4 4N -2 nitrostilbene NO 2J (MMONS) 4’-dimethylamfino OCH3 -N-4-stylbazolium j, o3 - 200 3125 1000 tosylate (DAST)or 0 3 (CH3)2N CH3 Styrylpyridinium PH cyanine dye 400 1490 470 ( SPCD ) SO4 (CH3 ½2N lh3 20

Detection of lower tropospheric responses to solar energetic particles at midlatitudes.

PubMed

Nicoll, K A; Harrison, R G

2014-06-06

Solar energetic particles (SEPs) occasionally contribute additional atmospheric ionization beyond that arising from the usual galactic cosmic ray background. During an SEP event associated with a solar flare on April 11, 2013, the vertical ionization rate profile obtained using a balloon-borne detector showed enhanced ionization with a 26% increase at 20 km, over Reading, United Kingdom. Fluctuations in atmospheric electrical parameters were also detected at the surface, beneath the balloon's trajectory. As no coincident changes in geomagnetism occurred, the electrical fluctuations are very likely to be associated with increased ionization, as observed by the balloon measurements. The lack of response of surface neutron monitors during this event indicates that energetic particles that are not detected at the surface by neutron monitors can nevertheless enter and influence the atmosphere's weather-generating regions.

An Investigation of the Ionization Structure of the Carina Spiral Arm with WHAM

NASA Astrophysics Data System (ADS)

Benjamin, Robert A.; Krishnarao, Dhanesh; Haffner, L. Matthew

2018-01-01

Recent investigations of the Sagittarius-Carina spiral arm with the Wisconsin H-alpha Mapper (Krishnarao et al 2017) show the presence of ionized gas stretching up to three kiloparsecs above and below the Carina section of this spiral arm. This arm segment, which wraps outside the solar circle in the fourth quadrant of the Galactic disk, seems to be unusual when compared to the other Milky Way spiral arms measured with WHAM. We review the status of what is known about the vertical ionization structure of the spiral arms of the Milky Way Galaxy and relate the properties of this spiral arm section to recent investigations of midplane HII regions and star formation in the Milky Way disk. We discuss potential implications of this star formation and ionization for our understanding of Milky Way Galactic structure.

Continental Scale Vegetation Structure Mapping Using Field Calibrated Landsat, ALOS Palsar And GLAS ICESat

NASA Astrophysics Data System (ADS)

Scarth, P.; Phinn, S. R.; Armston, J.; Lucas, R.

2015-12-01

Vertical plant profiles are important descriptors of canopy structure and are used to inform models of biomass, biodiversity and fire risk. In Australia, an approach has been developed to produce large area maps of vertical plant profiles by extrapolating waveform lidar estimates of vertical plant profiles from ICESat/GLAS using large area segmentation of ALOS PALSAR and Landsat satellite image products. The main assumption of this approach is that the vegetation height profiles are consistent across the segments defined from ALOS PALSAR and Landsat image products. More than 1500 field sites were used to develop an index of fractional cover using Landsat data. A time series of the green fraction was used to calculate the persistent green fraction continuously across the landscape. This was fused with ALOS PALSAR L-band Fine Beam Dual polarisation 25m data and used to segment the Australian landscapes. K-means clustering then grouped the segments with similar cover and backscatter into approximately 1000 clusters. Where GLAS-ICESat footprints intersected these clusters, canopy profiles were extracted and aggregated to produce a mean vertical vegetation profile for each cluster that was used to derive mean canopy and understorey height, depth and density. Due to the large number of returns, these retrievals are near continuous across the landscape, enabling them to be used for inventory and modelling applications. To validate this product, a radiative transfer model was adapted to map directional gap probability from airborne waveform lidar datasets to retrieve vertical plant profiles Comparison over several test sites show excellent agreement and work is underway to extend the analysis to improve national biomass mapping. The integration of the three datasets provide options for future operational monitoring of structure and AGB across large areas for quantifying carbon dynamics, structural change and biodiversity.

Measurement of track structure parameters of low and medium energy helium and carbon ions in nanometric volumes

NASA Astrophysics Data System (ADS)

Hilgers, G.; Bug, M. U.; Rabus, H.

2017-10-01

Ionization cluster size distributions produced in the sensitive volume of an ion-counting wall-less nanodosimeter by monoenergetic carbon ions with energies between 45 MeV and 150 MeV were measured at the TANDEM-ALPI ion accelerator facility complex of the LNL-INFN in Legnaro. Those produced by monoenergetic helium ions with energies between 2 MeV and 20 MeV were measured at the accelerator facilities of PTB and with a 241Am alpha particle source. C3H8 was used as the target gas. The ionization cluster size distributions were measured in narrow beam geometry with the primary beam passing the target volume at specified distances from its centre, and in broad beam geometry with a fan-like primary beam. By applying a suitable drift time window, the effective size of the target volume was adjusted to match the size of a DNA segment. The measured data were compared with the results of simulations obtained with the PTB Monte Carlo code PTra. Before the comparison, the simulated cluster size distributions were corrected with respect to the background of additional ionizations produced in the transport system of the ionized target gas molecules. Measured and simulated characteristics of the particle track structure are in good agreement for both types of primary particles and for both types of the irradiation geometry. As the range in tissue of the ions investigated is within the typical extension of a spread-out Bragg peak, these data are useful for benchmarking not only ‘general purpose’ track structure simulation codes, but also treatment planning codes used in hadron therapy. Additionally, these data sets may serve as a data base for codes modelling the induction of radiation damages at the DNA-level as they almost completely characterize the ionization component of the nanometric track structure.

Optical signatures of molecular particles via mass-selected cluster spectroscopy

NASA Technical Reports Server (NTRS)

Duncan, Michael A.

1990-01-01

A new molecular beam apparatus was developed to study optical absorption in cold (less than 100 K) atomic clusters and complexes produced by their condensation with simple molecular gases. In this instrument, ionized clusters produced in a laser vaporization nozzle source are mass selected and studied with photodissociation spectroscopy at visible and ultraviolet wavelengths. This new approach can be applied to synthesize and characterize numerous particulates and weakly bound complexes expected in planetary atmospheres and in comets.

Reprint of: Negative carbon cluster ion beams: New evidence for the special nature of C60

NASA Astrophysics Data System (ADS)

Liu, Y.; O'brien, S. C.; Zhang, Q.; Heath, J. R.; Tittel, F. K.; Curl, R. F.; Kroto, H. W.; Smalley, R. E.

2013-12-01

Cold carbon cluster negative ions are formed by supersonic expansion of a plasma created at the nozzle of a supersonic cluster beam source by an excimer laser pulse. The observed distribution of mass peaks for the Cn- ions for n > 40 demonstrates that the evidence previously given for the special stability of neutral C60 and the existence of spheroidal carbon shells cannot be an artifact of the ionization conditions.

Bright Young Star Clusters in NGC5253 with LEGUS

NASA Astrophysics Data System (ADS)

Calzetti, Daniela; Johnson, Kelsey E.; Adamo, Angela; Gallagher, John S.; Andrews, Jennifer E.; Smith, Linda J.; Clayton, Geoffrey C.; Lee, Janice C.; Sabbi, Elena; Ubeda, Leonardo; Kim, Hwihyun; Ryon, Jenna E.; Thilker, David A.; Bright, Stacey N.; Zackrisson, Erik; Kennicutt, Robert; de Mink, Selma E.; Whitmore, Bradley C.; Aloisi, Alessandra; Chandar, Rupali; Cignoni, Michele; Cook, David; Dale, Daniel A.; Elmegreen, Bruce; Elmegreen, Debra M.; Evans, Aaron S.; Fumagalli, Michele; Gouliermis, Dimitrios; Grasha, Kathryn; Grebel, Eva; Krumholz, Mark R.; Walterbos, Rene A. M.; Wofford, Aida; Brown, Thomas M.; Christian, Carol A.; Dobbs, Claire; Herrero-Davo`, Artemio; Kahre, Lauren; Messa, Matteo; Nair, Preethi; Nota, Antonella; Östlin, Göran; Pellerin, Anne; Sacchi, Elena; Schaerer, Daniel; Tosi, Monica

2016-01-01

Using UV-to-H broad and narrow-band HST imaging, we derive the ages and masses of the 11 brightest star clusters in the dwarf galaxy NGC5253. This galaxy, located at ~3 Mpc, hosts an intense starburst, which includes a centrally-concentrated dusty region with strong thermal radio emission (the `radio nebula'). The HST imaging includes data from the Cycle 21 Treasury Program LEGUS (Legacy ExtraGalactic UV Survey), in addition to narrow--band H-alpha (6563 A), P-beta (12820 A), and P-alpha (18756 A). The bright clusters have ages ~1-15 Myr and masses ~1E4 - 2.5E5 Msun. Two of the 11 star clusters are located within the radio nebula, and suffer from significant dust attenuation. Both are extremely young, with a best-fit age around 1 Myr, and masses ~7.5E4 and ~2.5E5 Msun, respectively. The most massive of the two `radio nebula' clusters is 2-4 times less massive than previously estimated and is embedded within a cloud of dust with A_V~50 mag. The two clusters account for about half of the ionizing photon rate in the radio nebula, and will eventually supply about 2/3 of the mechanical energy in present-day shocks. Additional sources are required to supply the remaining ionizing radiation, and may include very massive stars.

Ionized cluster beam deposition

NASA Technical Reports Server (NTRS)

Kirkpatrick, A. R.

1983-01-01

Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

Deep-down ionization of protoplanetary discs

NASA Astrophysics Data System (ADS)

Glassgold, A. E.; Lizano, S.; Galli, D.

2017-12-01

The possible occurrence of dead zones in protoplanetary discs subject to the magneto-rotational instability highlights the importance of disc ionization. We present a closed-form theory for the deep-down ionization by X-rays at depths below the disc surface dominated by far-ultraviolet radiation. Simple analytic solutions are given for the major ion classes, electrons, atomic ions, molecular ions and negatively charged grains. In addition to the formation of molecular ions by X-ray ionization of H2 and their destruction by dissociative recombination, several key processes that operate in this region are included, e.g. charge exchange of molecular ions and neutral atoms and destruction of ions by grains. Over much of the inner disc, the vertical decrease in ionization with depth into the disc is described by simple power laws, which can easily be included in more detailed modelling of magnetized discs. The new ionization theory is used to illustrate the non-ideal magnetohydrodynamic effects of Ohmic, Hall and Ambipolar diffusion for a magnetic model of a T Tauri star disc using the appropriate Elsasser numbers.

Bootstrap Percolation on Homogeneous Trees Has 2 Phase Transitions

NASA Astrophysics Data System (ADS)

Fontes, L. R. G.; Schonmann, R. H.

2008-09-01

We study the threshold θ bootstrap percolation model on the homogeneous tree with degree b+1, 2≤ θ≤ b, and initial density p. It is known that there exists a nontrivial critical value for p, which we call p f , such that a) for p> p f , the final bootstrapped configuration is fully occupied for almost every initial configuration, and b) if p< p f , then for almost every initial configuration, the final bootstrapped configuration has density of occupied vertices less than 1. In this paper, we establish the existence of a distinct critical value for p, p c , such that 0< p c < p f , with the following properties: 1) if p≤ p c , then for almost every initial configuration there is no infinite cluster of occupied vertices in the final bootstrapped configuration; 2) if p> p c , then for almost every initial configuration there are infinite clusters of occupied vertices in the final bootstrapped configuration. Moreover, we show that 3) for p< p c , the distribution of the occupied cluster size in the final bootstrapped configuration has an exponential tail; 4) at p= p c , the expected occupied cluster size in the final bootstrapped configuration is infinite; 5) the probability of percolation of occupied vertices in the final bootstrapped configuration is continuous on [0, p f ] and analytic on ( p c , p f ), admitting an analytic continuation from the right at p c and, only in the case θ= b, also from the left at p f .

Scattering Response of Sucrose Clusters with Intense XFEL Pulses in Water Window

NASA Astrophysics Data System (ADS)

Ho, Phay; Benedikt Daurer, Benedikt; Bielecki, Johan; Hantke, Max; Maia, Filipe; Knight, Chris; Hajdu, Janos; Young, Linda; Bostedt, Christoph

2017-04-01

We present a combined experimental and theoretical study about the effects of non-linear x-ray ionization dynamics on the scattering response of molecular clusters in the soft x-ray regime that includes and goes beyond the water window. Nanosized sucrose clusters were irradiated with intense XFEL pulses (photon energy from 500 to 1500 eV and pulse duration of 180 fs). Surprisingly, the measured scattering signals near the oxygen K-edge in the water window are found to be substantially smaller than those at higher photon energies. We employ Monte-Carlo/Molecular Dynamics calculations to investigate the x-ray processes as a function of pulse parameters (photon energy, bandwidth and pulse duration) and cluster size. We demonstrate the important role of resonant excitation (RE) in the molecular scattering response in the water window. In particular, 1s ->2p RE cycling enabled in the oxygen atom/ion provide additional ionization pathways which, combined with the long pulse duration, lead to substantial reduction in scattering power of sugar clusters for photon energies just below the oxygen K-edge. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Dept of Energy, Contract DE-AC02-06CH11357.

Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

PubMed Central

Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

2016-01-01

We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

Reduced repair capacity of a DNA clustered damage site comprised of 8-oxo-7,8-dihydro-2'-deoxyguanosine and 2-deoxyribonolactone results in an increased mutagenic potential of these lesions

DOE PAGES

Cunniffe, Siobhan; O’Neill, Peter; Greenberg, Marc M.; ...

2014-04-01

A signature of ionizing radiation is the induction of DNA clustered damaged sites. Non-double strand break (DSB) clustered damage has been shown to compromise the base excision repair pathway, extending the lifetimes of the lesions within the cluster, compared to isolated lesions. This increases the likelihood the lesions persist to replication and thus increasing the mutagenic potential of the lesions within the cluster. Lesions formed by ionizing radiation include 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) and 2-deoxyribonolactone (dL). dL poses an additional challenge to the cell as it is not repaired by the short-patch base excision repair pathway. Here we show recalcitrant dL repairmore » is reflected in mutations observed when DNA containing it and a proximal 8-oxodGuo is replicated in Escherichia coli. 8-oxodGuo in close proximity to dL on the opposing DNA strand results in an enhanced frequency of mutation of the lesions within the cluster and a 20 base sequence flanking the clustered damage site in an E. coli based plasmid assay. In vitro repair of a dL lesion is reduced when compared to the repair of an abasic (AP) site and a tetrahydrofuran (THF), and this is due mainly to a reduction in the activity of polymerase β, leading to retarded FEN1 and ligase 1 activities. This study has given insights in to the biological effects of clusters containing dL.« less

Clustering effects in ionic polymers: Molecular dynamics simulations.

PubMed

Agrawal, Anupriya; Perahia, Dvora; Grest, Gary S

2015-08-01

Ionic clusters control the structure, dynamics, and transport in soft matter. Incorporating a small fraction of ionizable groups in polymers substantially reduces the mobility of the macromolecules in melts. These ionic groups often associate into random clusters in melts, where the distribution and morphology of the clusters impact the transport in these materials. Here, using molecular dynamic simulations we demonstrate a clear correlation between cluster size and morphology with the polymer mobility in melts of sulfonated polystyrene. We show that in low dielectric media ladderlike clusters that are lower in energy compared with spherical assemblies are formed. Reducing the electrostatic interactions by enhancing the dielectric constant leads to morphological transformation from ladderlike clusters to globular assemblies. Decrease in electrostatic interaction significantly enhances the mobility of the polymer.

II Zw 40 - 30 Doradus on Steroids

NASA Astrophysics Data System (ADS)

Leitherer, Claus; Lee, Janice C.; Levesque, Emily M.

2017-11-01

We obtained HST COS G140L spectra of the enigmatic nearby blue compact dwarf galaxy II Zw 40. The galaxy hosts a nuclear super star cluster embedded in a radio-bright nebula, similar to those observed in the related blue compact dwarfs NGC 5253 and Henize 2-10. The ultraviolet spectrum of II Zw 40 is exceptional in terms of the strength of He II 1640, O III] 1666 and C III] 1909. We determined reddening, age, and the cluster mass from the ultraviolet data. The super nebula and the ionizing cluster exceed the ionizing luminosity and stellar mass of the local benchmark 30 Doradus by an order of magnitude. Comparison with stellar evolution models accounting for rotation reveals serious short-comings: these models do not account for the presence of Wolf-Rayet-like stars at young ages observed in II Zw 40. Photoionization modeling is used to probe the origin of the nebular lines and determine gas phase abundances. C/O is solar, in agreement with the result of the stellar-wind modeling.

Cluster formation in laser-induced ablation and evaporation of solids observed by laser ionization time-of-flight mass spectrometry and scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Tench, R. J.; Balooch, M.; Bernardez, L.; Allen, Mike J.; Siekhaus, W. J.; Olander, D. R.; Wang, W.

1990-04-01

Laser ionization time-of-flight mass analysis (LIMA) used pulses (5ns) of a frequency-quadrupled Nd-YAG laser (266 nm) focused onto spots of 4 to 100 microns diameter to ablate material, and a reflectron time of flight tube to mass-analyze the plume. The observed mass spectra for Si, Pt, SiC, and UO 2 varied in the distribution of ablation products among atoms, molecules and clusters, depending on laser power density and target material. Cleaved surfaces of highly oriented pyrolytic graphite (HOPG) positioned at room temperature either 10 cm away from materials ablated at 10(exp -5) Torr by 1 to 3 excimer laser (308 nm) pulses of 20 ns duration or 1 m away from materials vaporized at 10(exp -8) Torr by 10 Nd-Glass laser pulses of 1 ms duration were analyzed by Scanning Tunneling Microscopy (STM) in air with angstrom resolution. Clusters up to 30 A in diameter were observed.

Photometric properties of stars clusters with young or mixed age stellar populations

NASA Astrophysics Data System (ADS)

Mollá, M.; García-Vargas, M. L.; Martín-Manjón, M. L.

2013-05-01

The main goal of this work is to present and discuss the synthetic photometrical properties of stellar clusters resulting from the PopStar code. Colors in Johnson and SDSS systems, Hα and Hβ luminosities and equivalent widths, and ionizing region size, have been computed for a wide range of metallicities Z = 0.0001, 0.0004, 0.004,0.008,0.02 and 0.05, and ages, from 0.1 Myr to 20 Gyr in Mollá, Garc{í}a-Vargas, & Bressan (2009, MNRAS, 398, 451). Emission lines are shown in Mart{í}n-Manj{ó}n et al. (2010, MNRAS, 403, 2012). Now we calculate colors with the emission lines contribution to the broad band color, so colors include stellar and nebular components, plus the emission lines following the evolution of the cluster and the region geometry in a consistent way. We compare the Single Stellar Populations contaminated and uncontaminated colors (in both Johnson and SDSS systems) and show the importance of emission lines contribution when photometry is used as a tool to characterize stellar populations. With these models we may determine the physical properties of young ionizing clusters when only photometrical observations are available and these correspond to the isolated star forming regions, subtracted the contribution of the underlying population In most cases, however, the ionizing population is usually embedded in a large and complex system, and the observed photometrical properties are the result of the combination of both the young star-forming burst and the host-underlying older population. The second objective of our work is therefore to provide a grid of models for nearby galaxies able to interpret mixed regions where the separation of young and old population is not possible or reliable enough. We obtain a set of PopStar Spectral Energy Distributions (available at PopStar site and also in VO) and derived colors for mixed populations where an underlying host population is combined in different mass ratios with a recent, metal-rich ionizing burst. These colors, together with other photometrical parameters, like Hα radius of the ionized region, and Balmer lines equivalent width and luminosity allow to infer the physical properties of star-forming regions without any spectroscopic information. For details and a complete set of tables and figures see Mollá, García-Vargas, & Martín-Manjón (2012, MNRAS, submitted).

Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation.

PubMed

Gartmann, Thomas E; Hartweg, Sebastian; Ban, Loren; Chasovskikh, Egor; Yoder, Bruce L; Signorell, Ruth

2018-06-06

Low-energy electron scattering in water clusters (H2O)n with average cluster sizes of n < 700 is investigated by angle-resolved photoelectron spectroscopy using high harmonic radiation at photon energies of 14.0, 20.3, and 26.5 eV for ionization from the three outermost valence orbitals. The measurements probe the evolution of the photoelectron anisotropy parameter β as a function of cluster size. A remarkably steep decrease of β with increasing cluster size is observed, which for the largest clusters reaches liquid bulk values. Detailed electron scattering calculations reveal that neither gas nor condensed phase scattering can explain the cluster data. Qualitative agreement between experiment and simulations is obtained with scattering calculations that treat cluster scattering as an intermediate case between gas and condensed phase scattering.

Non-ideal magnetohydrodynamic simulations of the two-stage fragmentation model for cluster formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bailey, Nicole D.; Basu, Shantanu, E-mail: N.Bailey@leeds.ac.uk, E-mail: basu@uwo.ca

2014-01-01

We model molecular cloud fragmentation with thin-disk, non-ideal magnetohydrodynamic simulations that include ambipolar diffusion and partial ionization that transitions from primarily ultraviolet-dominated to cosmic-ray-dominated regimes. These simulations are used to determine the conditions required for star clusters to form through a two-stage fragmentation scenario. Recent linear analyses have shown that the fragmentation length scales and timescales can undergo a dramatic drop across the column density boundary that separates the ultraviolet- and cosmic-ray-dominated ionization regimes. As found in earlier studies, the absence of an ionization drop and regular perturbations leads to a single-stage fragmentation on pc scales in transcritical clouds, somore » that the nonlinear evolution yields the same fragment sizes as predicted by linear theory. However, we find that a combination of initial transcritical mass-to-flux ratio, evolution through a column density regime in which the ionization drop takes place, and regular small perturbations to the mass-to-flux ratio is sufficient to cause a second stage of fragmentation during the nonlinear evolution. Cores of size ∼0.1 pc are formed within an initial fragment of ∼pc size. Regular perturbations to the mass-to-flux ratio also accelerate the onset of runaway collapse.« less

Bruker biotyper matrix-assisted laser desorption ionization-time of flight mass spectrometry system for identification of Nocardia, Rhodococcus, Kocuria, Gordonia, Tsukamurella, and Listeria species.

PubMed

Hsueh, Po-Ren; Lee, Tai-Fen; Du, Shin-Hei; Teng, Shih-Hua; Liao, Chun-Hsing; Sheng, Wang-Hui; Teng, Lee-Jene

2014-07-01

We evaluated whether the Bruker Biotyper matrix-associated laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) system provides accurate species-level identifications of 147 isolates of aerobically growing Gram-positive rods (GPRs). The bacterial isolates included Nocardia (n = 74), Listeria (n = 39), Kocuria (n = 15), Rhodococcus (n = 10), Gordonia (n = 7), and Tsukamurella (n = 2) species, which had all been identified by conventional methods, molecular methods, or both. In total, 89.7% of Listeria monocytogenes, 80% of Rhodococcus species, 26.7% of Kocuria species, and 14.9% of Nocardia species (n = 11, all N. nova and N. otitidiscaviarum) were correctly identified to the species level (score values, ≥ 2.0). A clustering analysis of spectra generated by the Bruker Biotyper identified six clusters of Nocardia species, i.e., cluster 1 (N. cyriacigeorgica), cluster 2 (N. brasiliensis), cluster 3 (N. farcinica), cluster 4 (N. puris), cluster 5 (N. asiatica), and cluster 6 (N. beijingensis), based on the six peaks generated by ClinProTools with the genetic algorithm, i.e., m/z 2,774.477 (cluster 1), m/z 5,389.792 (cluster 2), m/z 6,505.720 (cluster 3), m/z 5,428.795 (cluster 4), m/z 6,525.326 (cluster 5), and m/z 16,085.216 (cluster 6). Two clusters of L. monocytogenes spectra were also found according to the five peaks, i.e., m/z 5,594.85, m/z 6,184.39, and m/z 11,187.31, for cluster 1 (serotype 1/2a) and m/z 5,601.21 and m/z 11,199.33 for cluster 2 (serotypes 1/2b and 4b). The Bruker Biotyper system was unable to accurately identify Nocardia (except for N. nova and N. otitidiscaviarum), Tsukamurella, or Gordonia species. Continuous expansion of the MALDI-TOF MS databases to include more GPRs is necessary. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

INTEGRAL-FIELD STELLAR AND IONIZED GAS KINEMATICS OF PECULIAR VIRGO CLUSTER SPIRAL GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cortés, Juan R.; Hardy, Eduardo; Kenney, Jeffrey D. P., E-mail: jcortes@alma.cl, E-mail: ehardy@nrao.cl, E-mail: jeff.kenney@yale.edu

2015-01-01

We present the stellar and ionized gas kinematics of 13 bright peculiar Virgo cluster galaxies observed with the DensePak Integral Field Unit at the WIYN 3.5 m telescope in order to look for kinematic evidence that these galaxies have experienced gravitational interactions or gas stripping. Two-dimensional maps of the stellar velocity V, stellar velocity dispersion σ, and the ionized gas velocity (Hβ and/or [O III]) are presented for the galaxies in the sample. The stellar rotation curves and velocity dispersion profiles are determined for 13 galaxies, and the ionized gas rotation curves are determined for 6 galaxies. Misalignments between themore » optical and kinematical major axes are found in several galaxies. While in some cases this is due to a bar, in other cases it seems to be associated with gravitational interaction or ongoing ram pressure stripping. Non-circular gas motions are found in nine galaxies, with various causes including bars, nuclear outflows, or gravitational disturbances. Several galaxies have signatures of kinematically distinct stellar components, which are likely signatures of accretion or mergers. For all of our galaxies, we compute the angular momentum parameter λ {sub R}. An evaluation of the galaxies in the λ {sub R} ellipticity plane shows that all but two of the galaxies have significant support from random stellar motions, and have likely experienced gravitational interactions. This includes some galaxies with very small bulges and truncated/compact Hα morphologies, indicating that such galaxies cannot be fully explained by simple ram pressure stripping, but must have had significant gravitational encounters. Most of the sample galaxies show evidence for ICM-ISM stripping as well as gravitational interactions, indicating that the evolution of a significant fraction of cluster galaxies is likely strongly impacted by both effects.« less

Characterization of AlN/AlGaN/GaN:C heterostructures grown on Si(111) using atom probe tomography, secondary ion mass spectrometry, and vertical current-voltage measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huber, Martin, E-mail: martin.huberVIH@infineon.com; Daumiller, Ingo; Andreev, Andrei

2016-03-28

Complementary studies of atom probe tomography, secondary ion mass spectrometry, and vertical current-voltage measurements are carried out in order to unravel the influence of C-doping of GaN on the vertical leakage current of AlN/AlGaN/GaN:C heterostructures. A systematic increment of the vertical blocking voltage at a given current density is observed in the structures, when moving from the nominally undoped conditions—corresponding to a residual C-background of ∼10{sup 17 }cm{sup −3}—to a C-content of ∼10{sup 19 }cm{sup −3} in the GaN layer. The value of the vertical blocking voltage saturates for C concentrations higher than ∼10{sup 19 }cm{sup −3}. Atom probe tomography confirms the homogeneitymore » of the GaN:C layers, demonstrating that there is no clustering at C-concentrations as high as 10{sup 20 }cm{sup −3}. It is inferred that the vertical blocking voltage saturation is not likely to be related to C-clustering.« less

Single impacts of keV fullerene ions on free standing graphene: Emission of ions and electrons from confined volume

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verkhoturov, Stanislav V.; Geng, Sheng; Schweikert, Emile A., E-mail: schweikert@chem.tamu.edu

We present the first data from individual C{sub 60} impacting one to four layer graphene at 25 and 50 keV. Negative secondary ions and electrons emitted in transmission were recorded separately from each impact. The yields for C{sub n}{sup −} clusters are above 10% for n ≤ 4, they oscillate with electron affinities and decrease exponentially with n. The result can be explained with the aid of MD simulation as a post-collision process where sufficient vibrational energy is accumulated around the rim of the impact hole for sputtering of carbon clusters. The ionization probability can be estimated by comparing experimentalmore » yields of C{sub n}{sup −} with those of C{sub n}{sup 0} from MD simulation, where it increases exponentially with n. The ionization probability can be approximated with ejecta from a thermally excited (3700 K) rim damped by cluster fragmentation and electron detachment. The experimental electron probability distributions are Poisson-like. On average, three electrons of thermal energies are emitted per impact. The thermal excitation model invoked for C{sub n}{sup −} emission can also explain the emission of electrons. The interaction of C{sub 60} with graphene is fundamentally different from impacts on 3D targets. A key characteristic is the high degree of ionization of the ejecta.« less

Stabilization of sulfuric acid dimers by ammonia, methylamine, dimethylamine, and trimethylamine

NASA Astrophysics Data System (ADS)

Jen, Coty N.; McMurry, Peter H.; Hanson, David R.

2014-06-01

This study experimentally explores how ammonia (NH3), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) affect the chemical formation mechanisms of electrically neutral clusters that contain two sulfuric acid molecules (dimers). Dimers may also contain undetectable compounds, such as water or bases, that evaporate upon ionization and sampling. Measurements were conducted using a glass flow reactor which contained a steady flow of humidified nitrogen with sulfuric acid concentrations of 107 to 109 cm-3. A known molar flow rate of a basic gas was injected into the flow reactor. The University of Minnesota Cluster Chemical Ionization Mass Spectrometer was used to measure the resulting sulfuric acid vapor and cluster concentrations. It was found that, for a given concentration of sulfuric acid vapor, the dimer concentration increases with increasing concentration of the basic gas, eventually reaching a plateau. The base concentrations at which the dimer concentrations saturate suggest NH3 < MA < TMA ≲ DMA in forming stabilized sulfuric acid dimers. Two heuristic models for cluster formation by acid-base reactions are developed to interpret the data. The models provide ranges of evaporation rate constants that are consistent with observations and leads to an analytic expression for nucleation rates that is consistent with atmospheric observations.

Secondary ion formation during electronic and nuclear sputtering of germanium

NASA Astrophysics Data System (ADS)

Breuer, L.; Ernst, P.; Herder, M.; Meinerzhagen, F.; Bender, M.; Severin, D.; Wucher, A.

2018-06-01

Using a time-of-flight mass spectrometer attached to the UNILAC beamline located at the GSI Helmholtz Centre for Heavy Ion Research, we investigate the formation of secondary ions sputtered from a germanium surface under irradiation by swift heavy ions (SHI) such as 5 MeV/u Au by simultaneously recording the mass spectra of the ejected secondary ions and their neutral counterparts. In these experiments, the sputtered neutral material is post-ionized via single photon absorption from a pulsed, intensive VUV laser. After post-ionization, the instrument cannot distinguish between secondary ions and post-ionized neutrals, so that both signals can be directly compared in order to investigate the ionization probability of different sputtered species. In order to facilitate an in-situ comparison with typical nuclear sputtering conditions, the system is also equipped with a conventional rare gas ion source delivering a 5 keV argon ion beam. For a dynamically sputter cleaned surface, it is found that the ionization probability of Ge atoms and Gen clusters ejected under electronic sputtering conditions is by more than an order of magnitude higher than that measured for keV sputtered particles. In addition, the mass spectra obtained under SHI irradiation show prominent signals of GenOm clusters, which are predominantly detected as positive or negative secondary ions. From the m-distribution for a given Ge nuclearity n, one can deduce that the sputtered material must originate from a germanium oxide matrix with approximate GeO stoichiometry, probably due to residual native oxide patches even at the dynamically cleaned surface. The results clearly demonstrate a fundamental difference between the ejection and ionization mechanisms in both cases, which is interpreted in terms of corresponding model calculations.

D region disturbances caused by electromagnetic pulses from lightning

NASA Technical Reports Server (NTRS)

Rodriguez, Juan V.; Inan, Umran S.; Bell, Timothy F.

1992-01-01

Attention is given to a simple formulation of the propagation and absorption in a magnetized collisional plasma of EM pulses from lightning which describes the effect of discharge orientation and radiated electric field on the structure and magnitude of heating and secondary ionization in the D region. Radiation from most lightning discharges can heat substantially, but only the most intense (not less than 20 V/m) are likely to cause ionization enhancements not less than 10 percent of the ambient in a single ionization cycle. This dependence on the radiated electric field is modified by the discharge radiation pattern: a horizontal cloud discharge tends to cause larger heating and ionizaton maxima while a vertical return stroke causes disturbances of a larger horizontal extent.

Semiconductor color-center structure and excitation spectra: Equation-of-motion coupled-cluster description of vacancy and transition-metal defect photoluminescence

NASA Astrophysics Data System (ADS)

Lutz, Jesse J.; Duan, Xiaofeng F.; Burggraf, Larry W.

2018-03-01

Valence excitation spectra are computed for deep-center silicon-vacancy defects in 3C, 4H, and 6H silicon carbide (SiC), and comparisons are made with literature photoluminescence measurements. Optimizations of nuclear geometries surrounding the defect centers are performed within a Gaussian basis-set framework using many-body perturbation theory or density functional theory (DFT) methods, with computational expenses minimized by a QM/MM technique called SIMOMM. Vertical excitation energies are subsequently obtained by applying excitation-energy, electron-attached, and ionized equation-of-motion coupled-cluster (EOMCC) methods, where appropriate, as well as time-dependent (TD) DFT, to small models including only a few atoms adjacent to the defect center. We consider the relative quality of various EOMCC and TD-DFT methods for (i) energy-ordering potential ground states differing incrementally in charge and multiplicity, (ii) accurately reproducing experimentally measured photoluminescence peaks, and (iii) energy-ordering defects of different types occurring within a given polytype. The extensibility of this approach to transition-metal defects is also tested by applying it to silicon-substituted chromium defects in SiC and comparing with measurements. It is demonstrated that, when used in conjunction with SIMOMM-optimized geometries, EOMCC-based methods can provide a reliable prediction of the ground-state charge and multiplicity, while also giving a quantitative description of the photoluminescence spectra, accurate to within 0.1 eV of measurement for all cases considered.

Renormalized coupled cluster approaches in the cluster-in-molecule framework: predicting vertical electron binding energies of the anionic water clusters (H2O)(n)(-).

PubMed

Xu, Peng; Gordon, Mark S

2014-09-04

Anionic water clusters are generally considered to be extremely challenging to model using fragmentation approaches due to the diffuse nature of the excess electron distribution. The local correlation coupled cluster (CC) framework cluster-in-molecule (CIM) approach combined with the completely renormalized CR-CC(2,3) method [abbreviated CIM/CR-CC(2,3)] is shown to be a viable alternative for computing the vertical electron binding energies (VEBE). CIM/CR-CC(2,3) with the threshold parameter ζ set to 0.001, as a trade-off between accuracy and computational cost, demonstrates the reliability of predicting the VEBE, with an average percentage error of ∼15% compared to the full ab initio calculation at the same level of theory. The errors are predominantly from the electron correlation energy. The CIM/CR-CC(2,3) approach provides the ease of a black-box type calculation with few threshold parameters to manipulate. The cluster sizes that can be studied by high-level ab initio methods are significantly increased in comparison with full CC calculations. Therefore, the VEBE computed by the CIM/CR-CC(2,3) method can be used as benchmarks for testing model potential approaches in small-to-intermediate-sized water clusters.

Benchmark study of ionization potentials and electron affinities of armchair single-walled carbon nanotubes using density functional theory

NASA Astrophysics Data System (ADS)

Zhou, Bin; Hu, Zhubin; Jiang, Yanrong; He, Xiao; Sun, Zhenrong; Sun, Haitao

2018-05-01

The intrinsic parameters of carbon nanotubes (CNTs) such as ionization potential (IP) and electron affinity (EA) are closely related to their unique properties and associated applications. In this work, we demonstrated the success of optimal tuning method based on range-separated (RS) density functionals for both accurate and efficient prediction of vertical IPs and electron affinities (EAs) of a series of armchair single-walled carbon nanotubes C20n H20 (n  =  2–6) compared to the high-level IP/EA equation-of-motion coupled-cluster method with single and double substitutions (IP/EA-EOM-CCSD). Notably, the resulting frontier orbital energies (–ε HOMO and –ε LUMO) from the tuning method exhibit an excellent approximation to the corresponding IPs and EAs, that significantly outperform other conventional density functionals. In addition, it is suggested that the RS density functionals that possess both a fixed amount of exact exchange in the short-range and a correct long-range asymptotic behavior are suitable for calculating electronic structures of finite-sized CNTs. Next the performance of density functionals for description of various molecular properties such as chemical potential, hardness and electrophilicity are assessed as a function of tube length. Thanks to the efficiency and accuracy of this tuning method, the related behaviors of much longer armchair single-walled CNTs until C200H20 were studied. Lastly, the present work is proved to provide an efficient theoretical tool for future materials design and reliable characterization of other interesting properties of CNT-based systems.

Electronic and ionization spectra of 1,1-diamino-2,2-dinitroethylene, FOX-7.

PubMed

Borges, Itamar

2014-03-01

Singlet, triplet and ionized states of the energetic molecule 1,1-diamino-2,2-dinitroethylene, known as FOX-7 or DADNE, were investigated using the symmetry-adapted-cluster configuration interaction (SAC-CI) ab initio wave function. The 20 computed singlet transitions, with 2 exceptions, were bright. The most intense singlet transitions were of the n₀→π type-typical of molecules having nitro groups. Fast intersystem crossing (ISC) from the 1¹A, 2¹A and 8¹A bright singlet transitions is possible. Other feasible ISC processes are discussed. The computed singlet and ionization spectra have similar features when compared to nitramide and N,N-dimethylnitramine molecules, which have only a nitro group. The ionization energies of the first 20 states have differences in comparison with Koopmans' energy values that can reach 3 eV. Moreover, the character of the first ionized states, dominated by single ionizations, is not the same when compared with the character resulting from application of Koopmans' theorem.

Giant plasmon excitation in single and double ionization of C60 by fast highly charged Si and O ions

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Tribedi, L. C.

2007-09-01

Se have investigated single and double ionization of C60 molecule in collisions with 2.33 MeV/u Siq+ (q=6-14) and 3.125 MeV/u Oq+ (q=5-8) projectiles. The projectile charge state dependence of the single and double ionization yields of C60 are then compared to those for an ion-atom collision system using Ne gas as a target. A large difference between the gas and the cluster target behaviour was partially explained in terms of a model based on collective excitation namely the giant dipole plasmon resonance (GDPR). The qualitative agreement between the data and GDPR model prediction for single and double ionization signifies the importance of single and double plasmon excitations in the ionization process. A large deviation of the GDPR model for triple and quadruple ionization from the experimental data imply the importance of the other low impact parameter processes such as evaporation, fragmentation and a possible solid-like dynamical screening.

Determination of ionization energies of CnN (n=4-12): Vacuum-ultraviolet (VUV) photoionization experiments and theoretical calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kostko, Oleg; Zhou, Jia; Sun, Bian Jian

2010-06-10

Results from single photon vacuum ultraviolet photoionization of astrophysically relevant CnN clusters, n = 4 - 12, in the photon energy range of 8.0 eV to 12.8 eV are presented. The experimental photoionization efficiency curves, combined with electronic structure calculations, provide improved ionization energies of the CnN species. A search through numerous nitrogen-terminated CnN isomers for n=4-9 indicates that the linear isomer has the lowest energy, and therefore should be the most abundant isomer in the molecular beam. Comparison with calculated results also shed light on the energetics of the linear CnN clusters, particularly in the trends of the even-carbonmore » and the odd-carbon series. These results can help guide the search of potential astronomical observations of these neutral molecules together with their cations in highly ionized regions or regions with a high UV/VUV photon flux (ranging from the visible to VUV with flux maxima in the Lyman- region) in the interstellar medium.« less

Determination of ionization energies of CnN (n=4-12): Vacuum-ultraviolet (VUV) photoionization experiments and theoretical calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kostko, Oleg; Zhou, Jia; Sun, Bian Jian

2010-03-02

Results from single photon vacuum ultraviolet photoionization of astrophysically relevant CnN clusters, n = 4 - 12, in the photon energy range of 8.0 eV to 12.8 eV are presented. The experimental photoionization efficiency curves, combined with electronic structure calculations, provide improved ionization energies of the CnN species. A search through numerous nitrogen-terminated CnN isomers for n=4-9 indicates that the linear isomer has the lowest energy, and therefore should be the most abundant isomer in the molecular beam. Comparison with calculated results also shed light on the energetics of the linear CnN clusters, particularly in the trends of the even-carbonmore » and the odd-carbon series. These results can help guide the search of potential astronomical observations of these neutral molecules together with their cations in highly ionized regions or regions with a high UV/VUV photon flux (ranging from the visible to VUV with flux maxima in the Lyman-a region) in the interstellar medium.« less

Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

PubMed

Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

2015-02-17

CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment.

Ion energy distributions and densities in the plume of Enceladus

NASA Astrophysics Data System (ADS)

Sakai, Shotaro; Cravens, Thomas E.; Omidi, Nojan; Perry, Mark E.; Waite, J. Hunter

2016-10-01

Enceladus has a dynamic plume that is emitting gas, including water vapor, and dust. The gas is ionized by solar EUV radiation, charge exchange, and electron impact and extends throughout the inner magnetosphere of Saturn. The charge exchange collisions alter the plasma composition. Ice grains (dust) escape from the vicinity of Enceladus and form the E ring, including a portion that is negatively charged by the local plasma. The inner magnetosphere within 10 RS (Saturn radii) contains a complex mixture of plasma, neutral gas, and dust that links back to Enceladus. In this paper we investigate the energy distributions, ion species and densities of water group ions in the plume of Enceladus using test particle and Monte Carlo methods that include collisional processes such as charge exchange and ion-neutral chemical reactions. Ion observations from the Cassini Ion and Neutral Mass Spectrometer (INMS) for E07 are presented for the first time. We use the modeling results to interpret observations made by the Cassini Plasma Spectrometer (CAPS) and the INMS. The low energy ions, as observed by CAPS, appear to be affected by a vertical electric field (EZ=-10 μV/m) in the plume. The EZ field may be associated with the charged dust and/or the pressure gradient of plasma. The model results, along with the results of earlier models, show that H3O+ ions created by chemistry are predominant in the plume, which agrees with INMS and CAPS data, but the INMS count rate in the plume for the model is several times greater than the data, which we do not fully understand. This composition and the total ion count found in the plume agree with INMS and CAPS data. On the other hand, the Cassini Langmuir Probe measured a maximum plume ion density more than 30,000 cm-3, which is far larger than the maximum ion density from our model, 900 cm-3. The model results also demonstrate that most of the ions in the plume are from the external magnetospheric flow and are not generated by local ionization. The origin of the ions in the plume was investigated using two different velocity models. Most ions were created by the interaction with background magnetospheric plasma and by photoionization. INMS and CAPS also detected water cluster ions. We will interpret these observations as a result of ion collisions with neutral water clusters, (H2O)n, originating in the tiger stripe vents as suggested by Tokar et al. (2009). We also estimated the process of generating cluster ions based on the INMS observations. We suggest that the most likely source is reaction of H3O+ with neutral water clusters or dimers such as (H2O)2 formed in the plume vents.

Clustering effects in ionic polymers: Molecular dynamics simulations

DOE PAGES

Agrawal, Anupriya; Perahia, Dvora; Grest, Gary S.

2015-08-18

Ionic clusters control the structure, dynamics, and transport in soft matter. Incorporating a small fraction of ionizable groups in polymers substantially reduces the mobility of the macromolecules in melts. Furthermore, these ionic groups often associate into random clusters in melts, where the distribution and morphology of the clusters impact the transport in these materials. Here, using molecular dynamic simulations we demonstrate a clear correlation between cluster size and morphology with the polymer mobility in melts of sulfonated polystyrene. We show that in low dielectric media ladderlike clusters that are lower in energy compared with spherical assemblies are formed. Reducing themore » electrostatic interactions by enhancing the dielectric constant leads to morphological transformation from ladderlike clusters to globular assemblies. Finally, decrease in electrostatic interaction significantly enhances the mobility of the polymer.« less

Non-DSB clustered DNA lesions. Does theory colocalize with the experiment?

NASA Astrophysics Data System (ADS)

Nikitaki, Zacharenia; Nikolov, Vladimir; Mavragani, Ifigeneia V.; Plante, Ianik; Emfietzoglou, Dimitris; Iliakis, George; Georgakilas, Alexandros G.

2016-11-01

Ionizing radiation results in various kinds of DNA lesions such as double strand breaks (DSBs) and other non-DSB base lesions. These lesions may be formed in close proximity (i.e., within a few nanometers) resulting in clustered types of DNA lesions. These damage clusters are considered the fingerprint of ionizing radiation, notably charged particles of high linear energy transfer (LET). Accumulating theoretical and experimental evidence suggests that the induction of these clustered lesions appears under various irradiation conditions but also as a result of high levels of oxidative stress. The biological significance of these clustered DNA lesions pertains to the inability of cells to process them efficiently compared to isolated DNA lesions. The results in the case of unsuccessful or erroneous repair can vary from mutations up to chromosomal instability. In this mini review, we discuss of several Monte Carlo simulations codes and experimental evidence regarding the induction and repair of radiation-induced non-DSB complex DNA lesions. We also critically present the most widely used methodologies (i.e., gel electrophoresis and fluorescence microscopy [in situ colocalization assays]). Based on the comparison of different approaches, we provide examples and suggestions for the improved detection of these lesions in situ. Based on the current status of knowledge, we conclude that there is a great need for improvement of the detection techniques at the cellular or tissue level, which will provide valuable information for understanding the mechanisms used by the cell to process clustered DNA lesions.

Massive Stars and the Ionization of the Diffuse Medium

NASA Astrophysics Data System (ADS)

Kahre, Lauren E.; Walterbos, Rene A. M.

2015-08-01

Diffuse ionized Gas (DIG, sometimes called the warm ionized medium or WIM) has been recognized as a major component of the interstellar medium (ISM) in disk galaxies. A general understanding of the characteristics of the DIG is emerging, but several questions remain unanswered. One of these is the ionization mechanism for this gas, believed to be connected to OB stars and HII regions. Using 5-band (NUV (2750 A), U, V, B, and I) photometric imaging data from the Hubble Space Telescope (HST) Legacy Extragalactic Ultraviolet Survey (LEGUS) and ground-based Halpha data from the Local Volume Legacy (LVL) survey and HST Halpha data from LEGUS, we will investigate the photoionization of HII regions and DIG in nearly 50 galaxies. The 5-band photometry will enable us to determine properties of the most massive stars and reddening corrections for specific regions within a galaxy. Luminosities and ages for groups and clusters will be obtained from SED-fitting of photometric data. For individual stars ages will be determined from isochrone-fitting using reddening-corrected color-magnitude diagrams. We can then obtain estimates of the ionizing luminosities by matching these photometric properties for massive stars and clusters to various stellar atmosphere models. We will compare these predictions to the inferred Lyman continuum production rates from reddening-corrected ground- and HST-based Halpha data for HII regions and DIG. This particular presentation will demonstrate the above process for a set of selected regions in galaxies within the LEGUS sample. It will subsequently be expanded to cover the full LEGUS sample, with the overall goals of obtaining a better understanding of the radiative energy feedback from massive stars on the ISM, particularly their ability to ionize the surrounding ISM over a wide range of spatial scales and SFR surface densities, and to connect the ionization of the ISM to HII region morphologies.

Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

PubMed Central

Li, Zheng; Vendrell, Oriol

2016-01-01

The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects. PMID:26798842

The Technical and Biological Reproducibility of Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS) Based Typing: Employment of Bioinformatics in a Multicenter Study.

PubMed

Oberle, Michael; Wohlwend, Nadia; Jonas, Daniel; Maurer, Florian P; Jost, Geraldine; Tschudin-Sutter, Sarah; Vranckx, Katleen; Egli, Adrian

2016-01-01

The technical, biological, and inter-center reproducibility of matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI TOF MS) typing data has not yet been explored. The aim of this study is to compare typing data from multiple centers employing bioinformatics using bacterial strains from two past outbreaks and non-related strains. Participants received twelve extended spectrum betalactamase-producing E. coli isolates and followed the same standard operating procedure (SOP) including a full-protein extraction protocol. All laboratories provided visually read spectra via flexAnalysis (Bruker, Germany). Raw data from each laboratory allowed calculating the technical and biological reproducibility between centers using BioNumerics (Applied Maths NV, Belgium). Technical and biological reproducibility ranged between 96.8-99.4% and 47.6-94.4%, respectively. The inter-center reproducibility showed a comparable clustering among identical isolates. Principal component analysis indicated a higher tendency to cluster within the same center. Therefore, we used a discriminant analysis, which completely separated the clusters. Next, we defined a reference center and performed a statistical analysis to identify specific peaks to identify the outbreak clusters. Finally, we used a classifier algorithm and a linear support vector machine on the determined peaks as classifier. A validation showed that within the set of the reference center, the identification of the cluster was 100% correct with a large contrast between the score with the correct cluster and the next best scoring cluster. Based on the sufficient technical and biological reproducibility of MALDI-TOF MS based spectra, detection of specific clusters is possible from spectra obtained from different centers. However, we believe that a shared SOP and a bioinformatics approach are required to make the analysis robust and reliable.

THE VERY MASSIVE STAR CONTENT OF THE NUCLEAR STAR CLUSTERS IN NGC 5253

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, L. J.; Crowther, P. A.; Calzetti, D.

2016-05-20

The blue compact dwarf galaxy NGC 5253 hosts a very young starburst containing twin nuclear star clusters, separated by a projected distance of 5 pc. One cluster (#5) coincides with the peak of the H α emission and the other (#11) with a massive ultracompact H ii region. A recent analysis of these clusters shows that they have a photometric age of 1 ± 1 Myr, in apparent contradiction with the age of 3–5 Myr inferred from the presence of Wolf-Rayet features in the cluster #5 spectrum. We examine Hubble Space Telescope ultraviolet and Very Large Telescope optical spectroscopy ofmore » #5 and show that the stellar features arise from very massive stars (VMSs), with masses greater than 100 M {sub ⊙}, at an age of 1–2 Myr. We further show that the very high ionizing flux from the nuclear clusters can only be explained if VMSs are present. We investigate the origin of the observed nitrogen enrichment in the circumcluster ionized gas and find that the excess N can be produced by massive rotating stars within the first 1 Myr. We find similarities between the NGC 5253 cluster spectrum and those of metal-poor, high-redshift galaxies. We discuss the presence of VMSs in young, star-forming galaxies at high redshift; these should be detected in rest-frame UV spectra to be obtained with the James Webb Space Telescope . We emphasize that population synthesis models with upper mass cutoffs greater than 100 M {sub ⊙} are crucial for future studies of young massive star clusters at all redshifts.« less

Role of isolated and clustered DNA damage and the post-irradiating repair process in the effects of heavy ion beam irradiation.

PubMed

Tokuyama, Yuka; Furusawa, Yoshiya; Ide, Hiroshi; Yasui, Akira; Terato, Hiroaki

2015-05-01

Clustered DNA damage is a specific type of DNA damage induced by ionizing radiation. Any type of ionizing radiation traverses the target DNA molecule as a beam, inducing damage along its track. Our previous study showed that clustered DNA damage yields decreased with increased linear energy transfer (LET), leading us to investigate the importance of clustered DNA damage in the biological effects of heavy ion beam radiation. In this study, we analyzed the yield of clustered base damage (comprising multiple base lesions) in cultured cells irradiated with various heavy ion beams, and investigated isolated base damage and the repair process in post-irradiation cultured cells. Chinese hamster ovary (CHO) cells were irradiated by carbon, silicon, argon and iron ion beams with LETs of 13, 55, 90 and 200 keV µm(-1), respectively. Agarose gel electrophoresis of the cells with enzymatic treatments indicated that clustered base damage yields decreased as the LET increased. The aldehyde reactive probe procedure showed that isolated base damage yields in the irradiated cells followed the same pattern. To analyze the cellular base damage process, clustered DNA damage repair was investigated using DNA repair mutant cells. DNA double-strand breaks accumulated in CHO mutant cells lacking Xrcc1 after irradiation, and the cell viability decreased. On the other hand, mouse embryonic fibroblast (Mef) cells lacking both Nth1 and Ogg1 became more resistant than the wild type Mef. Thus, clustered base damage seems to be involved in the expression of heavy ion beam biological effects via the repair process. © The Author 2015. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

ULTRAVIOLET ESCAPE FRACTIONS FROM GIANT MOLECULAR CLOUDS DURING EARLY CLUSTER FORMATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howard, Corey; Pudritz, Ralph; Klessen, Ralf

2017-01-01

The UV photon escape fraction from molecular clouds is a key parameter for understanding the ionization of the interstellar medium and extragalactic processes such as cosmic reionization. We present the ionizing photon flux and the corresponding photon escape fraction ( f {sub esc}) arising as a consequence of star cluster formation in a turbulent, 10{sup 6} M {sub ⊙} giant molecular cloud, simulated using the code FLASH. We make use of sink particles to represent young, star-forming clusters coupled with a radiative transfer scheme to calculate the emergent UV flux. We find that the ionizing photon flux across the cloudmore » boundary is highly variable in time and space due to the turbulent nature of the intervening gas. The escaping photon fraction remains at ∼5% for the first 2.5 Myr, followed by two pronounced peaks at 3.25 and 3.8 Myr with a maximum f {sub esc} of 30% and 37%, respectively. These peaks are due to the formation of large H ii regions that expand into regions of lower density, some of which reaching the cloud surface. However, these phases are short-lived, and f {sub esc} drops sharply as the H ii regions are quenched by the central cluster passing through high-density material due to the turbulent nature of the cloud. We find an average f {sub esc} of 15% with factor of two variations over 1 Myr timescales. Our results suggest that assuming a single value for f {sub esc} from a molecular cloud is in general a poor approximation, and that the dynamical evolution of the system leads to large temporal variation.« less

A Gemini view of the galaxy cluster RXC J1504-0248: insights on the nature of the central gaseous filaments

NASA Astrophysics Data System (ADS)

Soja, A. C.; Sodré, L., Jr.; Monteiro-Oliveira, R.; Cypriano, E. S.; Lima Neto, G. B.

2018-03-01

We revisit the galaxy cluster RXC J1504-0248, a remarkable example of a structure with a strong cool core in a near redshift (z = 0.216). We performed a combined analysis using photometric and spectroscopic data obtained at Gemini South Telescope. We estimated the cluster mass through gravitational lensing, obtaining M200 = 5.3 ± 0.4 × 1014h_{70}^{-1} M⊙ within R200 = 1.56 ± 0.04 h^{-1}_{70} Mpc, in agreement with a virial mass estimate. This cluster presents a prominent filamentary structure associated to its BCG, located mainly along its major axis and aligned with the X-ray emission. A combined study of three emission line diagnostic diagrams has shown that the filament emission falls in the so-called transition region of these diagrams. Consequently, several ionizing sources should be playing an meaningful role. We have argued that old stars, often invoked to explain LINER emission, should not be the major source of ionization. We have noticed that most of the filamentary emission has line ratios consistent with the shock excitation limits obtained from shock models. We also found that line fluxes are related to gas velocities (here estimated from line widths) by power-laws with slopes in the range expected from shock models. These models also show, however, that only ˜10% of Hα luminosity can be explained by shocks. We conclude that shocks probably associated to the cooling of the intracluster gas in a filamentary structure may indeed be contributing to the filament nebular emission, but can not be the major source of ionizing photons.

Computational tests of quantum chemical models for excited and ionized states of molecules with phosphorus and sulfur atoms.

PubMed

Hahn, David K; RaghuVeer, Krishans; Ortiz, J V

2014-05-15

Time-dependent density functional theory (TD-DFT) and electron propagator theory (EPT) are used to calculate the electronic transition energies and ionization energies, respectively, of species containing phosphorus or sulfur. The accuracy of TD-DFT and EPT, in conjunction with various basis sets, is assessed with data from gas-phase spectroscopy. TD-DFT is tested using 11 prominent exchange-correlation functionals on a set of 37 vertical and 19 adiabatic transitions. For vertical transitions, TD-CAM-B3LYP calculations performed with the MG3S basis set are lowest in overall error, having a mean absolute deviation from experiment of 0.22 eV, or 0.23 eV over valence transitions and 0.21 eV over Rydberg transitions. Using a larger basis set, aug-pc3, improves accuracy over the valence transitions via hybrid functionals, but improved accuracy over the Rydberg transitions is only obtained via the BMK functional. For adiabatic transitions, all hybrid functionals paired with the MG3S basis set perform well, and B98 is best, with a mean absolute deviation from experiment of 0.09 eV. The testing of EPT used the Outer Valence Green's Function (OVGF) approximation and the Partial Third Order (P3) approximation on 37 vertical first ionization energies. It is found that OVGF outperforms P3 when basis sets of at least triple-ζ quality in the polarization functions are used. The largest basis set used in this study, aug-pc3, obtained the best mean absolute error from both methods -0.08 eV for OVGF and 0.18 eV for P3. The OVGF/6-31+G(2df,p) level of theory is particularly cost-effective, yielding a mean absolute error of 0.11 eV.

Study on the influences of ionization region material arrangement on Hall thruster channel discharge characteristics

NASA Astrophysics Data System (ADS)

Xiang, HU; Ping, DUAN; Jilei, SONG; Wenqing, LI; Long, CHEN; Xingyu, BIAN

2018-02-01

There exists strong interaction between the plasma and channel wall in the Hall thruster, which greatly affects the discharge performance of the thruster. In this paper, a two-dimensional physical model is established based on the actual size of an Aton P70 Hall thruster discharge channel. The particle-in-cell simulation method is applied to study the influences of segmented low emissive graphite electrode biased with anode voltage on the discharge characteristics of the Hall thruster channel. The influences of segmented electrode placed at the ionization region on electric potential, ion number density, electron temperature, ionization rate, discharge current and specific impulse are discussed. The results show that, when segmented electrode is placed at the ionization region, the axial length of the acceleration region is shortened, the equipotential lines tend to be vertical with wall at the acceleration region, thus radial velocity of ions is reduced along with the wall corrosion. The axial position of the maximal electron temperature moves towards the exit with the expansion of ionization region. Furthermore, the electron-wall collision frequency and ionization rate also increase, the discharge current decreases and the specific impulse of the Hall thruster is slightly enhanced.

High Intensity Femtosecond XUV Pulse Interactions with Atomic Clusters: Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ditmire, Todd

We propose to expand our recent studies on the interactions of intense extreme ultraviolet (XUV) femtosecond pulses with atomic and molecular clusters. The work described follows directly from work performed under BES support for the past grant period. During this period we upgraded the THOR laser at UT Austin by replacing the regenerative amplifier with optical parametric amplification (OPA) using BBO crystals. This increased the contrast of the laser, the total laser energy to ~1.2 J , and decreased the pulse width to below 30 fs. We built a new all reflective XUV harmonic beam line into expanded lab space. This enabled an increase influence by a factor ofmore » 25 and an increase in the intensity by a factor of 50. The goal of the program proposed in this renewal is to extend this class of experiments to available higher XUV intensity and a greater range of wavelengths. In particular we plan to perform experiments to confirm our hypothesis about the origin of the high charge states in these exploding clusters, an effect which we ascribe to plasma continuum lowering (ionization potential depression) in a cluster nano-­plasma. To do this we will perform experiments in which XUV pulses of carefully chosen wavelength irradiate clusters composed of only low-Z atoms and clusters with a mixture of this low-­Z atom with higher Z atoms. The latter clusters will exhibit higher electron densities and will serve to lower the ionization potential further than in the clusters composed only of low Z atoms. This should have a significant effect on the charge states produced in the exploding cluster. We will also explore the transition of explosions in these XUV irradiated clusters from hydrodynamic expansion to Coulomb explosion. The work proposed here will explore clusters of a wider range of constituents, including clusters from solids. Experiments on clusters from solids will be enabled by development we performed during the past grant period in which we constructed and tested a cluster generator based on the Laser Ablation of Microparticles (LAM) method.« less

Higher-order equation-of-motion coupled-cluster methods for ionization processes.

PubMed

Kamiya, Muneaki; Hirata, So

2006-08-21

Compact algebraic equations defining the equation-of-motion coupled-cluster (EOM-CC) methods for ionization potentials (IP-EOM-CC) have been derived and computer implemented by virtue of a symbolic algebra system largely automating these processes. Models with connected cluster excitation operators truncated after double, triple, or quadruple level and with linear ionization operators truncated after two-hole-one-particle (2h1p), three-hole-two-particle (3h2p), or four-hole-three-particle (4h3p) level (abbreviated as IP-EOM-CCSD, CCSDT, and CCSDTQ, respectively) have been realized into parallel algorithms taking advantage of spin, spatial, and permutation symmetries with optimal size dependence of the computational costs. They are based on spin-orbital formalisms and can describe both alpha and beta ionizations from open-shell (doublet, triplet, etc.) reference states into ionized states with various spin magnetic quantum numbers. The application of these methods to Koopmans and satellite ionizations of N2 and CO (with the ambiguity due to finite basis sets eliminated by extrapolation) has shown that IP-EOM-CCSD frequently accounts for orbital relaxation inadequately and displays errors exceeding a couple of eV. However, these errors can be systematically reduced to tenths or even hundredths of an eV by IP-EOM-CCSDT or CCSDTQ. Comparison of spectroscopic parameters of the FH+ and NH+ radicals between IP-EOM-CC and experiments has also underscored the importance of higher-order IP-EOM-CC treatments. For instance, the harmonic frequencies of the A 2Sigma- state of NH+ are predicted to be 1285, 1723, and 1705 cm(-1) by IP-EOM-CCSD, CCSDT, and CCSDTQ, respectively, as compared to the observed value of 1707 cm(-1). The small adiabatic energy separation (observed 0.04 eV) between the X 2Pi and a 4Sigma- states of NH+ also requires IP-EOM-CCSDTQ for a quantitative prediction (0.06 eV) when the a 4Sigma- state has the low-spin magnetic quantum number (s(z) = 1/2). When the state with s(z) = 3/2 is sought, the energy separations converge much more rapidly with the IP-EOM-CCSD value (0.03 eV) already being close to the observed (0.04 eV).

APPI-MS: Effects of mobile phases and VUV lamps on the detection of PAH compounds

PubMed Central

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A.

2009-01-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of non-polar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e., ≤100 μL/min), while at a higher flow, photon absorption and ion-molecule reactions become significant. Under certain circumstances, APPI signal and S/N have been observed to excel at higher flow, which may be due to a non-photoionzation mechanism. To better understand APPI at higher flow rates, we have selected three lamps (Xe, Kr and Ar) and four mobile phases typical for reverse-phase, high-pressure liquid chromatography: acetonitrile, methanol, (1:1) acetonitrile:water and (1:1) methanol:water. As test compounds, three polyaromatic hydrocarbons are studied: benzo[a]pyrene, indeno[1,2,3-c,d]pyrene and benz[a]anthracene. We find that solvent photoabsorption cross-section is not the only parameter in explaining relative signal intensity, but that solvent photo-ion chemistry can also play a significant role. Three conclusions from this investigation are: (i) Methanol photoionization leads to protonated methanol clusters that can result in chemical ionization of analyte molecule; (ii) Use of the Ar lamp often results in greater signal and S/N; (iii) Acetonitrile photoionization is less efficient and resulting clusters are too strongly bound to efficiently chemically ionize the analyte, so that analyte ion formation is dominated by direct photoionization. PMID:17188507

APPI-MS: effects of mobile phases and VUV lamps on the detection of PAH compounds.

PubMed

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A

2007-04-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of nonpolar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e.,

Spitzer Infrared Spectrograph Observations of the Galactic Center: Quantifying the Extreme Ultraviolet/Soft X-ray Fluxes

NASA Astrophysics Data System (ADS)

Simpson, Janet P.

2018-04-01

It has long been shown that the extreme ultraviolet spectrum of the ionizing stars of H II regions can be estimated by comparing the observed line emission to detailed models. In the Galactic Center (GC), however, previous observations have shown that the ionizing spectral energy distribution (SED) of the local photon field is strange, producing both very low excitation ionized gas (indicative of ionization by late O stars) and also widespread diffuse emission from atoms too highly ionized to be found in normal H II regions. This paper describes the analysis of all GC spectra taken by Spitzer's Infrared Spectrograph and downloaded from the Spitzer Heritage Archive. In it, H II region densities and abundances are described, and serendipitously discovered candidate planetary nebulae, compact shocks, and candidate young stellar objects are tabulated. Models were computed with Cloudy, using SEDs from Starburst99 plus additional X-rays, and compared to the observed mid-infrared forbidden and recombination lines. The ages inferred from the model fits do not agree with recent proposed star formation sequences (star formation in the GC occurring along streams of gas with density enhancements caused by close encounters with the black hole, Sgr A*), with Sgr B1, Sgr C, and the Arches Cluster being all about the same age, around 4.5 Myr old, with similar X-ray requirements. The fits for the Quintuplet Cluster appear to give a younger age, but that could be caused by higher-energy photons from shocks from stellar winds or from a supernova.

The sensibility of SPE induced atmospheric photochemical response to the ionization rate variations.

NASA Astrophysics Data System (ADS)

Krivolutsky, Alexei A.; Kukoleva, Anna; Kuminov, Alexander; Maygkova, Irina

During Solar proton event (SPE) energetic particles affect neutral atmospheric chemistry (Jackman et al. 1990, Krivolutsky A.A. et al. 2001 ets. ). The calculations results for [NO] and [O3] changes have qualitative suitability with observations data from satellites (UARS, HALOE for N.P.), although the simulated result differs in value from observed ones for nitrogen compounds. It seems potential probable reasons for this diversity exist. The sensibility of SPE induced atmospheric response to the ionization rates was investigated. The solar proton fluxes data from two satellites were used for ionization rate calculations by the method Vitt and Jackman (1996): geo-stationary GOES-10 (orbit height ≈ 40000 km) and CORONAS (orbit height is ≈ 400 km) for period of SPE 28.10. 2003. Calculated time integral ion creation during SPE using low and high orbit data differs for 1.5. Differences in ionization rate vertical distribution from GOES and CORONAS were found. Using this different ionization data the atmospherical composition response has been simulated with 1D photochemical model. The corresponding differences are discussed.

Magnetically Controlled Upper Ionosphere of Mars

NASA Astrophysics Data System (ADS)

Majeed, T.; Al Aryani, O.; Al Mutawa, S.; Bougher, S. W.; Haider, S. A.

2017-12-01

The electron density (Ne) profiles measured by the Mars Express spacecraft over regions of strong crustal magnetic fields have shown anomalous characteristics of the topside plasma distribution with variable scale heights. One of such Ne profiles is located at 82oS and 180oE whose topside ionosphere is extended up to an altitude of 700 km. The crustal magnetic field at this southern site is nearly vertical and open to the access of solar wind plasma through magnetic reconnection with the interplanetary magnetic field. This can lead to the acceleration of electrons and ions during the daytime ionosphere. The downward accelerated electrons with energies >200 eV can penetrate deep into the Martian upper ionosphere along vertical magnetic field lines and cause heating, excitation and ionization of the background atmosphere. The upward acceleration of ions resulting from energy input by precipitating electrons can lead to enhance ion escape rate and modify scale heights of the topside ionosphere. We have developed a 1-D chemical diffusive model from 100 km to 400 km to interpret the Martian ionospheric structure at 82oS latitude. The primary source of ionization in the model is due to solar EUV radiation. An extra ionization source due to precipitating electrons of 0.25 keV, peaking near an altitude of 145 km is added in the model to reasonably reproduce the measured ionospheric structure below an altitude of 180 km. The behavior of the topside ionosphere can be interpreted by the vertical plasma transport caused by precipitating electrons. The vertical transport of plasma in our model is simulated by vertical ion velocities, whose values can be interpreted as drift velocities along magnetic field lines. We find that the variation of the topside Ne scale heights is sensitive to the magnitudes of upward and downward drifts with an imposed outward flux boundary condition at the top of the model. The model requires an upward flux of more than 107 ions cm-2 s-1 for both O2+ and O+, and drift speeds of 200 m/s to interpret the measured topside ionospheric structure for altitudes >180 km. The magnitudes of outward ion fluxes and drift velocities are compared with those simulated by existing models. The model results will be presented in comparison with the measured electron density profile. This work is supported by MBRSC, Dubai, UAE.

Facile time-of-flight methods for characterizing pulsed superfluid helium droplet beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Yunteng; Zhang, Jie; Li, Yang

2015-08-15

We present two facile time-of-flight (TOF) methods of detecting superfluid helium droplets and droplets with neutral dopants. Without an electron gun and with only a heated filament and pulsed electrodes, the electron impact ionization TOF mass spectrometer can resolve ionized helium clusters such as He{sub 2}{sup +} and He{sub 4}{sup +}, which are signatures of superfluid helium droplets. Without ionizing any helium atoms, multiphoton non-resonant laser ionization of CCl{sub 4} doped in superfluid helium droplets at 266 nm generates complex cluster ions of dopant fragments with helium atoms, including (He){sub n}C{sup +}, (He){sub n}Cl{sup +}, and (He){sub n}CCl{sup +}. Usingmore » both methods, we have characterized our cryogenic pulsed valve—the Even-Lavie valve. We have observed a primary pulse with larger helium droplets traveling at a slower speed and a rebound pulse with smaller droplets at a faster speed. In addition, the pickup efficiency of dopant is higher for the primary pulse when the nozzle temperature is higher than 13 K, and the total time duration of the doped droplet pulse is only on the order of 20 μs. These results stress the importance of fast and easy characterization of the droplet beam for sensitive measurements such as electron diffraction of doped droplets.« less

Photoionization in Ultraviolet Processing of Astrophysical Ice Analogs at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Woon, David E.

2004-01-01

Two recent experimental studies have demonstrated that amino acids or amino acid precursors are generated when astrophysical ice analogs are subjected to ultraviolet (UV) irradiation at cryogenic temperatures. Understanding the complete phenomenology of photoprocessing is critical to elucidating chemical reaction mechanisms that can function within an ice matrix under very cold conditions. Pushing beyond the much better characterized study of photolytic dissociation of chemical bonds through electronic excitation, this work explored the ability of UV radiation present in the interstellar medium to ionize small molecules embedded in ices. Quantum chemical calculations, including bulk solvation effects, were used to study the ionization of hydrogen (H2), water, and methanol (CH3OH) bound in small clusters of water. Ionization potentials were found to be much smaller in the condensed phase than in the gas phase; even a small cluster can account for large changes in the ionization potentials in ice, as well as the known formation of an OH--H3O+ pair in the case of H2O photoionization. To gauge the impact of photoionization on subsequent grain chemistry, the reaction between OH and CO in the presence of H3O+ was studied and compared with the potential energy surface without hydronium present, which is relevant to chemistry following photolysis. The differences indicate that the reaction is somewhat more likely to proceed to products (H + CO2) in the case of photoionization.

Quantum-Size Dependence of the Energy for Vacancy Formation in Charged Small Metal Clusters. Drop Model

NASA Astrophysics Data System (ADS)

Pogosov, V. V.; Reva, V. I.

2018-04-01

Self-consistent computations of the monovacancy formation energy are performed for Na N , Mg N , and Al N (12 < N ≤ 168) spherical clusters in the drop model for stable jelly. Scenarios of the Schottky vacancy formation and "bubble vacancy blowing" are considered. It is shown that the asymptotic behavior of the size dependences of the energy for the vacancy formation by these two mechanisms is different and the difference between the characteristics of a charged and neutral cluster is entirely determined by the difference between the ionization potentials of clusters and the energies of electron attachment to them.

Dynamics of the Coulomb explosion of large hydrogen iodide clusters irradiated by superintense ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Krainov, V. P.; Roshchupkin, A. S.

2001-12-01

Dynamics of the inner and outer above-barrier ionization and of the Coulomb explosion are calculated for large hydrogen iodide clusters irradiated by superintense ultrashort laser pulses. We have found that the Coulomb forces predominate in the expansion of these clusters in comparison with the hydrodynamic forces. The energy distribution of the iodine multiple atomic ions in laser focal volume is derived. Results of our calculations are in a good agreement with the recent experimental data of Tisch et al. [Phys. Rev. A 60, 3076 (1999)].

X-ray radiative transfer in protoplanetary disks. The role of dust and X-ray background fields

NASA Astrophysics Data System (ADS)

Rab, Ch.; Güdel, M.; Woitke, P.; Kamp, I.; Thi, W.-F.; Min, M.; Aresu, G.; Meijerink, R.

2018-01-01

Context. The X-ray luminosities of T Tauri stars are about two to four orders of magnitude higher than the luminosity of the contemporary Sun. As these stars are born in clusters, their disks are not only irradiated by their parent star but also by an X-ray background field produced by the cluster members. Aims: We aim to quantify the impact of X-ray background fields produced by young embedded clusters on the chemical structure of disks. Further, we want to investigate the importance of the dust for X-ray radiative transfer in disks. Methods: We present a new X-ray radiative transfer module for the radiation thermo-chemical disk code PRODIMO (PROtoplanetary DIsk MOdel), which includes X-ray scattering and absorption by both the gas and dust component. The X-ray dust opacities can be calculated for various dust compositions and dust-size distributions. For the X-ray radiative transfer we consider irradiation by the star and by X-ray background fields. To study the impact of X-rays on the chemical structure of disks we use the well established disk ionization tracers N2H+ and HCO+. Results: For evolved dust populations (e.g. grain growth), X-ray opacities are mostly dominated by the gas; only for photon energies E ≳ 5-10 keV do dust opacities become relevant. Consequently the local disk X-ray radiation field is only affected in dense regions close to the disk midplane. X-ray background fields can dominate the local X-ray disk ionization rate for disk radii r ≳ 20 au. However, the N2H+ and HCO+ column densities are only significantly affected in cases of low cosmic-ray ionization rates (≲10-19 s-1), or if the background flux is at least a factor of ten higher than the flux level of ≈10-5 erg cm-2 s-1 expected for clusters typical for the solar vicinity. Conclusions: Observable signatures of X-ray background fields in low-mass star-formation regions, like Taurus, are only expected for cluster members experiencing a strong X-ray background field (e.g. due to their location within the cluster). For the majority of the cluster members, the X-ray background field has relatively little impact on the disk chemical structure.

FT-ICR mass spectrometric and density functional theory studies of sulfate prenucleation clusters

NASA Astrophysics Data System (ADS)

Lemke, K. H.

2012-12-01

Recent mass spectrometric1 and relaxation spectroscopic studies2 of metal sulfate salts have demonstrated that aqueous clusters play an important role in sulfate prenucleation processes. While such studies provide evidence that that ion clusters are nucleation relevant species, ultra-high resolution mass spectrumetry, in particular, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) can provide additional valuable information about the molecular composition and stability of individual ion clusters. Prompted by the above studies, our group has begun a systematic survey of metal sulfate clusters using FT-ICR mass spectrometry. Here, I report stoichiometries, structures and thermodynamic properties of calcium sulfate ion clusters, both "dry" and microsolvated, using electrospray ionization FT-ICR mass spectrometry in combination with semi-empirical methods and M062X/aug-cc-PVXZ level density functional theory calculations. In electrosprayed dilute aqueous solutions of CaSO4 (1-20mM), droplet desolvation results in the formation of stable doubly-charged clusters of [Ca(CaSO4)m(H2O)n]+2 (m≤10 & n≤9) as well as larger quadruply-charged ion clusters [Ca2(CaSO4)m(H2O)n]+4 with m≤23 and n≤10, demonstrating considerable sulfate nucleation potential in undersaturated electrolyte solutions. An attempt was also made to assess the extent of ion cluster aggregation in solution prior to electrospray ionization by measuring ion mass spectra at different solution concentrations. In brief, an increase in calcium sulfate concentration from 1-10mM results in a continuous increase in polynuclear ion cluster species, while smaller clusters, for instance, Ca[CaSO4]+2 and corresponding hydrated forms, become increasingly less abundant. Building on semi-empirical methods, M062X calculations have been applied to predict calcium sulfate cluster geometries, both "dry" and microsolvated, as well as the size-dependent evolution of clustering and hydration energies. 1Schoeder et al. (2011) J.Am.Chem.Soc., 133, 2444; 2Chen et al. (2005) J.Sol.Chem., 34, 1045;

Correlation of Hydrogen-Atom Abstraction Reaction Efficiencies for Aryl Radicals with their Vertical Electron Affinities and the Vertical Ionization Energies of the Hydrogen Atom Donors

PubMed Central

Jing, Linhong; Nash, John J.

2009-01-01

The factors that control the reactivities of aryl radicals toward hydrogen-atom donors were studied by using a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer (FT – ICR). Hydrogen-atom abstraction reaction efficiencies for two substrates, cyclohexane and isopropanol, were measured for twenty-three structurally different, positively-charged aryl radicals, which included dehydrobenzenes, dehydronaphthalenes, dehydropyridines, and dehydro(iso)quinolines. A logarithmic correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) vertical electron affinities (EA) of the aryl radicals. Transition state energies calculated for three of the aryl radicals with isopropanol were found to correlate linearly with their (calculated) EAs. No correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) enthalpy changes for the reactions. Measurement of the reaction efficiencies for the reactions of several different hydrogen-atom donors with a few selected aryl radicals revealed a logarithmic correlation between the hydrogen-atom abstraction reaction efficiencies and the vertical ionization energies (IE) of the hydrogen-atom donors, but not the lowest homolytic X – H (X = heavy atom) bond dissociation energies of the hydrogen-atom donors. Examination of the hydrogen-atom abstraction reactions of twenty-nine different aryl radicals and eighteen different hydrogen-atom donors showed that the reaction efficiency increases (logarithmically) as the difference between the IE of the hydrogen-atom donor and the EA of the aryl radical decreases. This dependence is likely to result from the increasing polarization, and concomitant stabilization, of the transition state as the energy difference between the neutral and ionic reactants decreases. Thus, the hydrogen-atom abstraction reaction efficiency for an aryl radical can be “tuned” by structural changes that influence either the vertical EA of the aryl radical or the vertical IE of the hydrogen atom donor. PMID:19061320

Luminous phenomena and electromagnetic VHF wave emission originated from earthquake-related radon exhalation

NASA Astrophysics Data System (ADS)

Seki, A.; Tobo, I.; Omori, Y.; Muto, J.; Nagahama, H.

2013-12-01

Anomalous luminous phenomena and electromagnetic wave emission before or during earthquakes have been reported (e.g., the 1965 Matsushiro earthquake swarm). However, their mechanism is still unsolved, in spite of many models for these phenomena. Here, we propose a new model about luminous phenomena and electromagnetic wave emission during earthquake by focusing on atmospheric radon (Rn-222) and its daughter nuclides (Po-218 and Po-214). Rn-222, Po-218 and Po-214 are alpha emitters, and these alpha particles ionize atmospheric molecules. A light emission phenomenon, called 'the air luminescence', is caused by de-excitation of the ionized molecules of atmospheric nitrogen due to electron impact ionization from alpha particles. The de-excitation is from the second positive system of neutral nitrogen molecules and the first negative system of nitrogen molecule ion. Wavelengths of lights by these transitions include the visible light wavelength. So based on this mechanism, we proposed a new luminous phenomenon model before or during earthquake: 1. The concentration of atmospheric radon and its daughter nuclides increase anomalously before or during earthquakes, 2. Nitrogen molecules and their ions are excited by alpha particles emitted from Rn-222, Po-218 and Po-214, and air luminescence is generated by their de-excitation. Similarly, electromagnetic VHF wave emission can be explained by ionizing effect of radon and its daughter nuclides. Boyarchuk et al. (2005) proposed a model that electromagnetic VHF wave emission is originated when excited state of neutral clusters changes. Radon gas ionizes atmosphere and forms positively and negatively charged heavy particles. The process of ion hydration in ordinary air can be determined by the formation of complex chemically active structures of the various types of ion radicals. As a result of the association of such hydration radical ions, a neutral cluster, which is dipole quasi-molecules, is formed. A neutral cluster's rotation-rotation transition causes electromagnetic VHF wave emission. We also discuss a possibility of electromagnetic VHF wave emission from excitation of polyatomic molecules by alpha particles from Rn-222 and its daughter nuclides, similar to air luminescence by excitation of nitrogen molecule in the viewpoint of electromagnetic radiation in quantum theory.

Properties of QSO Metal-line Absorption Systems at High Redshifts: Nature and Evolution of the Absorbers and New Evidence on Escape of Ionizing Radiation from Galaxies

NASA Astrophysics Data System (ADS)

Boksenberg, Alec; Sargent, Wallace L. W.

2015-05-01

Using Voigt-profile-fitting procedures on Keck High Resolution Spectrograph spectra of nine QSOs, we identify 1099 C IV absorber components clumped in 201 systems outside the Lyman forest over 1.6 <~ z <~ 4.4. With associated Si IV, C II, Si II and N V where available, we investigate the bulk statistical and ionization properties of the components and systems and find no significant change in redshift for C IV and Si IV while C II, Si II and N V change substantially. The C IV components exhibit strong clustering, but no clustering is detected for systems on scales from 150 km s-1 out to 50,000 km s-1. We conclude that the clustering is due entirely to the peculiar velocities of gas present in the circumgalactic media of galaxies. Using specific combinations of ionic ratios, we compare our observations with model ionization predictions for absorbers exposed to the metagalactic ionizing radiation background augmented by proximity radiation from their associated galaxies and find that the generally accepted means of radiative escape by transparent channels from the internal star-forming sites is spectrally not viable for our stronger absorbers. We develop an active scenario based on runaway stars with resulting changes in the efflux of radiation that naturally enable the needed spectral convergence, and in turn provide empirical indicators of morphological evolution in the associated galaxies. Together with a coexisting population of relatively compact galaxies indicated by the weaker absorbers in our sample, the collective escape of radiation is sufficient to maintain the intergalactic medium ionized over the full range 1.9 < z <~ 4.4. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

HST-WFPC2 Observations of the Star Clusters in the Giant H II Regions of M33

NASA Astrophysics Data System (ADS)

Lee, Myung Gyoon; Park, Hong Soo; Kim, Sang Chul; Waller, William H.; Parker, Joel Wm.; Malumuth, Eliot M.; Hodge, Paul W.

We present a photometric study of the stars in ionizing star clusters embedded in several giant H II regions of M33 (CC93, IC 142, NGC 595, MA2, NGC 604 and NGC 588). Our photometry is based on the HST-WFPC2 images of these clusters. Color-magnitude diagrams and color-color diagrams of these clusters are obtained and are used for estimating the reddenings and ages of the clusters. The luminosity functions (LFs) and initial mass functions (IMFs) of the massive stars in these clusters are also derived. The slopes of the IMFs range from Γ = -0.5 to -2.1. Interestingly, it is found that the IMFs get steeper with increasing galactocentric distance and with decreasing [O/H] abundance.

Structure, electronic and magnetic properties of Mn{sub n} (n=2-8) clusters: A DFT investigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Vipin; Roy, Debesh R., E-mail: drr@ashd.svnit.ac.in

2016-05-06

A detail studyon the stability, electronic and magnetic properties of Mn{sub n} (n=2-8) cluster series is performed under the utilization ofdensity functional theory (DFT). The binding energy (B.E.), HOMO-LUMO energy gap (HLG), chemical hardness (η), ionization potential (I.P.), electron affinity (E.A)and electronegativity (χ) of these clusters are predicted. We have also studied the magnetic moments associated with the stable cluster isomers. The lowest energy structures for each cluster sizes aredetermined with a systematic search imposing all possible initial magnetic configuration on the cluster. All the calculations are carried out using a popular GGA functional PBE as proposed by Pardew, Burkemore » and Ernzerhof and implemented in the VASP program.« less

Quantum dynamics of charge state in silicon field evaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silaeva, Elena P.; Uchida, Kazuki; Watanabe, Kazuyuki, E-mail: kazuyuki@rs.kagu.tus.ac.jp

2016-08-15

The charge state of an ion field-evaporating from a silicon-atom cluster is analyzed using time-dependent density functional theory coupled to molecular dynamics. The final charge state of the ion is shown to increase gradually with increasing external electrostatic field in agreement with the average charge state of silicon ions detected experimentally. When field evaporation is triggered by laser-induced electronic excitations the charge state also increases with increasing intensity of the laser pulse. At the evaporation threshold, the charge state of the evaporating ion does not depend on the electrostatic field due to the strong contribution of laser excitations to themore » ionization process both at low and high laser energies. A neutral silicon atom escaping the cluster due to its high initial kinetic energy is shown to be eventually ionized by external electrostatic field.« less

The Pleiades Using Astronomical Spectroscopic Technique within the Range of H-{alpha} Region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zambri Zainuddin, Mohd; Muhyidin, Meer Ashwinkumar; Ahmad, Nazhatulshima

2011-03-30

The Pleiades is an open star cluster located in the constellation of Taurus, which mainly consists of hot and luminous B-type stars. Observations were conducted over five-day period in December 2009 at Langkawi National Observatory, Malaysia by using 20-inch telescope diameter of Ritchey-Chretien reflector telescope, together with SBIG Self Guided Spectrograph and SBIG ST-7 CCD camera. The spectra of seven main members of the cluster, namely Alcyone; Atlas; Celaeno; Electra; Maia; Merope and Taygeta; and of Alcyone B; a smaller component of Alcyone quadruple system, were obtained in the optical range of approximately 6300 A to 7100 A. This rangemore » was picked due to the vicinity of Balmer H-{alpha} spectral line at 6562.852 A. Alcyone, Electra and Merope were found to have H-{alpha} emissions possibly caused by the presence of equatorial circumstellar disks or envelopes made up of ejected matter. Electra and Merope in particular exhibited peculiar asymmetric double emission peaks, which could be evidence of one-armed density wave in each of their circumstellar disks. Atlas, Celaeno, Merope, Taygeta and Alcyone B showed strong H-{alpha} absorptions with broadening characteristic of high rotational velocities. As deduced from the spectra, the stars were found to have atmospheres with similar chemical content, with spectral lines characteristics of singly ionized silicon, singly ionized iron and singly ionized oxygen. The measured radial velocities of all eight stars also suggest that the cluster could someday disperse.« less

Characterization of the reactive and dissociative behavior of transition metal oxide cluster ions in the gas phase.

PubMed

Maleknia, S; Brodbelt, J; Pope, K

1991-05-01

The reactive and dissociative behavior of molybdenum and tungsten oxide cluster ions has been studied in the gas phase using a triple quadrupole mass spectrometer. Cluster ions (MO3) n (-) were formed via a simple thermal desorption/electron capture negative ionization method, and their structures were characterized by collision-activated dissociation (CAD). Typically, the clusters fragment by losses of neutral (MO3) units. Reactions of the oxide cluster ions with ethylene oxide, cyclohexene oxide, ethylene sulfide cyclohexene sulfide, 2,3-butanedione, and 2,4-pentanedione were examined, and product ions were characterized by CAD. The clusters react with ethylene oxide by addition of ethylene oxide or net addition of oxygen, whereas the clusters react with ethylene sulfide via net addition of one or two sulfur atoms. Reactions of the clusters with the diones result in addition of one or two dione units, in some cases with dehydration.

Reaction Dynamics Following Ionization of Ammonia Dimer Adsorbed on Ice Surface.

PubMed

Tachikawa, Hiroto

2016-09-22

The ice surface provides an effective two-dimensional reaction field in interstellar space. However, how the ice surface affects the reaction mechanism is still unknown. In the present study, the reaction of an ammonia dimer cation adsorbed both on water ice and cluster surface was theoretically investigated using direct ab initio molecular dynamics (AIMD) combined with our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) method, and the results were compared with reactions in the gas phase and on water clusters. A rapid proton transfer (PT) from NH3(+) to NH3 takes place after the ionization and the formation of intermediate complex NH2(NH4(+)) is found. The reaction rate of PT was significantly affected by the media connecting to the ammonia dimer. The time of PT was calculated to be 50 fs (in the gas phase), 38 fs (on ice), and 28-33 fs (on water clusters). The dissociation of NH2(NH4(+)) occurred on an ice surface. The reason behind the reaction acceleration on an ice surface is discussed.

The Emergence of Star Clusters

NASA Astrophysics Data System (ADS)

Calzetti, Daniela

2017-08-01

We propose to measure the timescale for the clearing of natal dust by young star clusters. We will augment existing archival UV-to-I imaging data with new WFC3/IR images at J, H, and Paschen-beta for a sample of six nearby star forming galaxies. Under the standard scenario that the clearing is performed by supernovae (> 3 Myr), simulations show that not enough ionizing photons can escape galaxies and reionize the Universe at z>6. However, the actual clearing timescale is poorly established. We will obtain accurate ages and extinctions for the embedded and emergent young clusters in our target galaxies, in order to: (1) determine whether dust clearing occurs before or after 3 Myr, (2) investigate environmental dependencies for the timescale, and (3) establish the principal mechanisms for enabling the escape of ionizing photons from galaxies. Our project provides the physical footing for future JWST observations aimed at determining the sources of reionization of the Universe. The combination of archival and new images will also equip the community with a lasting legacy of homogeneous UV-to-IR coverage for a sample of nearby galaxies.

Exploration of dynamical regimes of irradiated small protonated water clusters

NASA Astrophysics Data System (ADS)

Ndongmouo Taffoti, U. F.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.; Wang, Z. P.

2010-05-01

We explore from a theoretical perspective the dynamical response of small water clusters, (H2O)nH3O+ with n=1,2,3, to a short laser pulse for various frequencies, from infrared (IR) to ultra-violet (UV) and intensities (from 6×10^{13} W/cm^2 to 5×10^{14} W/cm^2). To that end, we use time-dependent local-density approximation for the electrons, coupled to molecular dynamics for the atomic cores (TDLDA-MD). The local-density approximation is augmented by a self-interaction correction (SIC) to allow for a correct description of electron emission. For IR frequencies, we see a direct coupling of the laser field to the very light H+ ions in the clusters. Resonant coupling (in the UV) and/or higher intensities lead to fast ionization with subsequent Coulomb explosion. The stability against Coulomb pressure increases with system size. Excitation to lower ionization stages induced strong ionic vibrations. The latter maintain a rather harmonic pattern in spite of the sizeable amplitudes (often 10% of the bond length).

Measurement of high-dynamic range x-ray Thomson scattering spectra for the characterization of nano-plasmas at LCLS

DOE PAGES

MacDonald, M. J.; Gorkhover, T.; Bachmann, B.; ...

2016-08-08

Atomic clusters can serve as ideal model systems for exploring ultrafast (~100 fs) laser-driven ionization dynamics of dense matter on the nanometer scale. Resonant absorption of optical laser pulses enables heating to temperatures on the order of 1 keV at near solid density conditions. To date, direct probing of transient states of such nano plasmas was limited to coherent x-ray imaging. Here we present the first measurement of spectrally-resolved incoherent x-ray scattering from clusters, enabling measurements of transient temperature, densities and ionization. Single shot x-ray Thomson scatterings signals were recorded at 120 Hz using a crystal spectrometer in combination withmore » a single-photon counting and energy-dispersive pnCCD. A precise pump laser collimation scheme enabled recording near background-free scattering spectra from Ar clusters with an unprecedented dynamic range of more than 3 orders of magnitude. As a result, such measurements are important for understanding collective effects in laser-matter interactions on femtosecond timescales, opening new routes for the development of schemes for their ultrafast control.« less

Measurement of high-dynamic range x-ray Thomson scattering spectra for the characterization of nano-plasmas at LCLS

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacDonald, M. J., E-mail: macdonm@umich.edu; SLAC National Accelerator Laboratory, Menlo Park, California 94025; Gorkhover, T.

2016-11-15

Atomic clusters can serve as ideal model systems for exploring ultrafast (∼100 fs) laser-driven ionization dynamics of dense matter on the nanometer scale. Resonant absorption of optical laser pulses enables heating to temperatures on the order of 1 keV at near solid density conditions. To date, direct probing of transient states of such nano-plasmas was limited to coherent x-ray imaging. Here we present the first measurement of spectrally resolved incoherent x-ray scattering from clusters, enabling measurements of transient temperature, densities, and ionization. Single shot x-ray Thomson scattering signals were recorded at 120 Hz using a crystal spectrometer in combination withmore » a single-photon counting and energy-dispersive pnCCD. A precise pump laser collimation scheme enabled recording near background-free scattering spectra from Ar clusters with an unprecedented dynamic range of more than 3 orders of magnitude. Such measurements are important for understanding collective effects in laser-matter interactions on femtosecond time scales, opening new routes for the development of schemes for their ultrafast control.« less

Evaluation of a buried vertical well leachate recirculation system for municipal solid waste landfills.

PubMed

Kadambala, Ravi; Powell, Jon; Singh, Karamjit; Townsend, Timothy G

2016-12-01

Vertical liquids addition systems have been used at municipal landfills as a leachate management method and to enhance biostabilization of waste. Drawbacks of these systems include a limitation on pressurized injection and the occurrence of seepage. A novel vertical well system that employed buried wells constructed below a lift of compacted waste was operated for 153 days at a landfill in Florida, USA. The system included 54 wells installed in six clusters of nine wells connected with a horizontally-oriented manifold system. A cumulative volume of 8430 m 3 of leachate was added intermittently into the well clusters over the duration of the project with no incidence of surface seeps. Achievable average flow rates ranged from 9.3 × 10 -4 m 3 s -1 to 14.2 × 10 -4 m 3 s -1 , which was similar to or greater than flow rates achieved in a previous study using traditional vertical wells at the same landfill site. The results demonstrated that pressurized liquids addition in vertical wells at municipal solid waste landfills can be achieved while avoiding typical operational and maintenance issues associated with seeps. © The Author(s) 2016.

Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zheng; Vendrell, Oriol

2016-01-13

The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. As a result, for situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20more » to 40 fs driven by strong non-adiabatic effects.« less

Design and calibration of a rocket-borne electron spectrometer for investigation of particle ionization in the nighttime midlatitude E region

NASA Technical Reports Server (NTRS)

Voss, H. D.; Smith, L. G.

1974-01-01

An explanation was developed for the formation, near midnight at midlatitudes, of a broad electron density layer extending approximately from 120 to 180 km and usually referred to as the intermediate E layer. The responsible mechanism is believed to be the converging vertical ion drifts resulting from winds of the solar semidiurnal tide. Numerical solutions of the continuity equation appropriate to the intermediate layer is described for particular models of ion drift, diffusion coefficents, and ionization production. Analysis of rocket observations of the layer show that the ionization rate is highly correlated with the planetary geomagnetic index, K sub p. Particle flux measurements support the idea that energetic electrons are the principal source of this ionization. A semiconductor spectrometer experiment for investigation of the particle flux, spectrum, and angular properties was designed and successfully flown on a Nike Apache rocket. A detailed description of the theory, design, and calibration of the experiment and some preliminary results presented.

Studies of the Twin Helix Parametric-resonance Ionization Cooling Channel with COSY INFINITY

DOE Office of Scientific and Technical Information (OSTI.GOV)

J.A. Maloney, K.B. Beard, R.P. Johnson, A. Afanasev, S.A. Bogacz, Y.S. Derbenev, V.S. Morozov, B. Erdelyi

2012-07-01

A primary technical challenge to the design of a high luminosity muon collider is an effective beam cooling system. An epicyclic twin-helix channel utilizing parametric-resonance ionization cooling has been proposed for the final 6D cooling stage. A proposed design of this twin-helix channel is presented that utilizes correlated optics between the horizontal and vertical betatron periods to simultaneously focus transverse motion of the beam in both planes. Parametric resonance is induced in both planes via a system of helical quadrupole harmonics. Ionization cooling is achieved via periodically placed wedges of absorbing material, with intermittent rf cavities restoring longitudinal momentum necessarymore » to maintain stable orbit of the beam. COSY INFINITY is utilized to simulate the theory at first order. The motion of particles around a hyperbolic fixed point is tracked. Comparison is made between the EPIC cooling channel and standard ionization cooling effects. Cooling effects are measured, after including stochastic effects, for both a single particle and a distribution of particles.« less

Matilda: A mass filtered nanocluster source

NASA Astrophysics Data System (ADS)

Kwon, Gihan

Cluster science provides a good model system for the study of the size dependence of electronic properties, chemical reactivity, as well as magnetic properties of materials. One of the main interests in cluster science is the nanoscale understanding of chemical reactions and selectivity in catalysis. Therefore, a new cluster system was constructed to study catalysts for applications in renewable energy. Matilda, a nanocluster source, consists of a cluster source and a Retarding Field Analyzer (RFA). A moveable AJA A310 Series 1"-diameter magnetron sputtering gun enclosed in a water cooled aggregation tube served as the cluster source. A silver coin was used for the sputtering target. The sputtering pressure in the aggregation tube was controlled, ranging from 0.07 to 1torr, using a mass flow controller. The mean cluster size was found to be a function of relative partial pressure (He/Ar), sputtering power, and aggregation length. The kinetic energy distribution of ionized clusters was measured with the RFA. The maximum ion energy distribution was 2.9 eV/atom at a zero pressure ratio. At high Ar flow rates, the mean cluster size was 20 ˜ 80nm, and at a 9.5 partial pressure ratio, the mean cluster size was reduced to 1.6nm. Our results showed that the He gas pressure can be optimized to reduce the cluster size variations. Results from SIMION, which is an electron optics simulation package, supported the basic function of an RFA, a three-element lens and the magnetic sector mass filter. These simulated results agreed with experimental data. For the size selection experiment, the channeltron electron multiplier collected ionized cluster signal at different positions during Ag deposition on a TEM grid for four and half hours. The cluster signal was high at the position for neutral clusters, which was not bent by a magnetic field, and the signal decreased rapidly far away from the neutral cluster region. For cluster separation according to mass to charge ratio in a magnetic sector mass filter, the ion energy of the cluster and its distribution must be precisely controlled by acceleration or deceleration. To verify the size separation, a high resolution microscope was required. Matilda provided narrow particle sized distribution from atomic scale to 4nm in size with different pressure ratio without additional mass filter. It is very economical way to produce relatively narrow particle size distribution.

Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. IV. Coulomb explosion of molecular heteroclusters

NASA Astrophysics Data System (ADS)

Last, Isidore; Jortner, Joshua

2004-11-01

In this paper we present a theoretical and computational study of the temporal dynamics and energetics of Coulomb explosion of (CD4)n and (CH4)n (n=55-4213) molecular heteroclusters in ultraintense (I=1016-1019W cm-2) laser fields, addressing the manifestation of electron dynamics, together with nuclear energetic and kinematic effects on the heterocluster Coulomb instability. The manifestations of the coupling between electron and nuclear dynamics were explored by molecular dynamics simulations for these heteroclusters coupled to Gaussian laser fields (pulse width τ=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for I⩽1017 W cm-2), and the attainment of cluster vertical ionization (CVI) (at I=1017 W cm-2 for cluster radius R0⩽31 Å). Nuclear kinematic effects on heterocluster Coulomb explosion are governed by the kinematic parameter η=qCmA/qAmC for (CA4)n clusters (A=H,D), where qj and mj (j=A,C) are the ionic charges and masses. Nonuniform heterocluster Coulomb explosion (η>1) manifests an overrun effect of the light ions relative to the heavy ions, exhibiting the expansion of two spatially separated subclusters, with the light ions forming the outer subcluster at the outer edge of the spatial distribution. Important features of the energetics of heterocluster Coulomb explosion originate from energetic triggering effects of the driving of the light ions by the heavy ions (C4+ for I=1017-1018W cm-2 and C6+ for I=1019 W cm-2), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R0) dependence of the energetics of uniform Coulomb explosion of heteroclusters (η=1) were derived, with the size dependence of the average (Ej,av) and maximal (Ej,M) ion energies being Ej,av=aR02 and Ej,M=(5a/3)R02, as well as for the ion energy distributions P(Ej)∝Ej1/2; Ej⩽Ej,M. These results for uniform Coulomb explosion serve as benchmark reference data for the assessment of the effects of nonuniform explosion, where the CVI scaling law for the energetics still holds, with deviations of the a coefficient, which increase with increasing η. Kinematic effects (for η>1) result in an isotope effect, predicting the enhancement (by 9%-11%) of EH,av for Coulomb explosion of (C4+H4+)η (η=3) relative to ED,av for Coulomb explosion of (C4+D4+)η (η=1.5), with the isotope effect being determined by the ratio of the kinematic parameters for the pair of Coulomb exploding clusters. Kinematic effects for nonuniform explosion also result in a narrow isotope dependent energy distribution (of width ΔE) of the light ions (with ΔE/EH,av≃0.3 and ΔE/ED,av≃0.4), with the distribution peaking at the high energy edge, in marked contrast with the uniform explosion case. Features of laser-heterocluster interactions were inferred from the analyses of the intensity dependent boundary radii (R0)I and the corresponding average D+ ion energies (ED,av)I, which provide a measure for optimization of the cluster size at intensity I for the neutron yield from dd nuclear fusion driven by Coulomb explosion (NFDCE) of these heteroclusters. We infer on the advantage of deuterium containing heteronuclear clusters, e.g., (CD4)n in comparison to homonuclear clusters, e.g., (D2)n/2, for dd NFDCE, where the highly charged heavy ions (e.g., C4+ or C6+) serve as energetic and kinematic triggers driving the D+ ions to a high (10-200 keV) energy domain.

THE BRIGHTEST YOUNG STAR CLUSTERS IN NGC 5253

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calzetti, D.; Johnson, K. E.; Adamo, A.

2015-10-01

The nearby dwarf starburst galaxy NGC 5253 hosts a number of young, massive star clusters, the two youngest of which are centrally concentrated and surrounded by thermal radio emission (the “radio nebula”). To investigate the role of these clusters in the starburst energetics, we combine new and archival Hubble Space Telescope images of NGC 5253 with wavelength coverage from 1500 Å to 1.9 μm in 13 filters. These include Hα, Pβ, and Pα, and the imaging from the Hubble Treasury Program LEGUS (Legacy Extragalactic UV Survey). The extraordinarily well-sampled spectral energy distributions enable modeling with unprecedented accuracy the ages, masses,more » and extinctions of the nine optically brightest clusters (M{sub V} < −8.8) and the two young radio nebula clusters. The clusters have ages ∼1–15 Myr and masses ∼1 × 10{sup 4}–2.5 × 10{sup 5} M{sub ⊙}. The clusters’ spatial location and ages indicate that star formation has become more concentrated toward the radio nebula over the last ∼15 Myr. The most massive cluster is in the radio nebula; with a mass ∼2.5 × 10{sup 5} M{sub ⊙} and an age ∼1 Myr, it is 2–4 times less massive and younger than previously estimated. It is within a dust cloud with A{sub V} ∼ 50 mag, and shows a clear near-IR excess, likely from hot dust. The second radio nebula cluster is also ∼1 Myr old, confirming the extreme youth of the starburst region. These two clusters account for about half of the ionizing photon rate in the radio nebula, and will eventually supply about 2/3 of the mechanical energy in present-day shocks. Additional sources are required to supply the remaining ionizing radiation, and may include very massive stars.« less

The Brightest Young Star Clusters in NGC 5253.

NASA Astrophysics Data System (ADS)

Calzetti, D.; Johnson, K. E.; Adamo, A.; Gallagher, J. S., III; Andrews, J. E.; Smith, L. J.; Clayton, G. C.; Lee, J. C.; Sabbi, E.; Ubeda, L.; Kim, H.; Ryon, J. E.; Thilker, D.; Bright, S. N.; Zackrisson, E.; Kennicutt, R. C.; de Mink, S. E.; Whitmore, B. C.; Aloisi, A.; Chandar, R.; Cignoni, M.; Cook, D.; Dale, D. A.; Elmegreen, B. G.; Elmegreen, D. M.; Evans, A. S.; Fumagalli, M.; Gouliermis, D. A.; Grasha, K.; Grebel, E. K.; Krumholz, M. R.; Walterbos, R.; Wofford, A.; Brown, T. M.; Christian, C.; Dobbs, C.; Herrero, A.; Kahre, L.; Messa, M.; Nair, P.; Nota, A.; Östlin, G.; Pellerin, A.; Sacchi, E.; Schaerer, D.; Tosi, M.

2015-10-01

The nearby dwarf starburst galaxy NGC 5253 hosts a number of young, massive star clusters, the two youngest of which are centrally concentrated and surrounded by thermal radio emission (the “radio nebula”). To investigate the role of these clusters in the starburst energetics, we combine new and archival Hubble Space Telescope images of NGC 5253 with wavelength coverage from 1500 Å to 1.9 μm in 13 filters. These include Hα, Pβ, and Pα, and the imaging from the Hubble Treasury Program LEGUS (Legacy Extragalactic UV Survey). The extraordinarily well-sampled spectral energy distributions enable modeling with unprecedented accuracy the ages, masses, and extinctions of the nine optically brightest clusters (MV < -8.8) and the two young radio nebula clusters. The clusters have ages ˜1-15 Myr and masses ˜1 × 104-2.5 × 105 M⊙. The clusters’ spatial location and ages indicate that star formation has become more concentrated toward the radio nebula over the last ˜15 Myr. The most massive cluster is in the radio nebula; with a mass ˜2.5 × 105 M⊙ and an age ˜1 Myr, it is 2-4 times less massive and younger than previously estimated. It is within a dust cloud with AV ˜ 50 mag, and shows a clear near-IR excess, likely from hot dust. The second radio nebula cluster is also ˜1 Myr old, confirming the extreme youth of the starburst region. These two clusters account for about half of the ionizing photon rate in the radio nebula, and will eventually supply about 2/3 of the mechanical energy in present-day shocks. Additional sources are required to supply the remaining ionizing radiation, and may include very massive stars. Based on observations obtained with the NASA/ESA Hubble Space Telescope, at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555.

Comparison of Three Plasma Sources for Ambient Desorption/Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

McKay, Kirsty; Salter, Tara L.; Bowfield, Andrew; Walsh, James L.; Gilmore, Ian S.; Bradley, James W.

2014-09-01

Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources.

Comparison of three plasma sources for ambient desorption/ionization mass spectrometry.

PubMed

McKay, Kirsty; Salter, Tara L; Bowfield, Andrew; Walsh, James L; Gilmore, Ian S; Bradley, James W

2014-09-01

Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling.

PubMed

Wang, Zhifan; Hu, Shu; Wang, Fan; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis set without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhifan; Hu, Shu; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis setmore » without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.« less

Reducing the Matrix Effect in Organic Cluster SIMS Using Dynamic Reactive Ionization

NASA Astrophysics Data System (ADS)

Tian, Hua; Wucher, Andreas; Winograd, Nicholas

2016-12-01

Dynamic reactive ionization (DRI) utilizes a reactive molecule, HCl, which is doped into an Ar cluster projectile and activated to produce protons at the bombardment site on the cold sample surface with the presence of water. The methodology has been shown to enhance the ionization of protonated molecular ions and to reduce salt suppression in complex biomatrices. In this study, we further examine the possibility of obtaining improved quantitation with DRI during depth profiling of thin films. Using a trehalose film as a model system, we are able to define optimal DRI conditions for depth profiling. Next, the strategy is applied to a multilayer system consisting of the polymer antioxidants Irganox 1098 and 1010. These binary mixtures have demonstrated large matrix effects, making quantitative SIMS measurement not feasible. Systematic comparisons of depth profiling of this multilayer film between directly using GCIB, and under DRI conditions, show that the latter enhances protonated ions for both components by 4- to 15-fold, resulting in uniform depth profiling in positive ion mode and almost no matrix effect in negative ion mode. The methodology offers a new strategy to tackle the matrix effect and should lead to improved quantitative measurement using SIMS.

Simulating 3D Stellar Winds and Diffuse X-ray Emissions from Gases in Non-equilibrium Ionization State

NASA Astrophysics Data System (ADS)

Long, Min; Sun, Wei; Niu, Shu; Zhou, Xin; Ji, Li

2017-08-01

We investigate the physical properties of stellar winds launched in super stellar clusters (SSCs). Chandra observations have detected the presence of diffuse X-ray emission caused by hot gas from such winds in SSCs, and provide the best probe for understanding interactions between the stellar winds and the complex nursery regions. However, the details of the origin of cluster winds, the mass and energy ejection, the formation of diffuse X-ray emission, the fraction of winds contribution to the distribution of diffuse X-ray emission still remain unclear. We developed a multiphysics hydrodynamic model including self-gravity, head conduction and performed 3D simulations with an unprecedented grid resolution due to adaptive mesh refinement (AMR) capability in a case study of NGC 3603, as a supplement to the analysis of the archived 500 ks Chandra observations. The synthetic emission will be computed by assuming the gas in a non-equilibrium ionization (NEI) state indicated by Chandra observation, not coronal ionization equilibrium (CIE) that most works assumed, by using a customized NEI calculation module based on AtomDB. The results will be compared to the Chandra observations.

Earthquake clouds and physical mechanism of their formation.

NASA Astrophysics Data System (ADS)

Doda, L.; Pulinets, S.

2006-12-01

The Lithosphere-Atmosphere-Ionosphere (LAI) coupling model created recently permitted to explain some unknown phenomena observed around the time of strong earthquakes. One of them is formation of special shape clouds, usually presented as the thin linear structures. It was discovered that these clouds are associated with the active tectonic faults or with the tectonic plate borders. They repeat the fault shape but usually are turned in relation to the fault position. Their formation is explained by the anomalous vertical electric field generated in the vicinity of active tectonic structure due to air ionization produced by the radon increased emanation. The new formed ions through the hydration process do not recombine and growth with time due to increased water molecules attachment to the ion. Simultaneously they move up driven by the anomalous electric field and drift in the crossed ExB fields. At the higher altitudes the large ion clusters become the centers of condensation and the cloud formation. Examples for the recent major earthquakes (Sumatra 2004, Kashmir 2005, Java 2006) are presented. The size and the angle of the cloud rotation in relation to the fault position permit to estimate the magnitude of the impending earthquake.

The new ClusterTrap setup

NASA Astrophysics Data System (ADS)

Martinez, F.; Marx, G.; Schweikhard, L.; Vass, A.; Ziegler, F.

2011-07-01

ClusterTrap has been designed to investigate properties of atomic clusters in the gas phase with particular emphasis on the dependence on the cluster size and charge state. The combination of cluster source, Penning trap and time-of-flight mass spectrometry allows a variety of experimental schemes including collision-induced dissociation, photo-dissociation, further ionization by electron impact, and electron attachment. Due to the storage capability of the trap extended-delay reaction experiments can be performed. Several recent modifications have resulted in an improved setup. In particular, an electrostatic quadrupole deflector allows the coupling of several sources or detectors to the Penning trap. Furthermore, a linear radio-frequency quadrupole trap has been added for accumulation and ion bunching and by switching the potential of a drift tube the kinetic energy of the cluster ions can be adjusted on their way towards or from the Penning trap. Recently, experiments on multiply negatively charged clusters have been resumed.

Radionuclide Ionization in Protoplanetary Disks: Calculations of Decay Product Radiative Transfer

NASA Astrophysics Data System (ADS)

Cleeves, L. Ilsedore; Adams, Fred C.; Bergin, Edwin A.; Visser, Ruud

2013-11-01

We present simple analytic solutions for the ionization rate ζSLR arising from the decay of short-lived radionuclides (SLRs) within protoplanetary disks. We solve the radiative transfer problem for the decay products within the disk, and thereby allow for the loss of radiation at low disk surface densities; energy loss becomes important outside R >~ 30 AU for typical disk masses Mg = 0.04 M ⊙. Previous studies of chemistry/physics in these disks have neglected the impact of ionization by SLRs, and often consider only cosmic rays (CRs), because of the high CR-rate present in the interstellar medium. However, recent work suggests that the flux of CRs present in the circumstellar environment could be substantially reduced by relatively modest stellar winds, resulting in severely modulated CR ionization rates, ζCR, equal to or substantially below that of SLRs (ζSLR <~ 10-18 s-1). We compute the net ionizing particle fluxes and corresponding ionization rates as a function of position within the disk for a variety of disk models. The resulting expressions are especially simple for the case of vertically Gaussian disks (frequently assumed in the literature). Finally, we provide a power-law fit to the ionization rate in the midplane as a function of gas disk surface density and time. Depending on location in the disk, the ionization rates by SLRs are typically in the range ζSLR ~ (1-10) × 10-19 s-1.

Comparison of Internal Energy Distributions of Ions Created by Electrospray Ionization and Laser Ablation-Liquid Vortex Capture-Electrospray Ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cahill, John F.; Kertesz, Vilmos; Ovchinnikova, Olga S.

2015-06-27

Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed non-contact liquid-vortex capture probe has been used to efficiently collect 355 nm UV laser ablated material in a continuous flow solvent stream in which the captured material dissolves and then undergoes electrospray ionization. This sampling and ionization approach has produced what appear to be classic electrospray ionization spectra; however, the softness of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. A series of benzlypyridinium salts, known as thermometer ions, were used to comparemore » internal energy distributions between electrospray ionization and the UV laser ablation liquid-vortex capture probe electrospray combination. Measured internal energy distributions were identical between the two techniques, even with differences in laser fluence (0.7-3.1 J cm-2) and when using UV-absorbing or non-UV-absorbing sample substrates. This data indicates ions formed directly by UV laser ablation, if any, are likely an extremely small constituent of the total ion signal observed. Instead, neutral molecules, clusters or particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream then electrosprayed are the predominant source of ion signal observed. The electrospray ionization process used controls the softness of the technique.« less

A coupled cluster theory with iterative inclusion of triple excitations and associated equation of motion formulation for excitation energy and ionization potential

NASA Astrophysics Data System (ADS)

Maitra, Rahul; Akinaga, Yoshinobu; Nakajima, Takahito

2017-08-01

A single reference coupled cluster theory that is capable of including the effect of connected triple excitations has been developed and implemented. This is achieved by regrouping the terms appearing in perturbation theory and parametrizing through two different sets of exponential operators: while one of the exponentials, involving general substitution operators, annihilates the ground state but has a non-vanishing effect when it acts on the excited determinant, the other is the regular single and double excitation operator in the sense of conventional coupled cluster theory, which acts on the Hartree-Fock ground state. The two sets of operators are solved as coupled non-linear equations in an iterative manner without significant increase in computational cost than the conventional coupled cluster theory with singles and doubles excitations. A number of physically motivated and computationally advantageous sufficiency conditions are invoked to arrive at the working equations and have been applied to determine the ground state energies of a number of small prototypical systems having weak multi-reference character. With the knowledge of the correlated ground state, we have reconstructed the triple excitation operator and have performed equation of motion with coupled cluster singles, doubles, and triples to obtain the ionization potential and excitation energies of these molecules as well. Our results suggest that this is quite a reasonable scheme to capture the effect of connected triple excitations as long as the ground state remains weakly multi-reference.

Halorhodopsin pumps Cl– and bacteriorhodopsin pumps protons by a common mechanism that uses conserved electrostatic interactions

PubMed Central

Gunner, M. R.

2014-01-01

Key mutations differentiate the functions of homologous proteins. One example compares the inward ion pump halorhodopsin (HR) and the outward proton pump bacteriorhodopsin (BR). Of the nine essential buried ionizable residues in BR, six are conserved in HR. However, HR changes three BR acids, D85 in a central cluster of ionizable residues, D96, nearer the intracellular, and E204, nearer the extracellular side of the membrane to the small, neutral amino acids T111, V122, and T230, respectively. In BR, acidic amino acids are stationary anions whose proton affinity is modulated by conformational changes, establishing a sequence of directed binding and release of protons. Multiconformation continuum electrostatics calculations of chloride affinity and residue protonation show that, in reaction intermediates where an acid is ionized in BR, a Cl– is bound to HR in a position near the deleted acid. In the HR ground state, Cl– binds tightly to the central cluster T111 site and weakly to the extracellular T230 site, recovering the charges on ionized BR-D85 and neutral E204 in BR. Imposing key conformational changes from the BR M intermediate into the HR structure results in the loss of Cl– from the central T111 site and the tight binding of Cl– to the extracellular T230 site, mirroring the changes that protonate BR-D85 and ionize E204 in BR. The use of a mobile chloride in place of D85 and E204 makes HR more susceptible to the environmental pH and salt concentrations than BR. These studies shed light on how ion transfer mechanisms are controlled through the interplay of protein and ion electrostatics. PMID:25362051

Lowest-energy structures and electronic properties of Na-Si binary clusters from ab initio global search.

PubMed

Sai, Linwei; Tang, Lingli; Zhao, Jijun; Wang, Jun; Kumar, Vijay

2011-11-14

The ground state structures of neutral and anionic clusters of Na(n)Si(m) (1 ≤ n ≤ 3, 1 ≤ m ≤ 11) have been determined using genetic algorithm incorporated in first principles total energy code. The size dependence of the structural and electronic properties is discussed in detail. It is found that the lowest-energy structures of Na(n)Si(m) clusters resemble those of the pure Si clusters. Interestingly, Na atoms in neutral Na(n)Si(m) clusters are usually well separated by the Si(m) skeleton, whereas Na atoms can form Na-Na bonds in some anionic clusters. The ionization potentials, adiabatic electron affinities, and photoelectron spectra are also calculated and the results compare well with the experimental data. © 2011 American Institute of Physics

Exploration of the Ionizable Metal Cluster-Electrode Surface Analogy: Infrared Spectroelectrochemistry of (Pt24(CO)30)n, (Pt26(CO)32)n, and (Pt38(CO) 44)n (n=0 to -10), and Comparisons with Potential-Dependent Spectra of CO adlayers on Platinum Surfaces

DTIC Science & Technology

1992-05-01

100"C under vacuum for 24 hours. The corresponding tetraethylammonium hexafluorophosphate (TEAH) was prepared similarly by using ammonium...the four electrolytes examined in acetonitrile (Table III). Nevertheless, use of lithium perchlorate in acetonitrile restricted the range of cluster

Closed-cage tungsten oxide clusters in the gas phase.

PubMed

Singh, D M David Jeba; Pradeep, T; Thirumoorthy, Krishnan; Balasubramanian, Krishnan

2010-05-06

During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

Chirally directed formation of nanometer-scale proline clusters.

PubMed

Myung, Sunnie; Fioroni, Marco; Julian, Ryan R; Koeniger, Stormy L; Baik, Mu-Hyun; Clemmer, David E

2006-08-23

Ion mobility measurements, combined with molecular mechanics simulations, are used to study enantiopure and racemic proline clusters formed by electrospray ionization. Broad distributions of cluster sizes and charge states are observed, ranging from clusters containing only a few proline units to clusters that contain more than 100 proline units (i.e., protonated clusters of the form [xPro + nH](n+) with x = 1 to >100 and n = 1-7). As the sizes of clusters increase, there is direct evidence for nanometer scale, chirally induced organization into specific structures. For n = 4 and 5, enantiopure clusters of approximately 50 to 100 prolines assemble into structures that are more elongated than the most compact structure that is observed from the racemic proline clusters. A molecular analogue, cis-4-hydroxy-proline, displays significantly different behavior, indicating that in addition to the rigidity of the side chain ring, intermolecular interactions are important in the formation of chirally directed clusters. This is the first case in which assemblies of chirally selective elongated structures are observed in this size range of amino acid clusters. Relationships between enantiopurity, cluster shape, and overall energetics are discussed.

Radiation-induced gene expression in the nematode Caenorhabditis elegans

NASA Technical Reports Server (NTRS)

Nelson, Gregory A.; Jones, Tamako A.; Chesnut, Aaron; Smith, Anna L.

2002-01-01

We used the nematode C. elegans to characterize the genotoxic and cytotoxic effects of ionizing radiation in a simple animal model emphasizing the unique effects of charged particle radiation. Here we demonstrate by RT-PCR differential display and whole genome microarray hybridization experiments that gamma rays, accelerated protons and iron ions at the same physical dose lead to unique transcription profiles. 599 of 17871 genes analyzed (3.4%) showed differential expression 3 hrs after exposure to 3 Gy of radiation. 193 were up-regulated, 406 were down-regulated and 90% were affected only by a single species of radiation. A novel statistical clustering technique identified the regulatory relationships between the radiation-modulated genes and showed that genes affected by each radiation species were associated with unique regulatory clusters. This suggests that independent homeostatic mechanisms are activated in response to radiation exposure as a function of track structure or ionization density.

A Radical-Mediated Pathway for the Formation of [M + H](+) in Dielectric Barrier Discharge Ionization.

PubMed

Wolf, Jan-Christoph; Gyr, Luzia; Mirabelli, Mario F; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

2016-09-01

Active capillary plasma ionization is a highly efficient ambient ionization method. Its general principle of ion formation is closely related to atmospheric pressure chemical ionization (APCI). The method is based on dielectric barrier discharge ionization (DBDI), and can be constructed in the form of a direct flow-through interface to a mass spectrometer. Protonated species ([M + H](+)) are predominantly formed, although in some cases radical cations are also observed. We investigated the underlying ionization mechanisms and reaction pathways for the formation of protonated analyte ([M + H](+)). We found that ionization occurs in the presence and in the absence of water vapor. Therefore, the mechanism cannot exclusively rely on hydronium clusters, as generally accepted for APCI. Based on isotope labeling experiments, protons were shown to originate from various solvents (other than water) and, to a minor extent, from gaseous impurities and/or self-protonation. By using CO2 instead of air or N2 as plasma gas, additional species like [M + OH](+) and [M - H](+) were observed. These gas-phase reaction products of CO2 with the analyte (tertiary amines) indicate the presence of a radical-mediated ionization pathway, which proceeds by direct reaction of the ionized plasma gas with the analyte. The proposed reaction pathway is supported with density functional theory (DFT) calculations. These findings add a new ionization pathway leading to the protonated species to those currently known for APCI. Graphical Abstract ᅟ.

Strong collective attraction in colloidal clusters on a liquid-air interface.

PubMed

Pergamenshchik, V M

2009-01-01

It is shown that in a cluster of many colloids, trapped at a liquid-air interface, the well-known vertical-force-induced pairwise logarithmic attraction changes to a strongly enhanced power-law attraction. In large two-dimensional clusters, the attraction energy scales as the inverse square of the distance between colloids. The enhancement is given by the ratio eta = (square of the capillary length) / (interface surface area per colloid) and can be as large as 10;{5} . This explains why a very small vertical force on colloids, which is too weak to bring two of them together, can stabilize many-body structures on a liquid-air interface. The profile of a cluster is shown to consist of a large slow collective envelope modulated by a fast low-amplitude perturbation due to individual colloids. A closed equation for the slow envelope, which incorporates an arbitrary power-law repulsion between colloids, is derived. For example, this equation is solved for a large circular cluster with the hard-core colloid repulsion. It is suggested that the predicted effect is responsible for mysterious stabilization of colloidal structures observed in experiments on a surface of isotropic liquid and nematic liquid crystal.

Ion formation mechanisms in UV-MALDI.

PubMed

Knochenmuss, Richard

2006-09-01

Matrix Assisted Laser Desorption/Ionization (MALDI) is a very widely used analytical method, but has been developed in a highly empirical manner. Deeper understanding of ionization mechanisms could help to design better methods and improve interpretation of mass spectra. This review summarizes current mechanistic thinking, with emphasis on the most common MALDI variant using ultraviolet laser excitation. A two-step framework is gaining acceptance as a useful model for many MALDI experiments. The steps are primary ionization during or shortly after the laser pulse, followed by secondary reactions in the expanding plume of desorbed material. Primary ionization in UV-MALDI remains somewhat controversial, the two main approaches are the cluster and pooling/photoionization models. Secondary events are less contentious, ion-molecule reaction thermodynamics and kinetics are often invoked, but details differ. To the extent that local thermal equilibrium is approached in the plume, the mass spectra may be straightforwardly interpreted in terms of charge transfer thermodynamics.

Results of rocket measurements of D-region ionization over Thumba in MAP

NASA Technical Reports Server (NTRS)

Chakrabarty, D. K.; Beig, G.; Garg, S. C.; Subrahmanyam, P.; Zalpuri, K. S.; Somayajulu, Y. V.; Rao, M. N. M.; Tandel, C. B.; Murlikrishna, T. R.

1989-01-01

Under MAP, two rockets were launched from Thumba (8.5 N, 76.8 E) around 1030 hrs Lt with identical payloads on 7 and 10 March 1986 for D region studies. Positive ion densities were measured by spherical probe and Gerdien condenser and electron densities were measured by Langmuir probe and propagation experiments. In both flights a valley in ionization height profile was noticed around 83 km. The density of ionization at this altitude was about 4 x 10(2) cu cm. A detailed positive ion-chemical scheme was used to reproduce the measured ionization height profiles. The density of NO needed to reproduce the valley in ionization at 83 km came around 5 x 10(5) cu cm. A photochemical treatment without diffusion process was found inadequate to explain this value of NO. Calculations showed that the value of vertical eddy diffusion needed to reproduce the value of NO was around 10(6)sq cm/s. Interestingly, the same value of eddy diffusion coefficient was obtained when derived in the manner described by Thrane and his coworkers using only the positive ion current data of spherical probes.

Shells, holes, worms, high-velocity gas and the z-distribution of gas in galaxies.

NASA Astrophysics Data System (ADS)

Rand, R. J.

The author gives an overview of the current observational understanding of vertically extended gas components in spiral galaxies and the various phenomena which come under such names as shells, holes, worms, and high-velocity gas. For the most part, the focus is on recent high-resolution interferometric studies. The author concentrates on cold gas, and briefly on warm ionized gas, in the Milky Way and a few nearby spirals. Along the way, it is seen how phenomena such as worms and shells may be related to the formation and maintenance of the vertically extended components.

Structural, electronic, vibrational and optical properties of Bin clusters

NASA Astrophysics Data System (ADS)

Liang, Dan; Shen, Wanting; Zhang, Chunfang; Lu, Pengfei; Wang, Shumin

2017-10-01

The neutral, anionic and cationic bismuth clusters with the size n up to 14 are investigated by using B3LYP functional within the regime of density functional theory and the LAN2DZ basis set. By analysis of the geometries of the Bin (n = 2-14) clusters, where cationic and anionic bismuth clusters are largely similar to those of neutral ones, a periodic effect by adding units with one to four atoms into smaller cluster to form larger cluster is drawn for the stable structures of bismuth clusters. An even-odd alteration is shown for the properties of the clusters, such as the calculated binding energies and dissociation energies, as well as frontier orbital energies, electron affinities, ionization energies. All the properties indicate that the Bi4 cluster is the most possible existence in bismuth-containing materials, which supports the most recent experiment. The orbital compositions, infrared and Raman activities and the ultraviolet absorption of the most possible tetramer bismuth cluster are given in detail to reveal the periodic tendency of adding bismuth atoms and the stability of tetramer bismuth cluster.

The Technical and Biological Reproducibility of Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS) Based Typing: Employment of Bioinformatics in a Multicenter Study

PubMed Central

Oberle, Michael; Wohlwend, Nadia; Jonas, Daniel; Maurer, Florian P.; Jost, Geraldine; Tschudin-Sutter, Sarah; Vranckx, Katleen; Egli, Adrian

2016-01-01

Background The technical, biological, and inter-center reproducibility of matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI TOF MS) typing data has not yet been explored. The aim of this study is to compare typing data from multiple centers employing bioinformatics using bacterial strains from two past outbreaks and non-related strains. Material/Methods Participants received twelve extended spectrum betalactamase-producing E. coli isolates and followed the same standard operating procedure (SOP) including a full-protein extraction protocol. All laboratories provided visually read spectra via flexAnalysis (Bruker, Germany). Raw data from each laboratory allowed calculating the technical and biological reproducibility between centers using BioNumerics (Applied Maths NV, Belgium). Results Technical and biological reproducibility ranged between 96.8–99.4% and 47.6–94.4%, respectively. The inter-center reproducibility showed a comparable clustering among identical isolates. Principal component analysis indicated a higher tendency to cluster within the same center. Therefore, we used a discriminant analysis, which completely separated the clusters. Next, we defined a reference center and performed a statistical analysis to identify specific peaks to identify the outbreak clusters. Finally, we used a classifier algorithm and a linear support vector machine on the determined peaks as classifier. A validation showed that within the set of the reference center, the identification of the cluster was 100% correct with a large contrast between the score with the correct cluster and the next best scoring cluster. Conclusions Based on the sufficient technical and biological reproducibility of MALDI-TOF MS based spectra, detection of specific clusters is possible from spectra obtained from different centers. However, we believe that a shared SOP and a bioinformatics approach are required to make the analysis robust and reliable. PMID:27798637

Extraction of object skeletons in multispectral imagery by the orthogonal regression fitting

NASA Astrophysics Data System (ADS)

Palenichka, Roman M.; Zaremba, Marek B.

2003-03-01

Accurate and automatic extraction of skeletal shape of objects of interest from satellite images provides an efficient solution to such image analysis tasks as object detection, object identification, and shape description. The problem of skeletal shape extraction can be effectively solved in three basic steps: intensity clustering (i.e. segmentation) of objects, extraction of a structural graph of the object shape, and refinement of structural graph by the orthogonal regression fitting. The objects of interest are segmented from the background by a clustering transformation of primary features (spectral components) with respect to each pixel. The structural graph is composed of connected skeleton vertices and represents the topology of the skeleton. In the general case, it is a quite rough piecewise-linear representation of object skeletons. The positions of skeleton vertices on the image plane are adjusted by means of the orthogonal regression fitting. It consists of changing positions of existing vertices according to the minimum of the mean orthogonal distances and, eventually, adding new vertices in-between if a given accuracy if not yet satisfied. Vertices of initial piecewise-linear skeletons are extracted by using a multi-scale image relevance function. The relevance function is an image local operator that has local maximums at the centers of the objects of interest.

Breakdown voltage reduction by field emission in multi-walled carbon nanotubes based ionization gas sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saheed, M. Shuaib M.; Muti Mohamed, Norani; Arif Burhanudin, Zainal, E-mail: zainabh@petronas.com.my

2014-03-24

Ionization gas sensors using vertically aligned multi-wall carbon nanotubes (MWCNT) are demonstrated. The sharp tips of the nanotubes generate large non-uniform electric fields at relatively low applied voltage. The enhancement of the electric field results in field emission of electrons that dominates the breakdown mechanism in gas sensor with gap spacing below 14 μm. More than 90% reduction in breakdown voltage is observed for sensors with MWCNT and 7 μm gap spacing. Transition of breakdown mechanism, dominated by avalanche electrons to field emission electrons, as decreasing gap spacing is also observed and discussed.

Perturbation corrections to Koopmans' theorem. V - A study with large basis sets

NASA Technical Reports Server (NTRS)

Chong, D. P.; Langhoff, S. R.

1982-01-01

The vertical ionization potentials of N2, F2 and H2O were calculated by perturbation corrections to Koopmans' theorem using six different basis sets. The largest set used includes several sets of polarization functions. Comparison is made with measured values and with results of computations using Green's functions.

Method for eliminating artifacts in CCD imagers

DOEpatents

Turko, B.T.; Yates, G.J.

1992-06-09

An electronic method for eliminating artifacts in a video camera employing a charge coupled device (CCD) as an image sensor is disclosed. The method comprises the step of initializing the camera prior to normal read out and includes a first dump cycle period for transferring radiation generated charge into the horizontal register while the decaying image on the phosphor being imaged is being integrated in the photosites, and a second dump cycle period, occurring after the phosphor image has decayed, for rapidly dumping unwanted smear charge which has been generated in the vertical registers. Image charge is then transferred from the photosites and to the vertical registers and read out in conventional fashion. The inventive method allows the video camera to be used in environments having high ionizing radiation content, and to capture images of events of very short duration and occurring either within or outside the normal visual wavelength spectrum. Resultant images are free from ghost, smear and smear phenomena caused by insufficient opacity of the registers and, and are also free from random damage caused by ionization charges which exceed the charge limit capacity of the photosites. 3 figs.

Nuclear fusion driven by Coulomb explosion of homonuclear and heteronuclear deuterium- and tritium-containing clusters

NASA Astrophysics Data System (ADS)

Last, Isidore; Jortner, Joshua

2001-12-01

The ionization and Coulomb explosion of homonuclear Dn and Tn (n=959-8007) and heteronuclear (D2O)n and (T2O)n (n=459-2171) clusters in very intense (I=5×1014-5×1018 W cm-2) laser fields is studied using classical dynamics simulations. The efficiency of the d+d and d+t nuclear fusion driven by the Coulomb explosion (NFDCE) is explored. The d+d NFDCE of (D2O)n heteronuclear clusters is enhanced by energetic and kinematic effects for D+, while for (T2O)n heteronuclear clusters the kinetic energy of T+ is dominated by energetic effects. The cluster size dependence of the fusion reaction yield has been established. The heteronuclear clusters provide considerably higher d+d and d+t fusion reaction yields than the homonuclear clusters of the same size. The clusters consisting of both D and T atoms can provide highly efficient d+t fusion reactions.

Delineation of Stenotrophomonas maltophilia isolates from cystic fibrosis patients by fatty acid methyl ester profiles and matrix-assisted laser desorption/ionization time-of-flight mass spectra using hierarchical cluster analysis and principal component analysis.

PubMed

Vidigal, Pedrina Gonçalves; Mosel, Frank; Koehling, Hedda Luise; Mueller, Karl Dieter; Buer, Jan; Rath, Peter Michael; Steinmann, Joerg

2014-12-01

Stenotrophomonas maltophilia is an opportunist multidrug-resistant pathogen that causes a wide range of nosocomial infections. Various cystic fibrosis (CF) centres have reported an increasing prevalence of S. maltophilia colonization/infection among patients with this disease. The purpose of this study was to assess specific fingerprints of S. maltophilia isolates from CF patients (n = 71) by investigating fatty acid methyl esters (FAMEs) through gas chromatography (GC) and highly abundant proteins by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), and to compare them with isolates obtained from intensive care unit (ICU) patients (n = 20) and the environment (n = 11). Principal component analysis (PCA) of GC-FAME patterns did not reveal a clustering corresponding to distinct CF, ICU or environmental types. Based on the peak area index, it was observed that S. maltophilia isolates from CF patients produced significantly higher amounts of fatty acids in comparison with ICU patients and the environmental isolates. Hierarchical cluster analysis (HCA) based on the MALDI-TOF MS peak profiles of S. maltophilia revealed the presence of five large clusters, suggesting a high phenotypic diversity. Although HCA of MALDI-TOF mass spectra did not result in distinct clusters predominantly composed of CF isolates, PCA revealed the presence of a distinct cluster composed of S. maltophilia isolates from CF patients. Our data suggest that S. maltophilia colonizing CF patients tend to modify not only their fatty acid patterns but also their protein patterns as a response to adaptation in the unfavourable environment of the CF lung. © 2014 The Authors.

Two-Dimensional Animal-Like Fractals in Thin Films

NASA Astrophysics Data System (ADS)

Gao, Hong-jun; Xue, Zeng-quan; Wu, Quan-de; Pang, Shi-jin

1996-02-01

We present a few unique animal-like fractal patterns in ionized-cluster-beam deposited fullerene-tetracyanoquinodimethane thin films. The fractal patterns consisting of animal-like aggregates such as "fishes" and "quasi-seahorses" have been characterized by transmission electron microscopy. The results indicate that the small aggregates of the animal-like body are composed of many single crystals whose crystalline directions are generally different. The formation of the fractal patterns can be attributed to the cluster-diffusion-limited aggregation.

Strong-field ionization of clusters using two-cycle pulses at 1.8 μm

PubMed Central

Schütte, Bernd; Ye, Peng; Patchkovskii, Serguei; Austin, Dane R.; Brahms, Christian; Strüber, Christian; Witting, Tobias; Ivanov, Misha Yu.; Tisch, John W. G.; Marangos, Jon P.

2016-01-01

The interaction of intense laser pulses with nanoscale particles leads to the production of high-energy electrons, ions, neutral atoms, neutrons and photons. Up to now, investigations have focused on near-infrared to X-ray laser pulses consisting of many optical cycles. Here we study strong-field ionization of rare-gas clusters (103 to 105 atoms) using two-cycle 1.8 μm laser pulses to access a new interaction regime in the limit where the electron dynamics are dominated by the laser field and the cluster atoms do not have time to move significantly. The emission of fast electrons with kinetic energies exceeding 3 keV is observed using laser pulses with a wavelength of 1.8 μm and an intensity of 1 × 1015 W/cm2, whereas only electrons below 500 eV are observed at 800 nm using a similar intensity and pulse duration. Fast electrons are preferentially emitted along the laser polarization direction, showing that they are driven out from the cluster by the laser field. In addition to direct electron emission, an electron rescattering plateau is observed. Scaling to even longer wavelengths is expected to result in a highly directional current of energetic electrons on a few-femtosecond timescale. PMID:28009012

New method for estimating clustering of DNA lesions induced by physical/chemical mutagens using fluorescence anisotropy.

PubMed

Akamatsu, Ken; Shikazono, Naoya; Saito, Takeshi

2017-11-01

We have developed a new method for estimating the localization of DNA damage such as apurinic/apyrimidinic sites (APs) on DNA using fluorescence anisotropy. This method is aimed at characterizing clustered DNA damage produced by DNA-damaging agents such as ionizing radiation and genotoxic chemicals. A fluorescent probe with an aminooxy group (AlexaFluor488) was used to label APs. We prepared a pUC19 plasmid with APs by heating under acidic conditions as a model for damaged DNA, and subsequently labeled the APs. We found that the observed fluorescence anisotropy (r obs ) decreases as averaged AP density (λ AP : number of APs per base pair) increases due to homo-FRET, and that the APs were randomly distributed. We applied this method to three DNA-damaging agents, 60 Co γ-rays, methyl methanesulfonate (MMS), and neocarzinostatin (NCS). We found that r obs -λ AP relationships differed significantly between MMS and NCS. At low AP density (λ AP  < 0.001), the APs induced by MMS seemed to not be closely distributed, whereas those induced by NCS were remarkably clustered. In contrast, the AP clustering induced by 60 Co γ-rays was similar to, but potentially more likely to occur than, random distribution. This simple method can be used to estimate mutagenicity of ionizing radiation and genotoxic chemicals. Copyright © 2017 Elsevier Inc. All rights reserved.

Ion-neutral Clustering of Bile Acids in Electrospray Ionization Across UPLC Flow Regimes

NASA Astrophysics Data System (ADS)

Brophy, Patrick; Broeckling, Corey D.; Murphy, James; Prenni, Jessica E.

2018-02-01

Bile acid authentic standards were used as model compounds to quantitatively evaluate complex in-source phenomenon on a UPLC-ESI-TOF-MS operated in the negative mode. Three different diameter columns and a ceramic-based microfluidic separation device were utilized, allowing for detailed descriptions of bile acid behavior across a wide range of flow regimes and instantaneous concentrations. A custom processing algorithm based on correlation analysis was developed to group together all ion signals arising from a single compound; these grouped signals produce verified compound spectra for each bile acid at each on-column mass loading. Significant adduction was observed for all bile acids investigated under all flow regimes and across a wide range of bile acid concentrations. The distribution of bile acid containing clusters was found to depend on the specific bile acid species, solvent flow rate, and bile acid concentration. Relative abundancies of each cluster changed non-linearly with concentration. It was found that summing all MS level (low collisional energy) ions and ion-neutral adducts arising from a single compound improves linearity across the concentration range (0.125-5 ng on column) and increases the sensitivity of MS level quantification. The behavior of each cluster roughly follows simple equilibrium processes consistent with our understanding of electrospray ionization mechanisms and ion transport processes occurring in atmospheric pressure interfaces. [Figure not available: see fulltext.

Superatoms as Building Blocks of New Materials

DTIC Science & Technology

2012-10-24

size regime. The adiabatic detachment energy (ADE) and vertical detachment energy ( VDE ) of Zn3O3 − and Zn3O4 − clusters were determined by anion...Zn3Om (m = 3,4,5) clusters, while the theoretical ADE and VDE values are compared with experimental results. The experimentally observed relative

On the SIMS Ionization Probability of Organic Molecules.

PubMed

Popczun, Nicholas J; Breuer, Lars; Wucher, Andreas; Winograd, Nicholas

2017-06-01

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α + ) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10 -5 . Our lab has developed a method for the direct determination of α + in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C 24 H 12 ), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C 60 cluster projectiles is of the order of 10 -3 , with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. Graphical Abstract .

Gas-phase lifetimes of nucleobase analogues by picosecond pumpionization and streak techniques.

PubMed

Blaser, Susan; Frey, Hans-Martin; Heid, Cornelia G; Leutwyler, Samuel

2014-01-01

The picosecond (ps) timescale is relevant for the investigation of many molecular dynamical processes such as fluorescence, nonradiative relaxation, intramolecular vibrational relaxation, molecular rotation and intermolecular energy transfer, to name a few. While investigations of ultrafast (femtosecond) processes of biological molecules, e.g. nucleobases and their analogues in the gas phase are available, there are few investigations on the ps time scale. We have constructed a ps pump-ionization setup and a ps streak camera fluorescence apparatus for the determination of lifetimes of supersonic jet-cooled and isolated molecules and clusters. The ps pump-ionization setup was used to determine the lifetimes of the nucleobase analogue 2-aminopurine (2AP) and of two 2AP˙(H2O)n water cluster isomers with n=1 and 2. Their lifetimes lie between 150 ps and 3 ns and are strongly cluster-size dependent. The ps streak camera setup was used to determine accurate fluorescence lifetimes of the uracil analogue 2-pyridone (2PY), its self-dimer (2PY)2, two isomers of its trimer (2PY)3 and its tetramer (2PY)4, which lie in the 7-12 ns range.

The shape and size distribution of H II regions near the percolation transition

NASA Astrophysics Data System (ADS)

Bag, Satadru; Mondal, Rajesh; Sarkar, Prakash; Bharadwaj, Somnath; Sahni, Varun

2018-06-01

Using Shapefinders, which are ratios of Minkowski functionals, we study the morphology of neutral hydrogen (H I) density fields, simulated using seminumerical technique (inside-out), at various stages of reionization. Accompanying the Shapefinders, we also employ the `largest cluster statistic' (LCS), originally proposed in Klypin & Shandarin, to study the percolation in both neutral and ionized hydrogen. We find that the largest ionized region is percolating below the neutral fraction x_{H I}≲ 0.728 (or equivalently z ≲ 9). The study of Shapefinders reveals that the largest ionized region starts to become highly filamentary with non-trivial topology near the percolation transition. During the percolation transition, the first two Shapefinders - `thickness' (T) and `breadth' (B) - of the largest ionized region do not vary much, while the third Shapefinder - `length' (L) - abruptly increases. Consequently, the largest ionized region tends to be highly filamentary and topologically quite complex. The product of the first two Shapefinders, T × B, provides a measure of the `cross-section' of a filament-like ionized region. We find that, near percolation, the value of T × B for the largest ionized region remains stable at ˜7 Mpc2 (in comoving scale) while its length increases with time. Interestingly, all large ionized regions have similar cross-sections. However, their length shows a power-law dependence on their volume, L ∝ V0.72, at the onset of percolation.

Relaxation times measurement in single and multiply excited xenon clusters

NASA Astrophysics Data System (ADS)

Serdobintsev, P. Yu.; Melnikov, A. S.; Pastor, A. A.; Timofeev, N. A.; Khodorkovskiy, M. A.

2018-05-01

Direct measurement of the rates of nonradiative relaxation processes in electronically excited xenon clusters was carried out. The clusters were created in a pulsed supersonic beam and two-photon excited by femtosecond laser pulses with a wavelength of 263 nm. The measurements were performed using the pump-probe method and electron spectroscopy. It is shown that relaxation of light clusters XeN (N < 15) predominantly occurs by desorption of excited xenon atoms with a characteristic time constant of 3 ps. Heavier electronically excited clusters (N > 10) vibrationally relax to the lowest electronically excited state at a rate of about 0.075 eV/ps. Multiply excited clusters are deactivated via energy exchange between excited centers with the ionization of one of them. The production of electrons in this process occurs with a delay of ˜4 ps from the pump pulse, and the process is completed in 10 ps.

Quantum chemistry in arbitrary dielectric environments: Theory and implementation of nonequilibrium Poisson boundary conditions and application to compute vertical ionization energies at the air/water interface

NASA Astrophysics Data System (ADS)

Coons, Marc P.; Herbert, John M.

2018-06-01

Widely used continuum solvation models for electronic structure calculations, including popular polarizable continuum models (PCMs), usually assume that the continuum environment is isotropic and characterized by a scalar dielectric constant, ɛ. This assumption is invalid at a liquid/vapor interface or any other anisotropic solvation environment. To address such scenarios, we introduce a more general formalism based on solution of Poisson's equation for a spatially varying dielectric function, ɛ(r). Inspired by nonequilibrium versions of PCMs, we develop a similar formalism within the context of Poisson's equation that includes the out-of-equilibrium dielectric response that accompanies a sudden change in the electron density of the solute, such as that which occurs in a vertical ionization process. A multigrid solver for Poisson's equation is developed to accommodate the large spatial grids necessary to discretize the three-dimensional electron density. We apply this methodology to compute vertical ionization energies (VIEs) of various solutes at the air/water interface and compare them to VIEs computed in bulk water, finding only very small differences between the two environments. VIEs computed using approximately two solvation shells of explicit water molecules are in excellent agreement with experiment for F-(aq), Cl-(aq), neat liquid water, and the hydrated electron, although errors for Li+(aq) and Na+(aq) are somewhat larger. Nonequilibrium corrections modify VIEs by up to 1.2 eV, relative to models based only on the static dielectric constant, and are therefore essential to obtain agreement with experiment. Given that the experiments (liquid microjet photoelectron spectroscopy) may be more sensitive to solutes situated at the air/water interface as compared to those in bulk water, our calculations provide some confidence that these experiments can indeed be interpreted as measurements of VIEs in bulk water.

Quantum chemistry in arbitrary dielectric environments: Theory and implementation of nonequilibrium Poisson boundary conditions and application to compute vertical ionization energies at the air/water interface.

PubMed

Coons, Marc P; Herbert, John M

2018-06-14

Widely used continuum solvation models for electronic structure calculations, including popular polarizable continuum models (PCMs), usually assume that the continuum environment is isotropic and characterized by a scalar dielectric constant, ε. This assumption is invalid at a liquid/vapor interface or any other anisotropic solvation environment. To address such scenarios, we introduce a more general formalism based on solution of Poisson's equation for a spatially varying dielectric function, ε(r). Inspired by nonequilibrium versions of PCMs, we develop a similar formalism within the context of Poisson's equation that includes the out-of-equilibrium dielectric response that accompanies a sudden change in the electron density of the solute, such as that which occurs in a vertical ionization process. A multigrid solver for Poisson's equation is developed to accommodate the large spatial grids necessary to discretize the three-dimensional electron density. We apply this methodology to compute vertical ionization energies (VIEs) of various solutes at the air/water interface and compare them to VIEs computed in bulk water, finding only very small differences between the two environments. VIEs computed using approximately two solvation shells of explicit water molecules are in excellent agreement with experiment for F - (aq), Cl - (aq), neat liquid water, and the hydrated electron, although errors for Li + (aq) and Na + (aq) are somewhat larger. Nonequilibrium corrections modify VIEs by up to 1.2 eV, relative to models based only on the static dielectric constant, and are therefore essential to obtain agreement with experiment. Given that the experiments (liquid microjet photoelectron spectroscopy) may be more sensitive to solutes situated at the air/water interface as compared to those in bulk water, our calculations provide some confidence that these experiments can indeed be interpreted as measurements of VIEs in bulk water.

HEAO-A2 observations of the X-ray spectra of the Centaurus and A1060 clusters of galaxies

NASA Technical Reports Server (NTRS)

Mitchell, R.; Mushotzky, R.

1979-01-01

The X-ray spectral observations of two low luminosity clusters of galaxies, Centaurus and A1060, are presented. An emission feature of the Centaurus cluster at 7.9 keV is detected at about one third of the strength of the 6.7 keV line. This higher energy line represents K sub beta emission from highly ionized iron. An isothermal model with an Fe emission line is discussed and it is shown that the model cannot fit the data of the Centaurus or the A1060 clusters. The implications of the two component nature of the continuum on the Fe abundance and the X-ray surface brightness distribution are discussed.

Nova-driven winds in globular clusters

NASA Technical Reports Server (NTRS)

Scott, E. H.; Durisen, R. H.

1978-01-01

Recent sensitive searches for H-alpha emission from ionized intracluster gas in globular clusters have set upper limits that conflict with theoretical predictions. It is suggested that nova outbursts heat the gas, producing winds that resolve this discrepancy. The incidence of novae in globular clusters, the conversion of kinetic energy of the nova shell to thermal energy of the intracluster gas, and the characteristics of the resultant winds are discussed. Calculated emission from the nova-driven models does not conflict with any observations to date. Some suggestions are made concerning the most promising approaches for future detection of intracluster gas on the basis of these models. The possible relationship of nova-driven winds to globular cluster X-ray sources is also considered.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keyshar, Kunttal; Berg, Morgann; Zhang, Xiang

Here, the values of the ionization energies of transition metal dichalcogenides (TMDs) are needed to assess their potential usefulness in semiconductor heterojunctions for high-performance optoelectronics. Here, we report on the systematic determination of ionization energies for three prototypical TMD monolayers (MoSe 2, WS 2, and MoS 2) on SiO 2 using photoemission electron microscopy with deep ultraviolet illumination. The ionization energy displays a progressive decrease from MoS 2, to WS 2, to MoSe 2, in agreement with predictions of density functional theory calculations. Combined with the measured energy positions of the valence band edge at the Brillouin zone center, wemore » deduce that, in the absence of interlayer coupling, a vertical heterojunction comprising any of the three TMD monolayers would form a staggered (type-II) band alignment. This band alignment could give rise to long-lived interlayer excitons that are potentially useful for valleytronics or efficient electron–hole separation in photovoltaics.« less

Earthquake relocation near the Leech River Fault, southern Vancouver Island

NASA Astrophysics Data System (ADS)

Li, G.; Liu, Y.; Regalla, C.

2015-12-01

The Leech River Fault (LRF), a northeast dipping thrust, extends across the southern tip of Vancouver Island in Southwest British Columbia, where local tectonic regime is dominated by the subduction of the Juan de Fuca plate beneath the North American plate at the present rate of 40-50 mm/year. British Columbia geologic map (Geoscience Map 2009-1A) shows that this area also consists of many crosscutting minor faults in addition to the San Juan Fault north of the LRF. To investigate the seismic evidence of the subsurface structures of these minor faults and of possible hidden active structures in this area, precise earthquake locations are required. In this study, we relocate 941 earthquakes reported by Canadian National Seismograph Network (CNSN) catalog from 2000 to 2015 within a 100km x 55km study area surrounding the LRF. We use HypoDD [Waldhauser, F., 2001] double-difference relocation method by combining P/S phase arrivals provided by the CNSN at 169 stations and waveform data with correlation coefficient values greater than 0.7 at 50 common stations and event separation less than 10km. A total of 900 out of the 931 events satisfy the above relocation criteria. Velocity model used is a 1-D model extracted from the Ramachandran et al. (2005) model. Average relative location errors estimated by the bootstrap method are 546.5m (horizontal) and 1128.6m (in depth). Absolute errors reported by SVD method for individual clusters are ~100m in both dimensions. We select 5 clusters visually according to their epicenters (see figure). Cluster 1 is parallel to the LRF and a thrust FID #60. Clusters 2 and 3 are bounded by two faults: FID #75, a northeast dipping thrust marking the southwestern boundary of the Wrangellia terrane, and FID #2 marking the northern boundary. Clusters 4 and 5, to the northeast and northwest of Victoria respectively, however, do not represent the surface traces of any mapped faults. The depth profile of Cluster 5 depicts a hidden northeast dipping structure, while other clusters illustrate near-vertical structures. Seismicity of Clusters 1 and 3 suggests vertically dipping patterns for FID #60 and FID #2, while Cluster 4 may reveal a hidden vertically dipping structure. It is noteworthy that most events in this area are deeper than 20km, but the explanation for such deep earthquakes is still unclear.

Unprecedented Ionization Processes in Mass Spectrometry Provide Missing Link between ESI and MALDI.

PubMed

Trimpin, Sarah; Lee, Chuping; Weidner, Steffen M; El-Baba, Tarick J; Lutomski, Corinne A; Inutan, Ellen D; Foley, Casey D; Ni, Chi-Kung; McEwen, Charles N

2018-03-05

In the field of mass spectrometry, producing intact, highly-charged protein ions from surfaces is a conundrum with significant potential payoff in application areas ranging from biomedical to clinical research. Here, we report on the ability to form intact, highly-charged protein ions on high vacuum time-of-flight mass spectrometers in the linear and reflectron modes achievable using experimental conditions that allow effective matrix removal from both the sample surfaces and from the charged clusters formed by the laser ablation event. The charge states are the highest reported on high vacuum mass spectrometers, yet they remain at only around a third of the highest charge obtained using laser ablation with a suitable matrix at atmospheric pressure. Other than physical instrument modifications, the key to forming abundant and stable highly-charged ions appears to be the volatility of the matrix used. Cumulative results suggest mechanistic links between the ionization process reported here and traditional ionization methods of electrospray ionization and matrix-assisted laser desorption/ionization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clustersmore » occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.« less

Hartree-Fock calculation of the differential photoionization cross sections of small Li clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galitskiy, S. A.; Artemyev, A. N.; Jänkälä, K.

2015-01-21

Cross sections and angular distribution parameters for the single-photon ionization of all electron orbitals of Li{sub 2−8} are systematically computed in a broad interval of the photoelectron kinetic energies for the energetically most stable geometry of each cluster. Calculations of the partial photoelectron continuum waves in clusters are carried out by the single center method within the Hartree-Fock approximation. We study photoionization cross sections per one electron and analyze in some details general trends in the photoionization of inner and outer shells with respect to the size and geometry of a cluster. The present differential cross sections computed for Li{submore » 2} are in a good agreement with the available theoretical data, whereas those computed for Li{sub 3−8} clusters can be considered as theoretical predictions.« less

Experimental Determination of the Ionization Energies of MoSe 2, WS 2, and MoS 2 on SiO 2 Using Photoemission Electron Microscopy

DOE PAGES

Keyshar, Kunttal; Berg, Morgann; Zhang, Xiang; ...

2017-07-19

Here, the values of the ionization energies of transition metal dichalcogenides (TMDs) are needed to assess their potential usefulness in semiconductor heterojunctions for high-performance optoelectronics. Here, we report on the systematic determination of ionization energies for three prototypical TMD monolayers (MoSe 2, WS 2, and MoS 2) on SiO 2 using photoemission electron microscopy with deep ultraviolet illumination. The ionization energy displays a progressive decrease from MoS 2, to WS 2, to MoSe 2, in agreement with predictions of density functional theory calculations. Combined with the measured energy positions of the valence band edge at the Brillouin zone center, wemore » deduce that, in the absence of interlayer coupling, a vertical heterojunction comprising any of the three TMD monolayers would form a staggered (type-II) band alignment. This band alignment could give rise to long-lived interlayer excitons that are potentially useful for valleytronics or efficient electron–hole separation in photovoltaics.« less

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources

NASA Astrophysics Data System (ADS)

Newsome, G. Asher; Ackerman, Luke K.; Johnson, Kevin J.

2016-01-01

Post-plasma ambient desorption/ionization (ADI) sources are fundamentally dependent on surrounding water vapor to produce protonated analyte ions. There are two reports of humidity effects on ADI spectra. However, it is unclear whether humidity will affect all ADI sources and analytes, and by what mechanism humidity affects spectra. Flowing atmospheric pressure afterglow (FAPA) ionization and direct analysis in real time (DART) mass spectra of various surface-deposited and gas-phase analytes were acquired at ambient temperature and pressure across a range of observed humidity values. A controlled humidity enclosure around the ion source and mass spectrometer inlet was used to create programmed humidity and temperatures. The relative abundance and fragmentation of molecular adduct ions for several compounds consistently varied with changing ambient humidity and also were controlled with the humidity enclosure. For several compounds, increasing humidity decreased protonated molecule and other molecular adduct ion fragmentation in both FAPA and DART spectra. For others, humidity increased fragment ion ratios. The effects of humidity on molecular adduct ion fragmentation were caused by changes in the relative abundances of different reagent protonated water clusters and, thus, a change in the average difference in proton affinity between an analyte and the population of water clusters. Control of humidity in ambient post-plasma ion sources is needed to create spectral stability and reproducibility.

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources.

PubMed

Newsome, G Asher; Ackerman, Luke K; Johnson, Kevin J

2016-01-01

Post-plasma ambient desorption/ionization (ADI) sources are fundamentally dependent on surrounding water vapor to produce protonated analyte ions. There are two reports of humidity effects on ADI spectra. However, it is unclear whether humidity will affect all ADI sources and analytes, and by what mechanism humidity affects spectra. Flowing atmospheric pressure afterglow (FAPA) ionization and direct analysis in real time (DART) mass spectra of various surface-deposited and gas-phase analytes were acquired at ambient temperature and pressure across a range of observed humidity values. A controlled humidity enclosure around the ion source and mass spectrometer inlet was used to create programmed humidity and temperatures. The relative abundance and fragmentation of molecular adduct ions for several compounds consistently varied with changing ambient humidity and also were controlled with the humidity enclosure. For several compounds, increasing humidity decreased protonated molecule and other molecular adduct ion fragmentation in both FAPA and DART spectra. For others, humidity increased fragment ion ratios. The effects of humidity on molecular adduct ion fragmentation were caused by changes in the relative abundances of different reagent protonated water clusters and, thus, a change in the average difference in proton affinity between an analyte and the population of water clusters. Control of humidity in ambient post-plasma ion sources is needed to create spectral stability and reproducibility.

Ionization energies and electron affinities from a random-phase-approximation many-body Green's-function method including exchange interactions

NASA Astrophysics Data System (ADS)

Heßelmann, Andreas

2017-06-01

A many-body Green's-function method employing an infinite order summation of ring and exchange-ring contributions to the self-energy is presented. The individual correlation and relaxation contributions to the quasiparticle energies are calculated using an iterative scheme which utilizes density fitting of the particle-hole, particle-particle and hole-hole densities. It is shown that the ionization energies and electron affinities of this approach agree better with highly accurate coupled-cluster singles and doubles with perturbative triples energy difference results than those obtained with second-order Green's-function approaches. An analysis of the correlation and relaxation terms of the self-energy for the direct- and exchange-random-phase-approximation (RPA) Green's-function methods shows that the inclusion of exchange interactions leads to a reduction of the two contributions in magnitude. These differences, however, strongly cancel each other when summing the individual terms to the quasiparticle energies. Due to this, the direct- and exchange-RPA methods perform similarly for the description of ionization energies (IPs) and electron affinities (EAs). The coupled-cluster reference IPs and EAs, if corrected to the adiabatic energy differences between the neutral and charged molecules, were shown to be in very good agreement with experimental measurements.

Low oxidation state aluminum-containing cluster anions: Cp{sup ∗}Al{sub n}H{sup −}, n = 1–3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xinxing; Ganteför, Gerd; Bowen, Kit, E-mail: AKandalam@wcupa.edu, E-mail: kbowen@jhu.edu

Three new, low oxidation state, aluminum-containing cluster anions, Cp*Al{sub n}H{sup −}, n = 1–3, were prepared via reactions between aluminum hydride cluster anions, Al{sub n}H{sub m}{sup −}, and Cp*H ligands. These were characterized by mass spectrometry, anion photoelectron spectroscopy, and density functional theory based calculations. Agreement between the experimentally and theoretically determined vertical detachment energies and adiabatic detachment energies validated the computed geometrical structures. Reactions between aluminum hydride cluster anions and ligands provide a new avenue for discovering low oxidation state, ligated aluminum clusters.

Metal-atom Interactions and Clustering in Organic Semiconductor Systems

NASA Astrophysics Data System (ADS)

Tomita, Yoko; Park, Tea-uk; Nakayama, Takashi

2017-07-01

The interatomic interactions and clustering of metal atoms have been studied by first-principles calculations in graphene, pentacene, and polyacetylene as representative organic systems. It is shown that long-range repulsive Coulomb interaction appears between metal atoms with small electronegativity such as Al due to their ionization on host organic molecules, inducing their scattered distribution in organic systems. On the other hand, metal atoms with large electronegativity such as Au are weakly bonded to organic molecules, easily diffuse in molecular solids, and prefer to combine with each other owing to their short-range strong metallic-bonding interaction, promoting metal cluster generation in organic systems.

Observations of and Influences on Low-Latitude Vertical Plasma Drifts

NASA Astrophysics Data System (ADS)

Miller, E. S.; Chartier, A.; Paxton, L. J.

2016-12-01

Many workers have suggested that the morphology (position and relative intensities) of the crests of the equatorial ionization anomaliesis related to the time history of the equatorial vertical drift. In this work, we compare observations of the vertical drift using an HF radiosignals of opportunity in the Central Pacific with UV 135.6-nm observations of the equatorial anomalies from the DMSP/SSUSI andTIMED/GUVI instruments. Furthermore, we explore the role of E region density in modulating the vertical plasma drift using a passive HFsounding experiment in the Caribbean. Coupling between nighttime medium-scale traveling ionospheric disturbances (MSTIDs) and sporadic-Elayers has been suggested as a growth-rate-increasing process. While we observe sporadic-E in the local hemisphere coincident to increases in thealtitude of the F-region altitude, we also observe uplifts without sporadic-E in the local hemisphere. Apart from the trivial explanation that sporadic-E is occurring in the conjugate hemisphere, another possible explanation is that the E region may enhance the vertical drift, but is not required to produce enhanced vertical drifts. These studies represent fruitful areas of future intersection between ground-based observations and ICON and GOLD science.

Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH{sub 3}){sub n} and (NH{sub 3}BH{sub 3}){sub n} ionized at 10.51 eV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu; Shin, Joong-Won

A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH{sub 3}BH{sub 3}) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH{sub 3}BH{sub 3}){sub n} and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms andmore » potential energy surfaces for ionized NH{sub 3}BH{sub 3}, NH{sub 3}, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH{sub 3}){sub x}H{sup +} dominate ammonia cluster mass spectra: our calculations show that formation of (NH{sub 3}){sub n−1}H{sup +} and NH{sub 2} from the nascent (NH{sub 3}){sub n}{sup +} has the lowest energy barrier for the system. The only common features for the (NH{sub 3}){sub n}{sup +} and (NH{sub 3}BH{sub 3}){sub n}{sup +} mass spectra under these conditions are found to be NH{sub y}{sup +} (y = 0,…,4) at m/z = 14–18. Molecular ions with both {sup 11}B and {sup 10}B isotopes are observed, and therefore, product ions observed for the (NH{sub 3}BH{sub 3}){sub n} cluster system derive from (NH{sub 3}BH{sub 3}){sub n} clusters themselves, not from the NH{sub 3} moiety of NH{sub 3}BH{sub 3} alone. NH{sub 3}BH{sub 2}{sup +} is the most abundant ionization product in the (NH{sub 3}BH{sub 3}){sub n}{sup +} cluster spectra: calculations support that for NH{sub 3}BH{sub 3}{sup +}, an H atom is lost from the BH{sub 3} moiety with an energy barrier of 0.67 eV. For (NH{sub 3}BH{sub 3}){sub 2}{sup +} and (NH{sub 3}BH{sub 3}){sub 3}{sup +} clusters, a B{sup δ+}⋯H{sup δ−}⋯{sup δ−}H⋯{sup δ+}B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH{sub 3}BH{sub 3}){sub n}{sup +} (n = 2, 3) dissociation is the breaking of the B{sup δ+}⋯H{sup δ−}⋯{sup δ−}H⋯{sup δ+}B moiety, leading to the subsequent release of H{sub 2} from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF natural bond orbital description of the valence electron distribution for the various clusters and monomers. Comparison of the present results with those found for solid NH{sub 3}BH{sub 3} suggests that NH{sub 3}BH{sub 3} can be a good hydrogen storage material.« less

Threshold photoionization and density functional theory studies of bimetallic-carbide nanocrystals and fragments: Ta3ZrC(y) (y = 0-4).

PubMed

Dryza, V; Metha, G F

2009-06-28

Gas-phase bimetallic tantalum-zirconium-carbide clusters are generated using a constructed double ablation cluster source. The Ta(3)ZrC(y) (y = 0-4) clusters are examined by photoionization efficiency spectroscopy to extract experimental ionization energies (IEs). The IE trend for the Ta(3)ZrC(y) cluster series is reasonably similar to that of the Ta(4)C(y) cluster series [V. Dryza et al., J. Phys. Chem. A 109, 11180 (2005)], although the IE reductions upon carbon addition are greater for the former. Complementary density functional theory calculations are performed for the various isomers constructed by attaching carbon atoms to the different faces of the tetrahedral Ta(3)Zr cluster. The good agreement between the experimental IE trend and that calculated for these isomers support a 2x2x2 face centered cubic nanocrystal structure for Ta(4)ZrC(4) and nanocrystal fragment structures for the smaller clusters.

Photoinduced intermolecular dynamics and subsequent fragmentation in VUV-ionized acetamide clusters

NASA Astrophysics Data System (ADS)

Tarkanovskaja, Marta; Kooser, Kuno; Levola, Helena; Nõmmiste, Ergo; Kukk, Edwin

2016-09-01

Photofragmentation of small gas-phase acetamide clusters (CH3CONH2)n (n ≤ 10) produced by a supersonic expansion source has been studied using time-of-flight ion mass spectroscopy combined with tunable vacuum-ultraviolet (VUV) synchrotron radiation. Fragmentation channels of acetamide clusters under VUV photoionization resulting in protonated and ammoniated clusters formation were identified with the discussion about the preceding intramolecular rearrangements. Acetamide-2,2,2-d3 clusters were also studied in an experiment with a gas discharge lamp as a VUV light source; comparison with the main experiment gave insights into the mechanism of formation of protonated acetamide clusters, indicating that proton transfer from amino group plays a dominant role in that process. Geometry of the acetamide dimer was discussed and the most stable arrangement was concluded to be achieved when subunits of the dimer are connected via two N—H⋯O —C hydrogen bonds. Also, the influence of the photon energy on the stability of the clusters and their fragmentation channels has been examined.

Mass spectrometric identification of intermediates in the O2-driven [4Fe-4S] to [2Fe-2S] cluster conversion in FNR

PubMed Central

Crack, Jason C.; Thomson, Andrew J.

2017-01-01

The iron-sulfur cluster containing protein Fumarate and Nitrate Reduction (FNR) is the master regulator for the switch between anaerobic and aerobic respiration in Escherichia coli and many other bacteria. The [4Fe-4S] cluster functions as the sensory module, undergoing reaction with O2 that leads to conversion to a [2Fe-2S] form with loss of high-affinity DNA binding. Here, we report studies of the FNR cluster conversion reaction using time-resolved electrospray ionization mass spectrometry. The data provide insight into the reaction, permitting the detection of cluster conversion intermediates and products, including a [3Fe-3S] cluster and persulfide-coordinated [2Fe-2S] clusters [[2Fe-2S](S)n, where n = 1 or 2]. Analysis of kinetic data revealed a branched mechanism in which cluster sulfide oxidation occurs in parallel with cluster conversion and not as a subsequent, secondary reaction to generate [2Fe-2S](S)n species. This methodology shows great potential for broad application to studies of protein cofactor–small molecule interactions. PMID:28373574

Unrepaired clustered DNA lesions induce chromosome breakage in human cells

PubMed Central

Asaithamby, Aroumougame; Hu, Burong; Chen, David J.

2011-01-01

Clustered DNA damage induced by ionizing radiation is refractory to repair and may trigger carcinogenic events for reasons that are not well understood. Here, we used an in situ method to directly monitor induction and repair of clustered DNA lesions in individual cells. We showed, consistent with biophysical modeling, that the kinetics of loss of clustered DNA lesions was substantially compromised in human fibroblasts. The unique spatial distribution of different types of DNA lesions within the clustered damages, but not the physical location of these damages within the subnuclear domains, determined the cellular ability to repair the damage. We then examined checkpoint arrest mechanisms and yield of gross chromosomal aberrations. Induction of nonrepairable clustered damage affected only G2 accumulation but not the early G2/M checkpoint. Further, cells that were released from the G2/M checkpoint with unrepaired clustered damage manifested a spectrum of chromosome aberrations in mitosis. Difficulties associated with clustered DNA damage repair and checkpoint release before the completion of clustered DNA damage repair appear to promote genome instability that may lead to carcinogenesis. PMID:21527720

Meso-zooplankton abundance and spatial distribution off Lützow-Holm Bay during austral summer 2007-2008

NASA Astrophysics Data System (ADS)

Makabe, Ryosuke; Tanimura, Atsushi; Tamura, Takeshi; Hirano, Daisuke; Shimada, Keishi; Hashihama, Fuminori; Fukuchi, Mitsuo

2017-06-01

To elucidate spatial differences in mesozooplankton community structure in local scale, vertical hauls using a 60-μm mesh closing net were carried out off Lützow-Holm Bay in January 2008. All of the zooplankton samples collected from three layers (0-100, 100-200, and 200-500 m) at seven stations were dominated by Oithona spp., Oncaea spp., Ctenocalanus citer, Microcalanus pygmaeus, and copepod nauplii. The cluster analysis of mesozooplankton abundances showed three distinct groups according to sampling depth, which appeared to be due to the preferential vertical distribution of dominant copepods. The other cluster analysis on integrated abundance upper 500 m revealed that mesozooplankton community structures at stations located on the western and eastern edges of the observation area (Cluster A) differed from those at the central stations (Cluster B). Abundance of copepod nauplii, Oithona spp., and C. citer differed between Clusters A and B, which was likely caused by differences in recruitment and early development in the dominant copepods, being associated with the timing and duration of ice edge blooms. This suggests that such heterogeneity in abundance and recruitment/development of dominant taxa was likely caused by local heterogeneity in sea ice dynamics. This may affect our understanding of zooplankton distribution.

Gas-phase synthesis of singly and multiply charged polyoxovanadate anions employing electrospray ionization and collision induced dissociation.

PubMed

Al Hasan, Naila M; Johnson, Grant E; Laskin, Julia

2013-09-01

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy(n-) and VxOyCl(n-) ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N(+), tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCl(n-) and VxOyCl(L)((n-1)-) clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl((1-2)-) and VxOy ((1-2)-) anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

NASA Astrophysics Data System (ADS)

Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia

2013-09-01

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy n- and VxOyCln- ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N+, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCln- and VxOyCl(L)(n-1)- clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl(1-2)- and VxOy (1-2)- anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147

NASA Astrophysics Data System (ADS)

Häberlen, Oliver D.; Chung, Sai-Cheong; Stener, Mauro; Rösch, Notker

1997-03-01

A series of gold clusters spanning the size range from Au6 through Au147 (with diameters from 0.7 to 1.7 nm) in icosahedral, octahedral, and cuboctahedral structure has been theoretically investigated by means of a scalar relativistic all-electron density functional method. One of the main objectives of this work was to analyze the convergence of cluster properties toward the corresponding bulk metal values and to compare the results obtained for the local density approximation (LDA) to those for a generalized gradient approximation (GGA) to the exchange-correlation functional. The average gold-gold distance in the clusters increases with their nuclearity and correlates essentially linearly with the average coordination number in the clusters. An extrapolation to the bulk coordination of 12 yields a gold-gold distance of 289 pm in LDA, very close to the experimental bulk value of 288 pm, while the extrapolated GGA gold-gold distance is 297 pm. The cluster cohesive energy varies linearly with the inverse of the calculated cluster radius, indicating that the surface-to-volume ratio is the primary determinant of the convergence of this quantity toward bulk. The extrapolated LDA binding energy per atom, 4.7 eV, overestimates the experimental bulk value of 3.8 eV, while the GGA value, 3.2 eV, underestimates the experiment by almost the same amount. The calculated ionization potentials and electron affinities of the clusters may be related to the metallic droplet model, although deviations due to the electronic shell structure are noticeable. The GGA extrapolation to bulk values yields 4.8 and 4.9 eV for the ionization potential and the electron affinity, respectively, remarkably close to the experimental polycrystalline work function of bulk gold, 5.1 eV. Gold 4f core level binding energies were calculated for sites with bulk coordination and for different surface sites. The core level shifts for the surface sites are all positive and distinguish among the corner, edge, and face-centered sites; sites in the first subsurface layer show still small positive shifts.

Improving liquid chromatography-mass spectrometry sensitivity using a subambient pressure ionization with nanoelectrospray (SPIN) interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Keqi; Page, Jason S.; Marginean, Ioan

2011-04-22

In this work the Subambient Pressure Ionization with Nanoelectrospray (SPIN) ion source and interface which operates at ~15-30 Torr is demonstrated to be compatible with gradient reversed-phase liquid chromatography-MS applications, exemplified here with the analysis of complex samples (a protein tryptic digest and a whole cell lysate). A low liquid chromatographic flow rate (100-400 nL/min) allowed stable electrospray to be established while avoiding electrical breakdown. Efforts to increase the operating pressure of the SPIN source relative to previously reported designs prevented solvent freezing and enhanced charged cluster/droplet desolvation. A 5-12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospraymore » ionization (ESI) source was obtained for detected peptides.« less

IR signature of the photoionization-induced hydrophobic-->hydrophilic site switching in phenol-Arn clusters

NASA Astrophysics Data System (ADS)

Ishiuchi, Shun-ichi; Sakai, Makoto; Tsuchida, Yuji; Takeda, Akihiro; Kawashima, Yasutake; Dopfer, Otto; Müller-Dethlefs, Klaus; Fujii, Masaaki

2007-09-01

IR spectra of phenol-Arn (PhOH-Arn) clusters with n =1 and 2 were measured in the neutral and cationic electronic ground states in order to determine the preferential intermolecular ligand binding motifs, hydrogen bonding (hydrophilic interaction) versus π bonding (hydrophobic interaction). Analysis of the vibrational frequencies of the OH stretching motion, νOH, observed in nanosecond IR spectra demonstrates that neutral PhOH-Ar and PhOH -Ar2 as well as cationic PhOH +-Ar have a π-bound structure, in which the Ar atoms bind to the aromatic ring. In contrast, the PhOH +-Ar2 cluster cation is concluded to have a H-bound structure, in which one Ar atom is hydrogen-bonded to the OH group. This π →H binding site switching induced by ionization was directly monitored in real time by picosecond time-resolved IR spectroscopy. The π-bound νOH band is observed just after the ionization and disappears simultaneously with the appearance of the H-bound νOH band. The analysis of the picosecond IR spectra demonstrates that (i) the π →H site switching is an elementary reaction with a time constant of ˜7ps, which is roughly independent of the available internal vibrational energy, (ii) the barrier for the isomerization reaction is rather low(<100cm-1), (iii) both the position and the width of the H-bound νOH band change with the delay time, and the time evolution of these spectral changes can be rationalized by intracluster vibrational energy redistribution occurring after the site switching. The observation of the ionization-induced switch from π bonding to H bonding in the PhOH +-Ar2 cation corresponds to the first manifestation of an intermolecular isomerization reaction in a charged aggregate.

Bipolar H II regions produced by cloud-cloud collisions

NASA Astrophysics Data System (ADS)

Whitworth, Anthony; Lomax, Oliver; Balfour, Scott; Mège, Pierre; Zavagno, Annie; Deharveng, Lise

2018-05-01

We suggest that bipolar H II regions may be the aftermath of collisions between clouds. Such a collision will produce a shock-compressed layer, and a star cluster can then condense out of the dense gas near the center of the layer. If the clouds are sufficiently massive, the star cluster is likely to contain at least one massive star, which emits ionizing radiation, and excites an H II region, which then expands, sweeping up the surrounding neutral gas. Once most of the matter in the clouds has accreted onto the layer, expansion of the H II region meets little resistance in directions perpendicular to the midplane of the layer, and so it expands rapidly to produce two lobes of ionized gas, one on each side of the layer. Conversely, in directions parallel to the midplane of the layer, expansion of the H II region stalls due to the ram pressure of the gas that continues to fall towards the star cluster from the outer parts of the layer; a ring of dense neutral gas builds up around the waist of the bipolar H II region, and may spawn a second generation of star formation. We present a dimensionless model for the flow of ionized gas in a bipolar H II region created according to the above scenario, and predict the characteristics of the resulting free-free continuum and recombination-line emission. This dimensionless model can be scaled to the physical parameters of any particular system. Our intention is that these predictions will be useful in testing the scenario outlined above, and thereby providing indirect support for the role of cloud-cloud collisions in triggering star formation.

Endohedral beryllium atoms in germanium clusters with eight and fewer vertices: how small can a cluster be and still encapsulate a central atom?

PubMed

Uţă, M M; King, R B

2012-05-31

Structures of the beryllium-centered germanium clusters Be@Ge(n)(z) (n = 8, 7, 6; z = -4, -2, 0, +2) have been investigated by density functional theory to provide some insight regarding the smallest metal cluster that can encapsulate an interstitial atom. The lowest energy structures of the eight-vertex Be@Ge(8)(z) clusters (z = -4, -2, 0, +2) all have the Be atom at the center of a closed polyhedron, namely, a D(4d) square antiprism for Be@Ge(8)(4-), a D(2d) bisdisphenoid for Be@Ge(8)(2-), an ideal O(h) cube for Be@Ge(8), and a C(2v) distorted cube for Be@Ge(8)(2+). The Be-centered cubic structures predicted for Be@Ge(8) and Be@Ge(8)(2+) differ from the previously predicted lowest energy structures for the isoelectronic Ge(8)(2-) and Ge(8). This appears to be related to the larger internal volume of the cube relative to other closed eight-vertex polyhedra. The lowest energy structures for the smaller seven- and six-vertex clusters Be@Ge(n)(z) (n = 7, 6; z = -4, -2, 0, +2) no longer have the Be atom at the center of a closed Ge(n) polyhedron. Instead, either the Ge(n) polyhedron has opened up to provide a larger volume for the Be atom or the Be atom has migrated to the surface of the polyhedron. However, higher energy structures are found in which the Be atom is located at the center of a Ge(n) (n = 7, 6) polyhedron. Examples of such structures are a centered C(2v) capped trigonal prismatic structure for Be@Ge(7)(2-), a centered D(5h) pentagonal bipyramidal structure for Be@Ge(7), a centered D(3h) trigonal prismatic structure for Be@Ge(6)(4-), and a centered octahedral structure for Be@Ge(6). Cluster buildup reactions of the type Be@Ge(n)(z) + Ge(2) → Be@Ge(n+2)(z) (n = 6, 8; z = -4, -2, 0, +2) are all predicted to be highly exothermic. This suggests that interstitial clusters having an endohedral atom inside a bare post transition element polyhedron with eight or fewer vertices are less than the optimum size. This is consistent with the experimental observation of several types of 10-vertex polyhedral bare post transition element clusters with interstitial atoms but the failure to observe such clusters with external polyhedra having eight or fewer vertices.

Vertical profiles of CO and CH4 in the lower and middle troposphere over the Eastern United States January 1978

NASA Technical Reports Server (NTRS)

Reichle, H. G., Jr.; Condon, E. P.

1979-01-01

Samples of tropospheric air were obtained over the Eastern United States during January of 1978. These samples were analyzed by gas chromatography using flame ionization detection to produce vertical profiles of carbon monoxide and methane from the surface to 8 km. The carbon monoxide mixing ratios at 35 deg N and 45 deg N agree with previously published values; however, the mixing ratio at 25 deg N was significantly lower than most published values. The methane mixing ratio was weakly dependent on latitude and has an average value of 1.64 ppm.

Photoelectron spectroscopy of nitromethane anion clusters

NASA Astrophysics Data System (ADS)

Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

2016-08-01

Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

Stepped wedge designs: insights from a design of experiments perspective.

PubMed

Matthews, J N S; Forbes, A B

2017-10-30

Stepped wedge designs (SWDs) have received considerable attention recently, as they are potentially a useful way to assess new treatments in areas such as health services implementation. Because allocation is usually by cluster, SWDs are often viewed as a form of cluster-randomized trial. However, since the treatment within a cluster changes during the course of the study, they can also be viewed as a form of crossover design. This article explores SWDs from the perspective of crossover trials and designed experiments more generally. We show that the treatment effect estimator in a linear mixed effects model can be decomposed into a weighted mean of the estimators obtained from (1) regarding an SWD as a conventional row-column design and (2) a so-called vertical analysis, which is a row-column design with row effects omitted. This provides a precise representation of "horizontal" and "vertical" comparisons, respectively, which to date have appeared without formal description in the literature. This decomposition displays a sometimes surprising way the analysis corrects for the partial confounding between time and treatment effects. The approach also permits the quantification of the loss of efficiency caused by mis-specifying the correlation parameter in the mixed-effects model. Optimal extensions of the vertical analysis are obtained, and these are shown to be highly inefficient for values of the within-cluster dependence that are likely to be encountered in practice. Some recently described extensions to the classic SWD incorporating multiple treatments are also compared using the experimental design framework. Copyright © 2017 John Wiley & Sons, Ltd.

Incomplete segregation of endorgan-specific vestibular ganglion cells in mice and rats

NASA Technical Reports Server (NTRS)

Maklad, A.; Fritzsch, B.

1999-01-01

The endorgan-specific distribution of vestibular ganglion cells was studied in neonatal and postnatal rats and mice using indocarbocyanine dye (DiI) and dextran amines for retrograde and anterograde labeling. Retrograde DiI tracing from the anterior vertical canal labeled neurons scattered throughout the whole superior vestibular ganglion, with denser labeling at the dorsal and central regions. Horizontal canal neurons were scattered along the dorsoventral axis with more clustering toward the dorsal and ventral poles of this axis. Utricular ganglion cells occupied predominantly the central region of the superior vestibular ganglion. This utricular population overlapped with both the anterior vertical and horizontal canals' ganglion cells. Posterior vertical canal neurons were clustered in the posterior part of the inferior vestibular ganglion. The saccular neurons were distributed in the two parts of the vestibular ganglion, the superior and inferior ganglia. Within the inferior ganglion, the saccular neurons were clustered in the anterior part. In the superior ganglion, the saccular neurons were widely scattered throughout the whole ganglion with more numerous neurons at the posterior half. Small and large neurons were labeled from all endorgans. Examination of the fiber trajectory within the superior division of the vestibular nerve showed no clear lamination of the fibers innervating the different endorgans. These results demonstrate an overlapping pattern between the different populations within the superior ganglion, while in the inferior ganglion, the posterior canal and saccular neurons show tighter clustering but incomplete segregation. This distribution implies that the ganglion cells are assigned for their target during development in a stochastic rather than topographical fashion.

Interatomic Coulombic decay cascades in multiply excited neon clusters

PubMed Central

Nagaya, K.; Iablonskyi, D.; Golubev, N. V.; Matsunami, K.; Fukuzawa, H.; Motomura, K.; Nishiyama, T.; Sakai, T.; Tachibana, T.; Mondal, S.; Wada, S.; Prince, K. C.; Callegari, C.; Miron, C.; Saito, N.; Yabashi, M.; Demekhin, Ph. V.; Cederbaum, L. S.; Kuleff, A. I.; Yao, M.; Ueda, K.

2016-01-01

In high-intensity laser light, matter can be ionized by direct multiphoton absorption even at photon energies below the ionization threshold. However on tuning the laser to the lowest resonant transition, the system becomes multiply excited, and more efficient, indirect ionization pathways become operative. These mechanisms are known as interatomic Coulombic decay (ICD), where one of the species de-excites to its ground state, transferring its energy to ionize another excited species. Here we show that on tuning to a higher resonant transition, a previously unknown type of interatomic Coulombic decay, intra-Rydberg ICD occurs. In it, de-excitation of an atom to a close-lying Rydberg state leads to electron emission from another neighbouring Rydberg atom. Moreover, systems multiply excited to higher Rydberg states will decay by a cascade of such processes, producing even more ions. The intra-Rydberg ICD and cascades are expected to be ubiquitous in weakly-bound systems exposed to high-intensity resonant radiation. PMID:27917867

Method and apparatus for confinement of ions in the presence of a neutral gas

DOEpatents

Peurrung, Anthony J.; Barlow, Stephan E.

1999-01-01

The present invention is an apparatus and method for combining ions with a neutral gas and flowing the mixture with a radial flow component through a magnetic field so that the weakly ionized gas is confined by the neutral gas. When the weakly ionized gas is present in sufficient density, a weakly ionized non-neutral plasma is formed that may be trapped in accordance with the present invention. Applications for a weakly ionized non-neutral plasma exploit the trap's ability to store and manipulate ionic species in the presence of neutral gas. The trap may be connected to a mass spectrometer thereby permitting species identification after a fixed period of time. Delicate and/or heavy particles such as clusters may be held and studied in a "gentle" environment. In addition, the trap can provide a relatively intense, low-energy source of a particular ion species for surface implantation or molecular chemistry. Finally, a long trap may permit spectroscopy of unprecedented accuracy to be performed on ionic species.

Onset of carbon-carbon bonding in Ta(5)C(y) (y = 0-6) clusters: a threshold photoionization and density functional theory study.

PubMed

Dryza, Viktoras; Alvino, Jason F; Metha, Gregory F

2010-04-01

We have used photoionization efficiency spectroscopy to determine ionization energies (IEs) of the gas-phase tantalum-carbide clusters Ta(5)C(y) (y = 0-6). The structures of the clusters observed in the experiment are assigned by comparing the experimental IEs with those of candidate isomers, calculated by density functional theory. Two competing geometries of the underlying Ta(5) cluster are found to be present in the assigned Ta(5)C(y) structures; either a "prolate" or "distorted oblate" trigonal bipyramid geometry. The onset of carbon-carbon bonding in the Ta(5)C(y) series is proposed to occur at y = 6, with the structure of Ta(5)C(6) containing two molecular C(2) units.

Multiple hydrogen bonds. Mass spectra of hydrogen bonded heterodimers. A comparison of ESI- and REMPI-ReTOF-MS.

PubMed

Taubitz, Jörg; Lüning, Ulrich; Grotemeyer, Jürgen

2004-11-07

Resonance enhanced multi-photon ionization-reflectron time of flight mass spectrometry is the analytical method of choice to observe hydrogen bonded supramolecules in the gas phase when protonation of basic centers competes with cluster formation.

Comparative genomics reveals phylogenetic distribution patterns of secondary metabolites in Amycolatopsis species.

PubMed

Adamek, Martina; Alanjary, Mohammad; Sales-Ortells, Helena; Goodfellow, Michael; Bull, Alan T; Winkler, Anika; Wibberg, Daniel; Kalinowski, Jörn; Ziemert, Nadine

2018-06-01

Genome mining tools have enabled us to predict biosynthetic gene clusters that might encode compounds with valuable functions for industrial and medical applications. With the continuously increasing number of genomes sequenced, we are confronted with an overwhelming number of predicted clusters. In order to guide the effective prioritization of biosynthetic gene clusters towards finding the most promising compounds, knowledge about diversity, phylogenetic relationships and distribution patterns of biosynthetic gene clusters is necessary. Here, we provide a comprehensive analysis of the model actinobacterial genus Amycolatopsis and its potential for the production of secondary metabolites. A phylogenetic characterization, together with a pan-genome analysis showed that within this highly diverse genus, four major lineages could be distinguished which differed in their potential to produce secondary metabolites. Furthermore, we were able to distinguish gene cluster families whose distribution correlated with phylogeny, indicating that vertical gene transfer plays a major role in the evolution of secondary metabolite gene clusters. Still, the vast majority of the diverse biosynthetic gene clusters were derived from clusters unique to the genus, and also unique in comparison to a database of known compounds. Our study on the locations of biosynthetic gene clusters in the genomes of Amycolatopsis' strains showed that clusters acquired by horizontal gene transfer tend to be incorporated into non-conserved regions of the genome thereby allowing us to distinguish core and hypervariable regions in Amycolatopsis genomes. Using a comparative genomics approach, it was possible to determine the potential of the genus Amycolatopsis to produce a huge diversity of secondary metabolites. Furthermore, the analysis demonstrates that horizontal and vertical gene transfer play an important role in the acquisition and maintenance of valuable secondary metabolites. Our results cast light on the interconnections between secondary metabolite gene clusters and provide a way to prioritize biosynthetic pathways in the search and discovery of novel compounds.

Studying Townsend and glow modes in an atmospheric-pressure DBD using mass spectrometry

NASA Astrophysics Data System (ADS)

McKay, Kirsty; Donaghy, David; He, Feng; Bradley, James W.

2018-01-01

Ambient molecular beam mass spectrometry has been employed to examine the effects of the mode of operation and the excitation waveform on the ionic content of a helium-based atmospheric-pressure parallel plate dielectric barrier discharge. By applying 10 kHz microsecond voltage pulses with a nanosecond rise times and 10 kHz sinusoidal voltage waveforms, distinctly different glow and Townsend modes were produced, respectively. Results showed a significant difference in the dominant ion species between the two modes. In the Townsend mode, molecular oxygen ions, atomic oxygen anions and nitric oxide anions are the most abundant species, however, in the glow mode water clusters ions and hydrated nitric oxygen anions dominate. Several hypotheses are put forward to explain these differences, including low electron densities and energies in the Townsend mode, more efficient ionization of water molecules through penning ionization and charge exchange with other species in glow mode, and large temperature gradients due to the pulsed nature of the glow mode, leading to more favorable conditions for cluster formation.

Influence of oxygen on the chemical stage of radiobiological mechanism

NASA Astrophysics Data System (ADS)

Barilla, Jiří; Lokajíček, Miloš V.; Pisaková, Hana; Simr, Pavel

2016-07-01

The simulation of the chemical stage of radiobiological mechanism may be very helpful in studying the radiobiological effect of ionizing radiation when the water radical clusters formed by the densely ionizing ends of primary or secondary charged particle may form DSBs damaging DNA molecules in living cells. It is possible to study not only the efficiency of individual radicals but also the influence of other species or radiomodifiers (mainly oxygen) being present in water medium during irradiation. The mathematical model based on Continuous Petri nets (proposed by us recently) will be described. It makes it possible to analyze two main processes running at the same time: chemical radical reactions and the diffusion of radical clusters formed during energy transfer. One may study the time change of radical concentrations due to the chemical reactions running during diffusion process. Some orientation results concerning the efficiency of individual radicals in DSB formation (in the case of Co60 radiation) will be presented; the influence of oxygen present in water medium during irradiation will be shown, too.

Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

NASA Astrophysics Data System (ADS)

Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

2017-04-01

Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (<200 ppt). We report on the effect of atmospheric water vapor and oxygen concentrations on instrument response for isoprene and a wide range of monoterpenes and sesquiterpenes. To gain mechanistic insight into the ion-molecule reactions and the role of water vapor and oxygen, we compare our measured sensitivities with a computational analysis of the charge distribution between the analyte, reagent ion and water molecules in the gas phase. These parameters provide insight on the ionization mechanism and provide parameters for quantification of organic molecules measured during field campaigns. References Kim, M. J., M. C. Zoerb, N. R. Campbell, K. J. Zimmermann, B. W. Blomquist, B. J. Huebert, and T. H. Bertram (2016), Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

Fluctuations in microwave background radiation due to secondary ionization of the intergalactic gas in the universe

NASA Technical Reports Server (NTRS)

Sunyayev, R. A.

1979-01-01

Secondary heating and ionization of the intergalactic gas at redshifts z approximately 10-30 could lead to the large optical depth of the Universe for Thomson scattering and could smooth the primordial fluctuations formed at z approximately 1500. It is shown that the gas motions connected with the large scale density perturbations at z approximately 10-15 must lead to the generation of secondary fluctuations of microwave background. The contribution of the rich clusters of galaxies and young galaxies to the fluctuations of microwave background is also estimated.

Capturing the Interplay of Dynamics and Networks through Parameterizations of Laplacian Operators

DTIC Science & Technology

2016-08-24

important vertices and communities in the network. Specifically, for each dynamical process in this framework, we define a centrality measure that...vertices as a potential cluster (or community ) with respect to this process. We show that the subset-quality function generalizes the traditional conductance...compare the different perspectives they create on network structure. Subjects Network Science and Online Social Networks Keywords Network, Community

Population buildup and vertical spread of dwarf mistletoe on young red and white firs in California

Treesearch

Robert F. Scharpf; John R. Parmeter Jr.

1976-01-01

Rate of population buildup of dwarf mistletoe, Arceuthobium abietinum Engelm. ex Munz., was slow in most small red firs and white firs 12 to 15 years after inoculation with the parasite. Where population buildup did occur, it remained clustered in the lower portions of tree crowns near inoculation sites. Maximum distance of vertical spread was 16...

Quantum mechanical calculations related to ionization and charge transfer in DNA

NASA Astrophysics Data System (ADS)

Cauët, E.; Valiev, M.; Weare, J. H.; Liévin, J.

2012-07-01

Ionization and charge migration in DNA play crucial roles in mechanisms of DNA damage caused by ionizing radiation, oxidizing agents and photo-irradiation. Therefore, an evaluation of the ionization properties of the DNA bases is central to the full interpretation and understanding of the elementary reactive processes that occur at the molecular level during the initial exposure and afterwards. Ab initio quantum mechanical (QM) methods have been successful in providing highly accurate evaluations of key parameters, such as ionization energies (IE) of DNA bases. Hence, in this study, we performed high-level QM calculations to characterize the molecular energy levels and potential energy surfaces, which shed light on ionization and charge migration between DNA bases. In particular, we examined the IEs of guanine, the most easily oxidized base, isolated and embedded in base clusters, and investigated the mechanism of charge migration over two and three stacked guanines. The IE of guanine in the human telomere sequence has also been evaluated. We report a simple molecular orbital analysis to explain how modifications in the base sequence are expected to change the efficiency of the sequence as a hole trap. Finally, the application of a hybrid approach combining quantum mechanics with molecular mechanics brings an interesting discussion as to how the native aqueous DNA environment affects the IE threshold of nucleobases.

Clustering Qualitative Data Based on Binary Equivalence Relations: Neighborhood Search Heuristics for the Clique Partitioning Problem

ERIC Educational Resources Information Center

Brusco, Michael J.; Kohn, Hans-Friedrich

2009-01-01

The clique partitioning problem (CPP) requires the establishment of an equivalence relation for the vertices of a graph such that the sum of the edge costs associated with the relation is minimized. The CPP has important applications for the social sciences because it provides a framework for clustering objects measured on a collection of nominal…

An application of cluster detection to scene analysis

NASA Technical Reports Server (NTRS)

Rosenfeld, A. H.; Lee, Y. H.

1971-01-01

Certain arrangements of local features in a scene tend to group together and to be seen as units. It is suggested that in some instances, this phenomenon might be interpretable as a process of cluster detection in a graph-structured space derived from the scene. This idea is illustrated using a class of scenes that contain only horizontal and vertical line segments.

Clusters of DNA induced by ionizing radiation: formation of short DNA fragments. I. Theoretical modeling

NASA Technical Reports Server (NTRS)

Holley, W. R.; Chatterjee, A.

1996-01-01

We have developed a general theoretical model for the interaction of ionizing radiation with chromatin. Chromatin is modeled as a 30-nm-diameter solenoidal fiber comprised of 20 turns of nucleosomes, 6 nucleosomes per turn. Charged-particle tracks are modeled by partitioning the energy deposition between primary track core, resulting from glancing collisions with 100 eV or less per event, and delta rays due to knock-on collisions involving energy transfers >100 eV. A Monte Carlo simulation incorporates damages due to the following molecular mechanisms: (1) ionization of water molecules leading to the formation of OH, H, eaq, etc.; (2) OH attack on sugar molecules leading to strand breaks: (3) OH attack on bases; (4) direct ionization of the sugar molecules leading to strand breaks; (5) direct ionization of the bases. Our calculations predict significant clustering of damage both locally, over regions up to 40 bp and over regions extending to several kilobase pairs. A characteristic feature of the regional damage predicted by our model is the production of short fragments of DNA associated with multiple nearby strand breaks. The shapes of the spectra of DNA fragment lengths depend on the symmetries or approximate symmetries of the chromatin structure. Such fragments have subsequently been detected experimentally and are reported in an accompanying paper (B. Rydberg, Radiat, Res. 145, 200-209, 1996) after exposure to both high- and low-LET radiation. The overall measured yields agree well quantitatively with the theoretical predictions. Our theoretical results predict the existence of a strong peak at about 85 bp, which represents the revolution period about the nucleosome. Other peaks at multiples of about 1,000 bp correspond to the periodicity of the particular solenoid model of chromatin used in these calculations. Theoretical results in combination with experimental data on fragmentation spectra may help determine the consensus or average structure of the chromatin fibers in mammalian DNA.

Redox-linked ionization of sulredoxin, an archaeal Rieske-type [2Fe-2S] protein from Sulfolobus sp. strain 7.

PubMed

Iwasaki, T; Imai, T; Urushiyama, A; Oshima, T

1996-11-01

"Sulredoxin" of Sulfolobus sp. strain 7 is an archaeal soluble Rieske-type [2Fe-2S] protein and was initially characterized by several spectroscopic techniques (Iwasaki, T., Isogai, T., Iizuka, T. , and Oshima, T. (1995) J. Bacteriol. 177, 2576-2582). It appears to have tightly linked ionization affecting the redox properties of the protein, which is characteristic of the Rieske FeS proteins found as part of the respiratory chain. Sulredoxin had an Em(low pH) value of +188 +/- 9 mV, and the slope of pH dependence of the midpoint redox potential indicated two ionization equilibria in the oxidized form with pKa(ox1) of 6.23 +/- 0.22 and pKa(ox2) of 8.57 +/- 0.20. The absorption, CD, and resonance Raman spectra of oxidized sulredoxin are consistent with the proposed St2FeSb2Fe[N(His)]t2 core structure, and deprotonation of one of the two putative coordinated histidine imidazoles, having the pKa(ox2) of 8.57 +/- 0.20, causes a decrease in the midpoint redox potential, the change in the optical and CD spectra, and the appearance of a new Raman transition at 278 cm-1, without major structural rearrangement of the [2Fe-2S] cluster as well as the overall protein conformation. The redox-linked ionization of sulredoxin is also contributed by local changes involving another ionizable group having the pKa(ox1) of 6.23 +/- 0. 22, which is probably attributed to a certain positively charged amino acid residue that may not be a ligand by itself but located very close to the cluster. We suggest that sulredoxin provides a new tractable model of the membrane-bound homologue of the respiratory chain, the Rieske FeS proteins of the cytochrome bc1-b6f complexes.

Modelling clustering of vertically aligned carbon nanotube arrays.

PubMed

Schaber, Clemens F; Filippov, Alexander E; Heinlein, Thorsten; Schneider, Jörg J; Gorb, Stanislav N

2015-08-06

Previous research demonstrated that arrays of vertically aligned carbon nanotubes (VACNTs) exhibit strong frictional properties. Experiments indicated a strong decrease of the friction coefficient from the first to the second sliding cycle in repetitive measurements on the same VACNT spot, but stable values in consecutive cycles. VACNTs form clusters under shear applied during friction tests, and self-organization stabilizes the mechanical properties of the arrays. With increasing load in the range between 300 µN and 4 mN applied normally to the array surface during friction tests the size of the clusters increases, while the coefficient of friction decreases. To better understand the experimentally obtained results, we formulated and numerically studied a minimalistic model, which reproduces the main features of the system with a minimum of adjustable parameters. We calculate the van der Waals forces between the spherical friction probe and bunches of the arrays using the well-known Morse potential function to predict the number of clusters, their size, instantaneous and mean friction forces and the behaviour of the VACNTs during consecutive sliding cycles and at different normal loads. The data obtained by the model calculations coincide very well with the experimental data and can help in adapting VACNT arrays for biomimetic applications.

Vertical Leaching of Allelochemicals Affecting Their Bioactivity and the Microbial Community of Soil.

PubMed

Xiao, Zhongxiang; Le, Chang; Xu, Zhenghao; Gu, Zhefeng; Lv, Junfei; Shamsi, Imran Haider

2017-09-13

Leaching of allelochemicals in soil is one of the fundamental processes that determines allelopathic activities but is often overlooked. In the present study, the vertical leaching of seven putative allelochemicals as well as one pesticide and one herbicide was investigated using polyvinyl chloride columns combined with a bioassay approach. The results indicated that the leachability of pretilachlor and imidacloprid were the best (Lf > 0.8), followed by vanillin and coumarin (Lf > 0.6). The leachability of daidzein, menthol, and m-tyrosine were medium (0.3 < Lf < 0.6). The lowest leachability has been observed on p-coumaric and p-hydroxybenzoic acids (Lf < 0.3). The chemicals were classified into three clusters according to the phospholipid fatty acid profile (i.e., vanillin in one cluster, coumarin and menthol in the second cluster, and the rest in the third cluster). Bioactivities of the chemicals changed dramatically. Germination of lettuce seeds was suppressed by imidacloprid and pretilachlor, and the suppression was concentration-dependent. The bioactivity of most of the allelochemicals were progressively decreased with the downward movement of chemicals. The results indicated that leaching mediated the microbial communities and the interactions of chemical-microorganism and modified the bioavailability of allelochemicals in soil.

Radiative Feedback of Forming Star Clusters on Their GMC Environments: Theory and Simulation

NASA Astrophysics Data System (ADS)

Howard, C. S.; Pudritz, R. E.; Harris, W. E.

2013-07-01

Star clusters form from dense clumps within a molecular cloud. Radiation from these newly formed clusters feeds back on their natal molecular cloud through heating and ionization which ultimately stops gas accretion into the cluster. Recent studies suggest that radiative feedback effects from a single cluster may be sufficient to disrupt an entire cloud over a short timescale. Simulating cluster formation on a large scale, however, is computationally demanding due to the high number of stars involved. For this reason, we present a model for representing the radiative output of an entire cluster which involves randomly sampling an initial mass function (IMF) as the cluster accretes mass. We show that this model is able to reproduce the star formation histories of observed clusters. To examine the degree to which radiative feedback shapes the evolution of a molecular cloud, we use the FLASH adaptive-mesh refinement hydrodynamics code to simulate cluster formation in a turbulent cloud. Unlike previous studies, sink particles are used to represent a forming cluster rather than individual stars. Our cluster model is then coupled with a raytracing scheme to treat radiative transfer as the clusters grow in mass. This poster will outline the details of our model and present preliminary results from our 3D hydrodynamical simulations.

Geometry of the Gene Expression Space of Individual Cells

PubMed Central

Korem, Yael; Szekely, Pablo; Hart, Yuval; Sheftel, Hila; Hausser, Jean; Mayo, Avi; Rothenberg, Michael E.; Kalisky, Tomer; Alon, Uri

2015-01-01

There is a revolution in the ability to analyze gene expression of single cells in a tissue. To understand this data we must comprehend how cells are distributed in a high-dimensional gene expression space. One open question is whether cell types form discrete clusters or whether gene expression forms a continuum of states. If such a continuum exists, what is its geometry? Recent theory on evolutionary trade-offs suggests that cells that need to perform multiple tasks are arranged in a polygon or polyhedron (line, triangle, tetrahedron and so on, generally called polytopes) in gene expression space, whose vertices are the expression profiles optimal for each task. Here, we analyze single-cell data from human and mouse tissues profiled using a variety of single-cell technologies. We fit the data to shapes with different numbers of vertices, compute their statistical significance, and infer their tasks. We find cases in which single cells fill out a continuum of expression states within a polyhedron. This occurs in intestinal progenitor cells, which fill out a tetrahedron in gene expression space. The four vertices of this tetrahedron are each enriched with genes for a specific task related to stemness and early differentiation. A polyhedral continuum of states is also found in spleen dendritic cells, known to perform multiple immune tasks: cells fill out a tetrahedron whose vertices correspond to key tasks related to maturation, pathogen sensing and communication with lymphocytes. A mixture of continuum-like distributions and discrete clusters is found in other cell types, including bone marrow and differentiated intestinal crypt cells. This approach can be used to understand the geometry and biological tasks of a wide range of single-cell datasets. The present results suggest that the concept of cell type may be expanded. In addition to discreet clusters in gene-expression space, we suggest a new possibility: a continuum of states within a polyhedron, in which the vertices represent specialists at key tasks. PMID:26161936

Infrared Multiple Photon Dissociation Spectroscopy Of Metal Cluster-Adducts

NASA Astrophysics Data System (ADS)

Cox, D. M.; Kaldor, A.; Zakin, M. R.

1987-01-01

Recent development of the laser vaporization technique combined with mass-selective detection has made possible new studies of the fundamental chemical and physical properties of unsupported transition metal clusters as a function of the number of constituent atoms. A variety of experimental techniques have been developed in our laboratory to measure ionization threshold energies, magnetic moments, and gas phase reactivity of clusters. However, studies have so far been unable to determine the cluster structure or the chemical state of chemisorbed species on gas phase clusters. The application of infrared multiple photon dissociation IRMPD to obtain the IR absorption properties of metal cluster-adsorbate species in a molecular beam is described here. Specifically using a high power, pulsed CO2 laser as the infrared source, the IRMPD spectrum for methanol chemisorbed on small iron clusters is measured as a function of the number of both iron atoms and methanols in the complex for different methanol isotopes. Both the feasibility and potential utility of IRMPD for characterizing metal cluster-adsorbate interactions are demonstrated. The method is generally applicable to any cluster or cluster-adsorbate system dependent only upon the availability of appropriate high power infrared sources.

Carbon atom and cluster sputtering under low-energy noble gas plasma bombardment

NASA Astrophysics Data System (ADS)

Oyarzabal, E.; Doerner, R. P.; Shimada, M.; Tynan, G. R.

2008-08-01

Exit-angle resolved carbon atom and cluster (C2 and C3) sputtering yields are measured during different noble gas (Xe, Kr, Ar, Ne, and He) ion bombardments from a plasma, for low incident energies (75-225 eV). A quadrupole mass spectrometer (QMS) is used to detect the fraction of sputtered neutrals that is ionized in the plasma and to obtain the angular distribution by changing the angle between the target normal and the QMS aperture. A one-dimensional Monte Carlo code is used to simulate the interaction of the plasma and the sputtered particles in the region between the sample and the QMS. The effective elastic scattering cross sections of C, C2, and C3 with the different bombarding gas neutrals are obtained by varying the distance between the sample and the QMS and by performing a best fit of the simulation results to the experimental results. The total sputtering yield (C+C2+C3) for each bombarding gas is obtained from weight-loss measurements and the sputtering yield for C, C2, and C3 is then calculated from the integration of the measured angular distribution, taking into account the scattering and ionization of the sputtered particles between the sample and the QMS. We observe undercosine angular distributions of the sputtered atoms and clusters for all the studied bombarding gases and a clear decrease of the atom to cluster (C2 and C3) sputtering ratio as the incident ion mass increases, changing from a carbon atom preferential erosion for the lower incident ion masses (He, Ne, and Ar) to a cluster preferential erosion for the higher incident ion masses (Kr and Xe).

AGS vertical beta function measurements for Run 15

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harper, C.; Ahrens, L.; Huang, H.

2016-10-07

One key parameter for running the AGS efficiently is by maintaining a low emittance. To measure emittance, one needs to measure the beta function throughout the cycle. This can be done by measuring the beta function at the ionization profile monitors (IPM) in the AGS. This tech note delves into the motivation, the measurement, and some strides that were made throughout Run15.

Method for eliminating artifacts in CCD imagers

DOEpatents

Turko, Bojan T.; Yates, George J.

1992-01-01

An electronic method for eliminating artifacts in a video camera (10) employing a charge coupled device (CCD) (12) as an image sensor. The method comprises the step of initializing the camera (10) prior to normal read out and includes a first dump cycle period (76) for transferring radiation generated charge into the horizontal register (28) while the decaying image on the phosphor (39) being imaged is being integrated in the photosites, and a second dump cycle period (78), occurring after the phosphor (39) image has decayed, for rapidly dumping unwanted smear charge which has been generated in the vertical registers (32). Image charge is then transferred from the photosites (36) and (38) to the vertical registers (32) and read out in conventional fashion. The inventive method allows the video camera (10) to be used in environments having high ionizing radiation content, and to capture images of events of very short duration and occurring either within or outside the normal visual wavelength spectrum. Resultant images are free from ghost, smear and smear phenomena caused by insufficient opacity of the registers (28) and (32), and are also free from random damage caused by ionization charges which exceed the charge limit capacity of the photosites (36) and (37).

Track structure in radiation biology: theory and applications.

PubMed

Nikjoo, H; Uehara, S; Wilson, W E; Hoshi, M; Goodhead, D T

1998-04-01

A brief review is presented of the basic concepts in track structure and the relative merit of various theoretical approaches adopted in Monte-Carlo track-structure codes are examined. In the second part of the paper, a formal cluster analysis is introduced to calculate cluster-distance distributions. Total experimental ionization cross-sections were least-square fitted and compared with the calculation by various theoretical methods. Monte-Carlo track-structure code Kurbuc was used to examine and compare the spectrum of the secondary electrons generated by using functions given by Born-Bethe, Jain-Khare, Gryzinsky, Kim-Rudd, Mott and Vriens' theories. The cluster analysis in track structure was carried out using the k-means method and Hartigan algorithm. Data are presented on experimental and calculated total ionization cross-sections: inverse mean free path (IMFP) as a function of electron energy used in Monte-Carlo track-structure codes; the spectrum of secondary electrons generated by different functions for 500 eV primary electrons; cluster analysis for 4 MeV and 20 MeV alpha-particles in terms of the frequency of total cluster energy to the root-mean-square (rms) radius of the cluster and differential distance distributions for a pair of clusters; and finally relative frequency distribution for energy deposited in DNA, single-strand break and double-strand breaks for 10MeV/u protons, alpha-particles and carbon ions. There are a number of Monte-Carlo track-structure codes that have been developed independently and the bench-marking presented in this paper allows a better choice of the theoretical method adopted in a track-structure code to be made. A systematic bench-marking of cross-sections and spectra of the secondary electrons shows differences between the codes at atomic level, but such differences are not significant in biophysical modelling at the macromolecular level. Clustered-damage evaluation shows: that a substantial proportion of dose ( 30%) is deposited by low-energy electrons; the majority of DNA damage lesions are of simple type; the complexity of damage increases with increased LET, while the total yield of strand breaks remains constant; and at high LET values nearly 70% of all double-strand breaks are of complex type.

The NGC 281 west cluster. I. Star formation in photoevaporating clumps.

NASA Astrophysics Data System (ADS)

Megeath, S. T.; Wilson, T. L.

1997-09-01

The NGC281 West molecular cloud is an excellent test case for studying star formation in the clumpy interface between a \\hii region and a giant molecular cloud. We present here a study based on new high resolution radio and near-infrared data. Using the IRAM 30-meter telescope, we have mapped the interface in the \\cotwo, \\coone, and \\cs transitions with FWHP beamwidths <= 22''. We have imaged the same region with the VLA in the 20, 6 and 2 cm continuum bands to obtain complementary maps of the ionized gas distribution with angular resolutions <= 13''. In addition, we have obtained near-infrared J and K'-band images to detect young stars in the interface. The 30-meter data shows the molecular gas is concentrated into three clumps with masses of 570, > 210, and 300 \\msun and average volume densities of 1.4, >1, and 2 x 10(4) \\cm. We detect \\cs emission in two of the clumps, indicating peak densities in excess of 5x 10(5) \\cm are attained in the clumps. A comparison of the \\co line data with the 20 cm continuum image suggests that the molecular clumps are being photoevaporated through their direct exposure to the UV radiation from neighboring OB stars. The luminosity and extent of the observed 20 cm emission is in good agreement with theoretical predictions. We use models of photoevaporative flows to estimate the pressure exerted on the clumps by the ionized gas and find that it exceeds the internal, turbulent pressure of the clumps by a factor of a 2.5. Although a pressure equilibrium is not excluded given the uncertainties inherent in determining the pressures of the ionized and molecular gases, our best estimates of the clumps and flow parameters favor the the existence of low velocity shocks (1.5 \\kms) in the clumps. The clumps exhibit broad, non-gaussian lineshapes and complex kinematical structures suggestive of shocks. Further evidence for shocks is found in a comparison of position-velocity diagrams with published numerical simulations of imploding spherical clumps. We discuss the possibility that the knots of \\cs emission may trace gas compressed by converging shock waves. The K'-band observations show a rich cluster of primarily low mass stars in the \\hii/molecular interface, which we argue is divided into two distinct sub-clusters. We associate one sub-cluster with the two clumps nearest the OB stars, and the second sub-cluster with the third clump. The two clumps nearest the OB stars contain an embedded population, suggesting that star formation is ongoing. We discuss the impact photoevaporation is having on star formation in these two clumps. We find that photoevaporation is dispersing the molecular gas from which the cluster is forming and estimate that the molecular gas will be completely evaporated in 5 Myr. Deep K'-band imaging of the two clumps show that the stars are detected primarily on the sides of the clumps facing the OB stars and in the adjoining \\hii region. We examine three explanations for this asymmetry: displacement of the clump centers from the cluster center by the acceleration of the molecular gas through photoevaporation (i.e. the rocket effect), unveiling of young, embedded stars by ionization-shock fronts, and the triggered formation of stars by shocks advancing into the clumps. If shock compression is indeed ongoing in the clumps, then we argue that there is a good case for shock triggered star formation.

Enhanced one-photon double ionization of atoms and molecules in an environment of different species.

PubMed

Stumpf, V; Kryzhevoi, N V; Gokhberg, K; Cederbaum, L S

2014-05-16

The correlated nature of electronic states in atoms and molecules is manifested in the simultaneous emission of two electrons after absorption of a single photon close to the respective threshold. Numerous observations in atoms and small molecules demonstrate that the double ionization efficiency close to threshold is rather small. In this Letter we show that this efficiency can be dramatically enhanced in the environment. To be specific, we concentrate on the case where the species in question has one or several He atoms as neighbors. The enhancement is achieved by an indirect process, where a He atom of the environment absorbs a photon and the resulting He(+) cation is neutralized fast by a process known as electron transfer mediated decay, producing thereby doubly ionized species. The enhancement of the double ionization is demonstrated in detail for the example of the Mg · He cluster. We show that the double ionization cross section of Mg becomes 3 orders of magnitude larger than the respective cross section of the isolated Mg atom. The impact of more neighbors is discussed and the extension to other species and environments is addressed.

Röntgen spheres around active stars

NASA Astrophysics Data System (ADS)

Locci, Daniele; Cecchi-Pestellini, Cesare; Micela, Giuseppina; Ciaravella, Angela; Aresu, Giambattista

2018-01-01

X-rays are an important ingredient of the radiation environment of a variety of stars of different spectral types and age. We have modelled the X-ray transfer and energy deposition into a gas with solar composition, through an accurate description of the electron cascade following the history of the primary photoelectron energy deposition. We test and validate this description studying the possible formation of regions in which X-rays are the major ionization channel. Such regions, called Röntgen spheres may have considerable importance in the chemical and physical evolution of the gas embedding the emitting star. Around massive stars the concept of Röntgen sphere appears to be of limited use, as the formation of extended volumes with relevant levels of ionization is efficient just in a narrow range of gas volume densities. In clouds embedding low-mass pre-main-sequence stars significant volumes of gas are affected by ionization levels exceeding largely the cosmic-ray background ionization. In clusters arising in regions of vigorous star formation X-rays create an ionization network pervading densely the interstellar medium, and providing a natural feedback mechanism, which may affect planet and star formation processes.

Fast Atom Ionization in Strong Electromagnetic Radiation

NASA Astrophysics Data System (ADS)

Apostol, M.

2018-05-01

The Goeppert-Mayer and Kramers-Henneberger transformations are examined for bound charges placed in electromagnetic radiation in the non-relativistic approximation. The consistent inclusion of the interaction with the radiation field provides the time evolution of the wavefunction with both structural interaction (which ensures the bound state) and electromagnetic interaction. It is shown that in a short time after switching on the high-intensity radiation the bound charges are set free. In these conditions, a statistical criterion is used to estimate the rate of atom ionization. The results correspond to a sudden application of the electromagnetic interaction, in contrast with the well-known ionization probability obtained by quasi-classical tunneling through classically unavailable non-stationary states, or other equivalent methods, where the interaction is introduced adiabatically. For low-intensity radiation the charges oscillate and emit higher-order harmonics, the charge configuration is re-arranged and the process is resumed. Tunneling ionization may appear in these circumstances. Extension of the approach to other applications involving radiation-induced charge emission from bound states is discussed, like ionization of molecules, atomic clusters or proton emission from atomic nuclei. Also, results for a static electric field are included.

Large-scale magnetic field in the accretion discs of young stars: the influence of magnetic diffusion, buoyancy and Hall effect

NASA Astrophysics Data System (ADS)

Khaibrakhmanov, S. A.; Dudorov, A. E.; Parfenov, S. Yu.; Sobolev, A. M.

2017-01-01

We investigate the fossil magnetic field in the accretion and protoplanetary discs using the Shakura and Sunyaev approach. The distinguishing feature of this study is the accurate solution of the ionization balance equations and the induction equation with Ohmic diffusion, magnetic ambipolar diffusion, buoyancy and the Hall effect. We consider the ionization by cosmic rays, X-rays and radionuclides, radiative recombinations, recombinations on dust grains and also thermal ionization. The buoyancy appears as the additional mechanism of magnetic flux escape in the steady-state solution of the induction equation. Calculations show that Ohmic diffusion and magnetic ambipolar diffusion constraint the generation of the magnetic field inside the `dead' zones. The magnetic field in these regions is quasi-vertical. The buoyancy constraints the toroidal magnetic field strength close to the disc inner edge. As a result, the toroidal and vertical magnetic fields become comparable. The Hall effect is important in the regions close to the borders of the `dead' zones because electrons are magnetized there. The magnetic field in these regions is quasi-radial. We calculate the magnetic field strength and geometry for the discs with accretion rates (10^{-8}-10^{-6}) {M}_{⊙} {yr}^{-1}. The fossil magnetic field geometry does not change significantly during the disc evolution while the accretion rate decreases. We construct the synthetic maps of dust emission polarized due to the dust grain alignment by the magnetic field. In the polarization maps, the `dead' zones appear as the regions with the reduced values of polarization degree in comparison to those in the adjacent regions.

Evidence for formation of DNA repair centers and dose-response nonlinearity in human cells

PubMed Central

Neumaier, Teresa; Swenson, Joel; Pham, Christopher; Polyzos, Aris; Lo, Alvin T.; Yang, PoAn; Dyball, Jane; Asaithamby, Aroumougame; Chen, David J.; Bissell, Mina J.; Thalhammer, Stefan; Costes, Sylvain V.

2012-01-01

The concept of DNA “repair centers” and the meaning of radiation-induced foci (RIF) in human cells have remained controversial. RIFs are characterized by the local recruitment of DNA damage sensing proteins such as p53 binding protein (53BP1). Here, we provide strong evidence for the existence of repair centers. We used live imaging and mathematical fitting of RIF kinetics to show that RIF induction rate increases with increasing radiation dose, whereas the rate at which RIFs disappear decreases. We show that multiple DNA double-strand breaks (DSBs) 1 to 2 μm apart can rapidly cluster into repair centers. Correcting mathematically for the dose dependence of induction/resolution rates, we observe an absolute RIF yield that is surprisingly much smaller at higher doses: 15 RIF/Gy after 2 Gy exposure compared to approximately 64 RIF/Gy after 0.1 Gy. Cumulative RIF counts from time lapse of 53BP1-GFP in human breast cells confirmed these results. The standard model currently in use applies a linear scale, extrapolating cancer risk from high doses to low doses of ionizing radiation. However, our discovery of DSB clustering over such large distances casts considerable doubts on the general assumption that risk to ionizing radiation is proportional to dose, and instead provides a mechanism that could more accurately address risk dose dependency of ionizing radiation. PMID:22184222

Simulation of the GEM detector for BM@N experiment

NASA Astrophysics Data System (ADS)

Baranov, Dmitriy; Rogachevsky, Oleg

2017-03-01

The Gas Electron Multiplier (GEM) detector is one of the basic parts of the BM@N experiment included in the NICA project. The simulation model that takes into account features of signal generation process in an ionization GEM chamber is presented in this article. Proper parameters for the simulation were extracted from data retrieved with the help of Garfield++ (a toolkit for the detailed simulation of particle detectors). Due to this, we are able to generate clusters in layers of the micro-strip readout that correspond to clusters retrieved from a real physics experiment.

Modelling ultraviolet-line diagnostics of stars, the ionized and the neutral interstellar medium in star-forming galaxies

NASA Astrophysics Data System (ADS)

Vidal-García, A.; Charlot, S.; Bruzual, G.; Hubeny, I.

2017-09-01

We combine state-of-the-art models for the production of stellar radiation and its transfer through the interstellar medium (ISM) to investigate ultraviolet-line diagnostics of stars, the ionized and the neutral ISM in star-forming galaxies. We start by assessing the reliability of our stellar population synthesis modelling by fitting absorption-line indices in the ISM-free ultraviolet spectra of 10 Large Magellanic Cloud clusters. In doing so, we find that neglecting stochastic sampling of the stellar initial mass function in these young (∼10-100 Myr), low-mass clusters affects negligibly ultraviolet-based age and metallicity estimates but can lead to significant overestimates of stellar mass. Then, we proceed and develop a simple approach, based on an idealized description of the main features of the ISM, to compute in a physically consistent way the combined influence of nebular emission and interstellar absorption on ultraviolet spectra of star-forming galaxies. Our model accounts for the transfer of radiation through the ionized interiors and outer neutral envelopes of short-lived stellar birth clouds, as well as for radiative transfer through a diffuse intercloud medium. We use this approach to explore the entangled signatures of stars, the ionized and the neutral ISM in ultraviolet spectra of star-forming galaxies. We find that, aside from a few notable exceptions, most standard ultraviolet indices defined in the spectra of ISM-free stellar populations are prone to significant contamination by the ISM, which increases with metallicity. We also identify several nebular-emission and interstellar-absorption features, which stand out as particularly clean tracers of the different phases of the ISM.

Influences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Zhijun; Gu, Quanli; Department of Chemistry, University of Oklahoma, Norman, Oklahoma 73019

2015-07-21

4-propylaniline complexes with one and two argon atoms formed in the molecular beam were studied in the first excited electronic state, S{sub 1}, using resonance enhanced two-photon ionization spectroscopy and in the cation ground state, D{sub 0}, using mass analyzed threshold ionization spectroscopy. The combination of electronic and cationic spectra of the clusters allows two conformations to be identified in both aniline-Ar{sub 1} and aniline-Ar{sub 2}, which are assigned to either the gauche configuration or anti-configuration of 4-propylaniline. The gauche isomer exhibits complex bands shifted 29 cm{sup −1} and 89 cm{sup −1} from the S{sub 1} origin bands and 83more » cm{sup −1} and 148 cm{sup −1} from the ionization potential assigned to the Ar{sub 1} and Ar{sub 2} complexes, respectively. For the anti-rotamer, the corresponding shifts actually become nearly additive, 53 cm{sup −1} and 109 cm{sup −1} for the S{sub 1} origin bands, and 61 cm{sup −1} and 125 cm{sup −1} for the ionization potentials. Ab initio calculations provide insights into the influences of the propyl and amino groups on the positions of the argon atoms within the clusters. In addition, the binding energy of one argon with the gauche isomer of 4-propylaniline has been measured to be 550 ± 5 cm{sup −1} in the D{sub 0} state, 496 ± 5 cm{sup −1} in the S{sub 1} state, and 467 ± 5 cm{sup −1} in the neutral ground state, S{sub 0}.« less

Effect of rotating electric field on 3D complex (dusty) plasma

NASA Astrophysics Data System (ADS)

Wörner, L.; Nosenko, V.; Ivlev, A. V.; Zhdanov, S. K.; Thomas, H. M.; Morfill, G. E.; Kroll, M.; Schablinski, J.; Block, D.

2011-06-01

The effect of rotating electric field on 3D particle clusters suspended in rf plasma was studied experimentally. Spheroidal clusters were suspended inside a glass box mounted on the lower horizontal rf electrode, with gravity partially balanced by thermophoretic force. Clusters rotated in the horizontal plane, in response to rotating electric field that was created inside the box using conducting coating on its inner surfaces ("rotating wall" technique). Cluster rotation was always in the direction of applied field and had a shear in the vertical direction. The angular speed of rotation was 104-107 times lower than applied frequency. The experiment is compared to a recent theory.

Wiggler magnetic field assisted third harmonic generation in expanding clusters

NASA Astrophysics Data System (ADS)

Vij, Shivani

2018-04-01

A simple theoretical model is constructed to study the wiggler magnetic field assisted third harmonic generation of intense short pulse laser in a cluster in its expanding phase. The ponderomotive force of laser causes density perturbations in cluster electron density which couples with wiggler magnetic field to produce a nonlinear current that generates transverse third harmonic. An intense short pulse laser propagating through a gas embedded with atomic clusters, converts it into hot plasma balls via tunnel ionization. Initially, the electron plasma frequency inside the clusters ω pe > \\sqrt{3}{ω }1 (with ω 1 being the frequency of the laser). As the cluster expands under Coulomb force and hydrodynamic pressure, ω pe decreases to \\sqrt{3}{ω }1. At this time, there is resonant enhancement in the efficiency of the third harmonic generation. The efficiency of third harmonic generation is enhanced due to cluster plasmon resonance and by phase matching due to wiggler magnetic field. The effect of cluster size on the expansion rate is studied to observe that the clusters of different radii would expand differently. The impact of laser intensity and wiggler magnetic field on the efficiency of third harmonic generation is also explored.

Non-LTE radiating acoustic shocks and Ca II K2V bright points

NASA Technical Reports Server (NTRS)

Carlsson, Mats; Stein, Robert F.

1992-01-01

We present, for the first time, a self-consistent solution of the time-dependent 1D equations of non-LTE radiation hydrodynamics in solar chromospheric conditions. The vertical propagation of sinusoidal acoustic waves with periods of 30, 180, and 300 s is calculated. We find that departures from LTE and ionization recombination determine the temperature profiles of the shocks that develop. In LTE almost all the thermal energy goes into ionization, so the temperature rise is very small. In non-LTE, the finite transition rates delay the ionization to behind the shock front. The compression thus goes into thermal energy at the shock front leading to a high temperature amplitude. Further behind the shock front, the delayed ionization removes energy from the thermal pool, which reduces the temperature, producing a temperature spike. The 180 s waves reproduce the observed temporal changes in the calcium K line profiles quite well. The observed wing brightening pattern, the violet/red peak asymmetry and the observed line center behavior are all well reproduced. The short-period waves and the 5 minute period waves fail especially in reproducing the observed behavior of the wings.

Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. IV. Coulomb explosion of molecular heteroclusters.

PubMed

Last, Isidore; Jortner, Joshua

2004-11-01

In this paper we present a theoretical and computational study of the temporal dynamics and energetics of Coulomb explosion of (CD4)(n) and (CH4)(n) (n=55-4213) molecular heteroclusters in ultraintense (I=10(16)-10(19) W cm(-2)) laser fields, addressing the manifestation of electron dynamics, together with nuclear energetic and kinematic effects on the heterocluster Coulomb instability. The manifestations of the coupling between electron and nuclear dynamics were explored by molecular dynamics simulations for these heteroclusters coupled to Gaussian laser fields (pulse width tau=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for I< or =10(17) W cm(-2)), and the attainment of cluster vertical ionization (CVI) (at I=10(17) W cm(-2) for cluster radius R(0)< or =31 A). Nuclear kinematic effects on heterocluster Coulomb explosion are governed by the kinematic parameter eta=q(C)m(A)/q(A)m(C) for (CA(4))(n) clusters (A=H,D), where q(j) and m(j) (j=A,C) are the ionic charges and masses. Nonuniform heterocluster Coulomb explosion (eta >1) manifests an overrun effect of the light ions relative to the heavy ions, exhibiting the expansion of two spatially separated subclusters, with the light ions forming the outer subcluster at the outer edge of the spatial distribution. Important features of the energetics of heterocluster Coulomb explosion originate from energetic triggering effects of the driving of the light ions by the heavy ions (C(4+) for I=10(17)-10(18) W cm(-2) and C(6+) for I=10(19) W cm(-2)), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R(0)) dependence of the energetics of uniform Coulomb explosion of heteroclusters (eta=1) were derived, with the size dependence of the average (E(j,av)) and maximal (E(j,M)) ion energies being E(j,av)=aR(0) (2) and E(j,M)=(5a/3)R(0) (2), as well as for the ion energy distributions P(E(j)) proportional to E(j) (1/2); E(j)< or =E(j,M). These results for uniform Coulomb explosion serve as benchmark reference data for the assessment of the effects of nonuniform explosion, where the CVI scaling law for the energetics still holds, with deviations of the a coefficient, which increase with increasing eta. Kinematic effects (for eta>1) result in an isotope effect, predicting the enhancement (by 9%-11%) of E(H,av) for Coulomb explosion of (C(4+)H(4) (+))(eta) (eta=3) relative to E(D,av) for Coulomb explosion of (C(4+)D(4) (+))(eta) (eta=1.5), with the isotope effect being determined by the ratio of the kinematic parameters for the pair of Coulomb exploding clusters. Kinematic effects for nonuniform explosion also result in a narrow isotope dependent energy distribution (of width DeltaE) of the light ions (with DeltaE/E(H,av) approximately 0.3 and DeltaE/E(D,av) approximately 0.4), with the distribution peaking at the high energy edge, in marked contrast with the uniform explosion case. Features of laser-heterocluster interactions were inferred from the analyses of the intensity dependent boundary radii (R(0))(I) and the corresponding average D+ ion energies (E(D,av))(I), which provide a measure for optimization of the cluster size at intensity I for the neutron yield from dd nuclear fusion driven by Coulomb explosion (NFDCE) of these heteroclusters. We infer on the advantage of deuterium containing heteronuclear clusters, e.g., (CD4)(n) in comparison to homonuclear clusters, e.g., (D2)(n/2), for dd NFDCE, where the highly charged heavy ions (e.g., C4+ or C6+) serve as energetic and kinematic triggers driving the D+ ions to a high (10-200 keV) energy domain. (c) 2004 American Institute of Physics.

Application of Coaxial Ion Gun for Film Generation and Ion Implantation

NASA Astrophysics Data System (ADS)

Takatsu, Mikio; Asai, Tomohiko; Kurumi, Satoshi; Suzuki, Kaoru; Hirose, Hideharu; Masutani, Shigeyuki

A magnetized coaxial plasma gun (MCPG) is here utilized for deposition on high-melting-point metals. MCPGs have hitherto been studied mostly in the context of nuclear fusion research, for particle and magnetic helicity injection and spheromak formation. During spheromak formation, the electrode materials are ionized and mixed into the plasmoid. In this study, this ablation process by gun-current sputtering is enhanced for metallic thin-film generation. In the proposed system geometry, only ionized materials are electromagnetically accelerated by the self-Lorentz force, with ionized operating gas as a magnetized thermal plasmoid, contributing to the thin-film deposition. This reduces the impurity and non-uniformity of the deposited thin-film. Furthermore, as the ions are accelerated in a parallel direction to the injection axis, vertical implantation of the ions into the substrate surface is achieved. To test a potential application of the developed system, experiments were conducted involving the formation of a buffer layer on hard ceramics, for use in dental materials.

Truncation of the Binary Distribution Function in Globular Cluster Formation

NASA Astrophysics Data System (ADS)

Vesperini, E.; Chernoff, David F.

1996-02-01

We investigate a population of primordial binaries during the initial stage of evolution of a star cluster. For our calculations we assume that equal-mass stars form rapidly in a tidally truncated gas cloud, that ˜10% of the stars are in binaries, and that the resulting star cluster undergoes an epoch of violent relaxation. We study the collisional interaction of the binaries and single stars, in particular, the ionization of the binaries and the energy exchange between binaries and single stars. We find that for large N systems (N > 1000), even the most violent beginning leaves the binary distribution function largely intact. Hence, the binding energy originally tied up in the cloud's protostellar pairs is preserved during the relaxation process, and the binaries are available to interact at later times within the virialized cluster.

HEAO A-2 observations of the X-ray spectra of the Centaurus and A1060 clusters of galaxies

NASA Technical Reports Server (NTRS)

Mitchell, R.; Mushotzky, R.

1980-01-01

X-ray spectral observations of two nearby low-luminosity clusters of galaxies are presented. For the Centaurus cluster an emission feature at 7.9 keV is detected at about one-third of the strength of the 6.7 keV line. This higher energy line represents K-beta emission from highly ionized iron. In addition, it is demonstrated that for neither the Centaurus nor the A1060 cluster can an isothermal model with an Fe emission line adequately fit the data. Instead, the simplest models which provide acceptable fits include a second, harder component which may be either a second exponential or a power law. The implications of the two-component nature of the continuum on the Fe abundance and the X-ray surface-brightness distribution are discussed.

Integrative analysis of signaling pathways and diseases associated with the miR-106b/25 cluster and their function study in berberine-induced multiple myeloma cells.

PubMed

Gu, Chunming; Li, Tianfu; Yin, Zhao; Chen, Shengting; Fei, Jia; Shen, Jianping; Zhang, Yuan

2017-05-01

Berberine (BBR), a traditional Chinese herbal medicine compound, has emerged as a novel class of anti-tumor agent. Our previous microRNA (miRNA) microarray demonstrated that miR-106b/25 was significantly down-regulated in BBR-treated multiple myeloma (MM) cells. Here, systematic integration showed that miR-106b/25 cluster is involved in multiple cancer-related signaling pathways and tumorigenesis. MiREnvironment database revealed that multiple environmental factors (drug, ionizing radiation, hypoxia) affected the miR-106b/25 cluster expression. By targeting the seed region in the miRNA, tiny anti-mir106b/25 cluster (t-anti-mir106b/25 cluster) significantly induced suppression in cell viability and colony formation. Western blot validated that t-anti-miR-106b/25 cluster effectively inhibited the expression of P38 MAPK and phospho-P38 MAPK in MM cells. These findings indicated the miR-106b/25 cluster functioned as oncogene and might provide a novel molecular insight into MM.

Direct versus indirect many-body methods for calculating vertical electron affinities: applications to F -, OH - , NH 2-, CN -, Cl -, SH - and PH 2-

NASA Astrophysics Data System (ADS)

Ortiz, J. V.

1987-05-01

Electron propagator theory (EPT) is applied to calculating vertical ionization energies of the anions F -, Cl -, OH -,SH -, NH 2-, PH 2- and CN -. Third-order and outer valence approximation (OVA) quasiparticle calculations are compared with ΔMBPT(4) (MBPT, many-body perturbation theory) results using the same basis sets. Agreement with experiment is satisfactory for EPT calculations except for F - and OH -, while the ΔMBPT treatments fail for CN -. EPT(OVA) estimates are reliable when the discrepancy between second- and third-order results is small. Computational aspects are discussed, showing relative merits of direct and indirect methods for evaluating electron binding energies.

Changes in urban-related precipitation in the summer over three city clusters in China

NASA Astrophysics Data System (ADS)

Zhao, Deming; Wu, Jian

2017-09-01

The impacts of urban surface expansion on the summer precipitations over three city clusters [Beijing-Tianjin-Hebei (BTH), the Yangtze River Delta (YRD), and the Pearl River Delta (PRD)] in eastern China under different monsoonal circulation backgrounds were explored using the nested fifth-generation Penn State/NCAR Mesoscale Model version 3.7 (MM5 V3.7), including the urban-related thermal and dynamical parameters. Ten-year integrations were performed using satellite image data from 2000 and 2010 to represent the urban surface distributions and expansions in China. Changes in the precipitation revealed obvious subregional characteristics, which could be explained by the influences of the vertical wind velocity and moisture flux. With urban-related warming, vertical wind motion generally intensified over urban surface-expanded areas. Meanwhile, the increase in impervious surface areas induced rapid rainwater runoff into drains, and the Bowen ratio increased over urban areas, which further contributed to changes in the local moisture fluxes in these regions. The intensities of the changes in precipitation were inconsistent over the three city clusters, although the changes in vertical motion and local evaporation were similar, which indicates that the changes in precipitation cannot be solely explained by the changes in the local evaporation-related moisture flux. The changes in precipitation were also influenced by the changes in the East Asian summer monsoon (EASM) circulation and the corresponding moisture flux, which are expressed in marked subregional characteristics. Therefore, the influence of urban-related precipitation over the three city clusters in China, for which changes in moisture flux from both the impacted local evaporation and EASM circulation should be considered, varied based on the precipitation changes of only a single city.

PROM7: 1D modeler of solar filaments or prominences

NASA Astrophysics Data System (ADS)

Gouttebroze, P.

2018-05-01

PROM7 is an update of PROM4 (ascl:1306.004) and computes simple models of solar prominences and filaments using Partial Radiative Distribution (PRD). The models consist of plane-parallel slabs standing vertically above the solar surface. Each model is defined by 5 parameters: temperature, density, geometrical thickness, microturbulent velocity and height above the solar surface. It solves the equations of radiative transfer, statistical equilibrium, ionization and pressure equilibria, and computes electron and hydrogen level population and hydrogen line profiles. Moreover, the code treats calcium atom which is reduced to 3 ionization states (Ca I, Ca II, CA III). Ca II ion has 5 levels which are useful for computing 2 resonance lines (H and K) and infrared triplet (to 8500 A).

Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

PubMed

El-Shall, M Samy

2008-07-01

Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information on the oligomers formed by gas-phase polymerization can be obtained using the mass-selected ion mobility technique where the measured collision cross-sections of the selected oligomer ions and collision-induced dissociation can provide fairly accurate structural identifications. The identification of the structures of the dimers and trimers formed in the gas-phase thermal polymerization of styrene confirms that the polymerization proceeds according to the Mayo mechanism. Similarly, the ion mobility technique has been utilized to confirm the formation of benzene cations by intracluster polymerization following the ionization of acetylene clusters. Finally, it has been shown that polymerization of styrene vapor on the surface of activated nanoparticles can lead to the incorporation of a variety of metal and metal oxide nanoparticles within polystyrene films. The ability to probe the reactivity and structure of the small growing oligomers in the gas phase can provide fundamental insight into mechanisms of polymerization that are difficult to obtain from condensed-phase studies. These experiments are also important for understanding the growth mechanisms of complex organics in flames, combustion processes, interstellar clouds, and solar nebula where gas-phase reactions, cluster polymerization, and surface catalysis on dust nanoparticles represent the major synthetic pathways. This research can lead to the discovery of novel initiation mechanisms and reaction pathways with applications in the synthesis of oligomers and nanocomposites with unique and improved properties.

Disturbance zonal and vertical plasma drifts in the Peruvian sector during solar minimum phases

NASA Astrophysics Data System (ADS)

Santos, A. M.; Abdu, M. A.; Souza, J. R.; Sobral, J. H. A.; Batista, I. S.

2016-03-01

In the present work, we investigate the behavior of the equatorial F region zonal plasma drifts over the Peruvian region under magnetically disturbed conditions during two solar minimum epochs, one of them being the recent prolonged solar activity minimum. The study utilizes the vertical and zonal components of the plasma drifts measured by the Jicamarca (11.95°S; 76.87°W) incoherent scatter radar during two events that occurred on 10 April 1997 and 24 June 2008 and model calculation of the zonal drift in a realistic ionosphere simulated by the Sheffield University Plasmasphere-Ionosphere Model-INPE. Two main points are focused: (1) the connection between electric fields and plasma drifts under prompt penetration electric field during a disturbed periods and (2) anomalous behavior of daytime zonal drift in the absence of any magnetic storm. A perfect anticorrelation between vertical and zonal drifts was observed during the night and in the initial and growth phases of the magnetic storm. For the first time, based on a realistic low-latitude ionosphere, we will show, on a detailed quantitative basis, that this anticorrelation is driven mainly by a vertical Hall electric field induced by the primary zonal electric field in the presence of an enhanced nighttime E region ionization. It is shown that an increase in the field line-integrated Hall-to-Pedersen conductivity ratio (∑H/∑P), which can arise from precipitation of energetic particles in the region of the South American Magnetic Anomaly, is capable of explaining the observed anticorrelation between the vertical and zonal plasma drifts. Evidence for the particle ionization is provided from the occurrence of anomalous sporadic E layers over the low-latitude station, Cachoeira Paulista (22.67°S; 44.9°W)—Brazil. It will also be shown that the zonal plasma drift reversal to eastward in the afternoon two hours earlier than its reference quiet time pattern is possibly caused by weakening of the zonal wind system during the prolonged solar minimum period.

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

DOE Office of Scientific and Technical Information (OSTI.GOV)

You, Zhi-Qiang; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu; Mewes, Jan-Michael

2015-11-28

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations failsmore » to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents.« less

Infrared absorption of methanol-water clusters (CH3OH)n(H2O), n = 1-4, recorded with the VUV-ionization/IR-depletion technique

NASA Astrophysics Data System (ADS)

Lee, Yu-Fang; Kelterer, Anne-Marie; Matisz, Gergely; Kunsági-Máté, Sándor; Chung, Chao-Yu; Lee, Yuan-Pern

2017-04-01

We recorded infrared (IR) spectra in the CH- and OH-stretching regions of size-selected clusters of methanol (M) with one water molecule (W), represented as MnW, n = 1-4, in a pulsed supersonic jet using the photoionization/IR-depletion technique. Vacuum ultraviolet emission at 118 nm served as the source of ionization in a time-of-flight mass spectrometer to detect clusters MnW as protonated forms Mn-1WH+. The variations in intensities of Mn-1WH+ were monitored as the wavelength of the IR laser light was tuned across the range 2700-3800 cm-1. IR spectra of size-selected clusters were obtained on processing of the observed action spectra of the related cluster-ions according to a mechanism that takes into account the production and loss of each cluster due to IR photodissociation. Spectra of methanol-water clusters in the OH region show significant variations as the number of methanol molecules increases, whereas those in the CH region are similar for all clusters. Scaled harmonic vibrational wavenumbers and relative IR intensities predicted with the M06-2X/aug-cc-pVTZ method for the methanol-water clusters are consistent with our experimental results. For dimers, absorption bands of a structure WM with H2O as a hydrogen-bond donor were observed at 3570, 3682, and 3722 cm-1, whereas weak bands of MW with methanol as a hydrogen-bond donor were observed at 3611 and 3753 cm-1. For M2W, the free OH band of H2O was observed at 3721 cm-1, whereas a broad feature was deconvoluted to three bands near 3425, 3472, and 3536 cm-1, corresponding to the three hydrogen-bonded OH-stretching modes in a cyclic structure. For M3W, the free OH shifted to 3715 cm-1, and the hydrogen-bonded OH-stretching bands became much broader, with a weak feature near 3179 cm-1 corresponding to the symmetric OH-stretching mode of a cyclic structure. For M4W, the observed spectrum agrees unsatisfactorily with predictions for the most stable cyclic structure, indicating significant contributions from branched isomers, which is distinctly different from M5 of which the cyclic form dominates.

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia

2013-07-02

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including V xO y n– and V xO yCl n– ions (x = 1–14, y = 2–36, n = 1–3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V 14O 36Cl(L) 5 (L = Et 4N +, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged V xO yCl n– and V xOmore » yCl(L) (n–1)– clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller V xO yCl (1–2)– and V xO y (1–2)– anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged V xO yCl and V xO y species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of V xO yCl and V xO y anions through low-energy CID. Finally and furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.« less

Infrared absorption of methanol-water clusters (CH3OH)n(H2O), n = 1-4, recorded with the VUV-ionization/IR-depletion technique.

PubMed

Lee, Yu-Fang; Kelterer, Anne-Marie; Matisz, Gergely; Kunsági-Máté, Sándor; Chung, Chao-Yu; Lee, Yuan-Pern

2017-04-14

We recorded infrared (IR) spectra in the CH- and OH-stretching regions of size-selected clusters of methanol (M) with one water molecule (W), represented as M n W, n = 1-4, in a pulsed supersonic jet using the photoionization/IR-depletion technique. Vacuum ultraviolet emission at 118 nm served as the source of ionization in a time-of-flight mass spectrometer to detect clusters M n W as protonated forms M n-1 WH + . The variations in intensities of M n-1 WH + were monitored as the wavelength of the IR laser light was tuned across the range 2700-3800 cm -1 . IR spectra of size-selected clusters were obtained on processing of the observed action spectra of the related cluster-ions according to a mechanism that takes into account the production and loss of each cluster due to IR photodissociation. Spectra of methanol-water clusters in the OH region show significant variations as the number of methanol molecules increases, whereas those in the CH region are similar for all clusters. Scaled harmonic vibrational wavenumbers and relative IR intensities predicted with the M06-2X/aug-cc-pVTZ method for the methanol-water clusters are consistent with our experimental results. For dimers, absorption bands of a structure WM with H 2 O as a hydrogen-bond donor were observed at 3570, 3682, and 3722 cm -1 , whereas weak bands of MW with methanol as a hydrogen-bond donor were observed at 3611 and 3753 cm -1 . For M 2 W, the free OH band of H 2 O was observed at 3721 cm -1 , whereas a broad feature was deconvoluted to three bands near 3425, 3472, and 3536 cm -1 , corresponding to the three hydrogen-bonded OH-stretching modes in a cyclic structure. For M 3 W, the free OH shifted to 3715 cm -1 , and the hydrogen-bonded OH-stretching bands became much broader, with a weak feature near 3179 cm -1 corresponding to the symmetric OH-stretching mode of a cyclic structure. For M 4 W, the observed spectrum agrees unsatisfactorily with predictions for the most stable cyclic structure, indicating significant contributions from branched isomers, which is distinctly different from M 5 of which the cyclic form dominates.

An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

DOE PAGES

Van Berkel, Gary J.; Kertesz, Vilmos

2015-08-25

RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creatingmore » a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.« less

Equation of motion coupled cluster methods for electron attachment and ionization potential in fullerenes C60 and C70

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhaskaran-Nair, Kiran; Kowalski, Karol; Moreno, Juana

Discovery of fullerenes has opened a entirely new chapter in chemistry due to their wide range of properties which holds exciting applications in numerous disciplines of science. The Nobel Prize in Chemistry 1996 was awarded jointly to Robert F. Curl Jr., Sir Harold W. Kroto and Richard E. Smalley in recoginition for their discovery of this new carbon allotrope. In this letter we are reporting ionization potential and electron attachment studies on fullerenes (C60 and C70) obtained with novel parallel implementation of the EA-EOM-CCSD and IP-EOM-CCSD methods in NWChem program package.

Scientific authorship and collaboration network analysis on malaria research in Benin: papers indexed in the web of science (1996-2016).

PubMed

Azondekon, Roseric; Harper, Zachary James; Agossa, Fiacre Rodrigue; Welzig, Charles Michael; McRoy, Susan

2018-01-01

To sustain the critical progress made, prioritization and a multidisciplinary approach to malaria research remain important to the national malaria control program in Benin. To document the structure of the malaria collaborative research in Benin, we analyze authorship of the scientific documents published on malaria from Benin. We collected bibliographic data from the Web Of Science on malaria research in Benin from January 1996 to December 2016. From the collected data, a mulitigraph co-authorship network with authors representing vertices was generated. An edge was drawn between two authors when they co-author a paper. We computed vertex degree, betweenness, closeness, and eigenvectors among others to identify prolific authors. We further assess the weak points and how information flow in the network. Finally, we perform a hierarchical clustering analysis, and Monte-Carlo simulations. Overall, 427 publications were included in this study. The generated network contained 1792 authors and 116,388 parallel edges which converted in a weighted graph of 1792 vertices and 95,787 edges. Our results suggested that prolific authors with higher degrees tend to collaborate more. The hierarchical clustering revealed 23 clusters, seven of which form a giant component containing 94% of all the vertices in the network. This giant component has all the characteristics of a small-world network with a small shortest path distance between pairs of three, a diameter of 10 and a high clustering coefficient of 0.964. However, Monte-Carlo simulations suggested our observed network is an unusual type of small-world network. Sixteen vertices were identified as weak articulation points within the network. The malaria research collaboration network in Benin is a complex network that seems to display the characteristics of a small-world network. This research reveals the presence of closed research groups where collaborative research likely happens only between members. Interdisciplinary collaboration tends to occur at higher levels between prolific researchers. Continuously supporting, stabilizing the identified key brokers and most productive authors in the Malaria research collaborative network is an urgent need in Benin. It will foster the malaria research network and ensure the promotion of junior scientists in the field.

Fragmentation dynamics of ionized neon clusters (Ne(n), n=3-14) embedded in helium nanodroplets.

PubMed

Bonhommeau, David; Halberstadt, Nadine; Viel, Alexandra

2006-01-14

We report a theoretical study of the nonadiabatic fragmentation dynamics of ionized neon clusters embedded in helium nanodroplets for cluster sizes up to n=14 atoms. The dynamics of the neon atoms is modeled using the molecular dynamics with quantum transitions method of Tully [J. Chem. Phys. 93, 1061 (1990)] with the nuclei treated classically and transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model to which induced dipole-induced dipole interactions are added. The effect of the spin-orbit interaction is also discussed. The helium environment is modeled by a friction force acting on charged atoms whose speed exceeds the critical Landau velocity. The dependence of the fragment size distribution on the friction strength and on the initial nanodroplet size is investigated. By comparing with the available experimental data obtained for Ne3+ and Ne4+, a reasonable value for the friction coefficient, the only parameter of the model, is deduced. This value is then used to predict the effect of the helium environment on the dissociation dynamics of larger neon clusters, n=5-14. The results show stabilization of larger fragments than in the gas phase, but fragmentation is not completely caged. In addition, two types of dynamics are characterized for Ne4+: fast and explosive, therefore leaving no time for friction to cool down the process when dynamics starts on one of the highest electronic states, and slower, therefore leading to some stabilization by helium when it starts on one of the lowest electronic states.

Source of Global Scale Variations in the Midday Vertical Content of Ionospheric Metal Ions

NASA Technical Reports Server (NTRS)

Joiner, J.; Grebowsky, J. M.; Pesnell, W. D.; Aikin, A. C.; Goldberg, Richard A.

1999-01-01

An analysis of long baseline NIMBUS 7 SBUV (Solar Backscatter UV Spectrometer) observations of the latitudinal variation of the noontime vertical Mg' content above approx. 70 km have revealed seasonal, solar activity and magnetic activity dependencies in the Mg+ content. The distributions were categorized in terms of magnetic coordinates partially because transport processes lifting metallic ions from the main meteor ionization layer below 100 km up into the F- region and down again are controlled by electrodynamical processes. Alternatively, the Nimbus Mg+ distributions may simply be a result of ion/neutral chemistry changes resulting from atmospheric changes and not dynamics. In such a case magnetic control would not dominate the distributions. Using in situ satellite measurements of metal ions from the Atmosphere Explorer satellites in the region above the main meteor layer and published sounding rocket measurements of the main metallic ion layers, the effects of the dynamics on the vertical content are delineated. The consequences of atmospheric changes on the vertical content are explored by separating the Nimbus measurements in a geodetic frame of reference.

Ionized Gas Kinematics at High Resolution. IV. Star Formation and a Rotating Core in the Medusa (NGC 4194)

NASA Technical Reports Server (NTRS)

Beck, Sara C.; Lacy, John; Neff, Susan Gale; Turner, Jean; Greathouse, Thomas; Neff, Susan

2014-01-01

NGC 4194 is a post-merger starburst known as The Medusa for its striking tidal features.We present here a detailed study of the structure and kinematics of ionized gas in the central 0.65 kpc of the Medusa. The data include radio continuum maps with resolution up to 0".18 (35 pc) and a 12.8 micron [Ne II] data cube with spectral resolution approx. 4 km/s: the first high-resolution, extinction-free observations of this remarkable object. The ionized gas has the kinematic signature of a core in solid-body rotation. The starburst has formed a complex of bright compact H II regions, probably excited by deeply embedded super star clusters, but none of these sources is a convincing candidate for a Galactic nucleus. The nuclei of the merger partners that created the Medusa have not yet been identified.

Method and apparatus for confinement of ions in the presence of a neutral gas

DOEpatents

Peurrung, A.J.; Barlow, S.E.

1999-08-03

The present invention is an apparatus and method for combining ions with a neutral gas and flowing the mixture with a radial flow component through a magnetic field so that the weakly ionized gas is confined by the neutral gas. When the weakly ionized gas is present in sufficient density, a weakly ionized non-neutral plasma is formed that may be trapped in accordance with the present invention. Applications for a weakly ionized non-neutral plasma exploit the trap`s ability to store and manipulate ionic species in the presence of neutral gas. The trap may be connected to a mass spectrometer thereby permitting species identification after a fixed period of time. Delicate and/or heavy particles such as clusters may be held and studied in a ``gentle`` environment. In addition, the trap can provide a relatively intense, low-energy source of a particular ion species for surface implantation or molecular chemistry. Finally, a long trap may permit spectroscopy of unprecedented accuracy to be performed on ionic species. 4 figs.

The Ionization History of The Intergalactic Medium:

NASA Technical Reports Server (NTRS)

Madau, Piero

2003-01-01

The funded project seeked a unified description of the ionization, physical structure, and evolution of the intergalactic medium (IGM) and quasar intervening absorption systems. We proposed to conduct theoretical studies of the IGM and QSO absorbers in the context of current theories of galaxy formation, developing and using numerical and analytical techniques aimed at a detailed modeling of cosmological radiative transfer, gas dynamics, and thermal and ionization evolution. The ionization history of the IGM has important implications for the metagalactic UV background, intergalactic helium absorption 21-cm tomography, metal absorption systems, fluctuations in the microwave background, and the cosmic rate of structure and star formation. All the original objectives of our program have been achieved, and the results widely used and quoted by the community. Indeed, they remain relevant as the level and complexity of research in this area has increased substantially since our proposal was submitted, due to new discoveries on galaxy formation and evolution, a flood of high-quality data on the distant universe, new theoretical ideas and direct numerical simulations of structure formation in hierarchical clustering theories.

StarBooster Demonstrator Cluster Configuration Analysis/Verification Program

NASA Technical Reports Server (NTRS)

DeTurris, Dianne J.

2003-01-01

In order to study the flight dynamics of the cluster configuration of two first stage boosters and upper-stage, flight-testing of subsonic sub-scale models has been undertaken using two glideback boosters launched on a center upper-stage. Three high power rockets clustered together were built and flown to demonstrate vertical launch, separation and horizontal recovery of the boosters. Although the boosters fly to conventional aircraft landing, the centerstage comes down separately under its own parachute. The goal of the project has been to collect data during separation and flight for comparison with a six degree of freedom simulation. The configuration for the delta wing canard boosters comes from a design by Starcraft Boosters, Inc. The subscale rockets were constructed of foam covered in carbon or fiberglass and were launched with commercially available solid rocket motors. The first set of boosters built were 3-ft tall with a 4-ft tall centerstage, and two additional sets of boosters were made that were each over 5-ft tall with a 7.5 ft centerstage. The rocket cluster is launched vertically, then after motor bum out the boosters are separated and flown to a horizontal landing under radio-control. An on-board data acquisition system recorded data during both the launch and glide phases of flight.

Dynamical pattern formation in a low-concentration magnetorheological fluid under two orthogonal sinusoidal fields

NASA Astrophysics Data System (ADS)

Yépez, L. D.; Carrillo, J. L.; Donado, F.; Sausedo-Solorio, J. M.; Miranda-Romagnoli, P.

2016-06-01

The dynamical pattern formation of clusters of magnetic particles in a low-concentration magnetorheological fluid, under the influence of a superposition of two perpendicular sinusoidal fields, is studied experimentally. By varying the frequency and phase shift of the perpendicular fields, this configuration enables us to experimentally analyze a wide range of field configurations, including the case of a pure rotating field and the case of an oscillating unidirectional field. The fields are applied parallel to the horizontal plane where the fluid lies or in the vertical plane. For fields applied in the horizontal plane, we observed that, when the ratio of the frequencies increases, the average cluster size exhibits a kind of periodic resonances. When the phase shift between the fields is varied, the average chain length reaches maximal values for the cases of the rotating field and the unidirectional case. We analyze and discuss these results in terms of a weighted average of the time-dependent Mason number. In the case of a rotating field on the vertical plane, we also observe that the competition between the magnetic and the viscous forces determines the average cluster size. We show that this configuration generates a series of physically meaningful self-organization of clusters and transport phenomena.

Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

PubMed

Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

2009-04-02

We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

Computational Studies on the Anharmonic Dynamics of Molecular Clusters

NASA Astrophysics Data System (ADS)

Mancini, John S.

Molecular nanoclusters present ideal systems to probe the physical forces and dynamics that drive the behavior of larger bulk systems. At the nanocluster limit the first instances of several phenomena can be observed including the breaking of hydrogen and molecular bonds. Advancements in experimental and theoretical techniques have made it possible to explore these phenomena in great detail. The most fruitful of these studies have involved the use of both experimental and theoretical techniques to leverage to strengths of the two approaches. This dissertation seeks to explore several important phenomena of molecular clusters using new and existing theoretical methodologies. Three specific systems are considered, hydrogen chloride clusters, mixed water and hydrogen chloride clusters and the first cluster where hydrogen chloride autoionization occurs. The focus of these studies remain as close as possible to experimentally observable phenomena with the intention of validating, simulating and expanding on experimental work. Specifically, the properties of interested are those related to the vibrational ground and excited state dynamics of these systems. Studies are performed using full and reduced dimensional potential energy surface alongside advanced quantum mechanical methods including diffusion Monte Carlo, vibrational configuration interaction theory and quasi-classical molecular dynamics. The insight gained from these studies are great and varied. A new on-they-fly ab initio method for studying molecular clusters is validated for (HCl)1--6. A landmark study of the dissociation energy and predissociation mechanism of (HCl)3 is reported. The ground states of mixed (HCl)n(H2O)m are found to be highly delocalized across multiple stationary point configurations. Furthermore, it is identified that the consideration of this delocalization is required in vibrational excited state calculations to achieve agreement with experimental measurements. Finally, the theoretical infrared spectra for the first case of HCl ionization in (H 2O)m is reported, H+(H2O) 3Cl--. The calculation indicates that the ionized cluster's spectra is much more complex than any pervious harmonic predictions, with a large number of the system's infrared active peaks resulting from overtones of lower frequency molecular motions.

Transmission Geometry Laser Ablation into a Non-Contact Liquid Vortex Capture Probe for Mass Spectrometry Imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ovchinnikova, Olga S; Bhandari, Deepak; Lorenz, Matthias

2014-01-01

RATIONALE: Capture of material from a laser ablation plume into a continuous flow stream of solvent provides the means for uninterrupted sampling, transport and ionization of collected material for coupling with mass spectral analysis. Reported here is the use of vertically aligned transmission geometry laser ablation in combination with a new non-contact liquid vortex capture probe coupled with electrospray ionization for spot sampling and chemical imaging with mass spectrometry. Methods: A vertically aligned continuous flow liquid vortex capture probe was positioned directly underneath a sample surface in a transmission geometry laser ablation (355 nm, 10 Hz, 7 ns pulse width)more » setup to capture into solution the ablated material. The outlet of the vortex probe was coupled to the Turbo V ion source of an AB SCIEX TripleTOF 5600+ mass spectrometer. System operation and performance metrics were tested using inked patterns and thin tissue sections. Glass slides and slides designed especially for laser capture microdissection, viz., DIRECTOR slides and PEN 1.0 (polyethylene naphthalate) membrane slides, were used as sample substrates. Results: The estimated capture efficiency of laser ablated material was 24%, which was enabled by the use of a probe with large liquid surface area (~ 2.8 mm2) and with gravity to help direct ablated material vertically down towards the probe. The swirling vortex action of the liquid surface potentially enhanced capture and dissolution of not only particulates, but also gaseous products of the laser ablation. The use of DIRECTOR slides and PEN 1.0 (polyethylene naphthalate) membrane slides as sample substrates enabled effective ablation of a wide range of sample types (basic blue 7, polypropylene glycol, insulin and cyctochrome c) without photodamage using a UV laser. Imaging resolution of about 6 m was demonstrated for stamped ink on DIRECTOR slides based on the ability to distinguish features present both in the optical and in the chemical image. This imaging resolution was 20 times better than the previous best reported results with laser ablation/liquid sample capture mass spectrometry imaging. Using thin sections of brain tissue the chemical image of a selected lipid was obtained with an estimated imaging resolution of about 50 um. Conclusions: A vertically aligned, transmission geometry laser ablation liquid vortex capture probe, electrospray ionization mass spectrometry system provides an effective means for spatially resolved spot sampling and imaging with mass spectrometry.« less

Transmission geometry laser ablation into a non-contact liquid vortex capture probe for mass spectrometry imaging.

PubMed

Ovchinnikova, Olga S; Bhandari, Deepak; Lorenz, Matthias; Van Berkel, Gary J

2014-08-15

Capture of material from a laser ablation plume into a continuous flow stream of solvent provides the means for uninterrupted sampling, transport and ionization of collected material for coupling with mass spectral analysis. Reported here is the use of vertically aligned transmission geometry laser ablation in combination with a new non-contact liquid vortex capture probe coupled with electrospray ionization for spot sampling and chemical imaging with mass spectrometry. A vertically aligned continuous flow liquid vortex capture probe was positioned directly underneath a sample surface in a transmission geometry laser ablation (355 nm, 10 Hz, 7 ns pulse width) set up to capture into solution the ablated material. The outlet of the vortex probe was coupled to the Turbo V™ ion source of an AB SCIEX TripleTOF 5600+ mass spectrometer. System operation and performance metrics were tested using inked patterns and thin tissue sections. Glass slides and slides designed especially for laser capture microdissection, viz., DIRECTOR(®) slides and PEN 1.0 (polyethylene naphthalate) membrane slides, were used as sample substrates. The estimated capture efficiency of laser-ablated material was 24%, which was enabled by the use of a probe with large liquid surface area (~2.8 mm(2) ) and with gravity to help direct ablated material vertically down towards the probe. The swirling vortex action of the liquid surface potentially enhanced capture and dissolution not only of particulates, but also of gaseous products of the laser ablation. The use of DIRECTOR(®) slides and PEN 1.0 (polyethylene naphthalate) membrane slides as sample substrates enabled effective ablation of a wide range of sample types (basic blue 7, polypropylene glycol, insulin and cyctochrome c) without photodamage using a UV laser. Imaging resolution of about 6 µm was demonstrated for stamped ink on DIRECTOR(®) slides based on the ability to distinguish features present both in the optical and in the chemical image. This imaging resolution was 20 times better than the previous best reported results with laser ablation/liquid sample capture mass spectrometry imaging. Using thin sections of brain tissue the chemical image of a selected lipid was obtained with an estimated imaging resolution of about 50 µm. A vertically aligned, transmission geometry laser ablation liquid vortex capture probe, electrospray ionization mass spectrometry system provides an effective means for spatially resolved spot sampling and imaging with mass spectrometry. Published in 2014. This article is a U.S. Government work and is in the public domain in the USA.

A model for the infrared emission from an OB star cluster environment

NASA Technical Reports Server (NTRS)

Leisawitz, D.

1991-01-01

A model for the infrared emission from the neighborhood of an OB star cluster is described. The distribution of gas and dust around the stars, properties of the dust, and the cluster and interstellar radiation fields are variable. The model can be applied to regions around clusters embedded to various degrees in their parental molecular clouds (i.e., compact H II regions, blister-type H II regions, and the tenuous H II regions ionized by naked O stars). The model is used to simulate IRAS observations of a typical blister H II region. Infrared surface brightness and spectral energy distributions are predicted and the impact of limited spatial resolution is illustrated. The model results are shown to be consistent with observations of the exemplary outer Galaxy OB cluster NGC 7380. It is planned to use the model as a diagnostic tool to probe the physical conditions and dust properties in star-formation regions and, ultimately, in an interpretation of the spectral energy distributions of spiral galaxies.

The very massive star content of the nuclear star clusters in NGC 5253

NASA Astrophysics Data System (ADS)

Smith, Linda J.; Crowther, Paul A.; Calzetti, Daniela

2017-11-01

The blue compact dwarf galaxy NGC 5253 hosts a very young starburst containing twin nuclear star clusters. Calzetti et al. (2015) find that the two clusters have an age of 1 Myr, in contradiction to the age of 3-5 Myr inferred from the presence of Wolf-Rayet (W-R) spectral features. We use Hubble Space Telescope (HST) far-ultraviolet (FUV) and ground-based optical spectra to show that the cluster stellar features arise from very massive stars (VMS), with masses greater than 100 M⊙, at an age of 1-2 Myr. We discuss the implications of this and show that the very high ionizing flux can only be explained by VMS. We further discuss our findings in the context of VMS contributing to He ii λ1640 emission in high redshift galaxies, and emphasize that population synthesis models with upper mass cut-offs greater than 100 M⊙ are crucial for future studies of young massive clusters.

Structure assignment, electronic properties, and magnetism quenching of endohedrally doped neutral silicon clusters, Si(n)Co (n = 10-12).

PubMed

Li, Yejun; Tam, Nguyen Minh; Claes, Pieterjan; Woodham, Alex P; Lyon, Jonathan T; Ngan, Vu Thi; Nguyen, Minh Tho; Lievens, Peter; Fielicke, André; Janssens, Ewald

2014-09-18

The structures of neutral cobalt-doped silicon clusters have been assigned by a combined experimental and theoretical study. Size-selective infrared spectra of neutral Si(n)Co (n = 10-12) clusters are measured using a tunable IR-UV two-color ionization scheme. The experimental infrared spectra are compared with calculated spectra of low-energy structures predicted at the B3P86 level of theory. It is shown that the Si(n)Co (n = 10-12) clusters have endohedral caged structures, where the silicon frameworks prefer double-layered structures encapsulating the Co atom. Electronic structure analysis indicates that the clusters are stabilized by an ionic interaction between the Co dopant atom and the silicon cage due to the charge transfer from the silicon valence sp orbitals to the cobalt 3d orbitals. Strong hybridization between the Co dopant atom and the silicon host quenches the local magnetic moment on the encapsulated Co atom.

Laser desorption/ionization from nanostructured surfaces: nanowires, nanoparticle films and silicon microcolumn arrays

NASA Astrophysics Data System (ADS)

Chen, Yong; Luo, Guanghong; Diao, Jiajie; Chornoguz, Olesya; Reeves, Mark; Vertes, Akos

2007-04-01

Due to their optical properties and morphology, thin films formed of nanoparticles are potentially new platforms for soft laser desorption/ionization (SLDI) mass spectrometry. Thin films of gold nanoparticles (with 12±1 nm particle size) were prepared by evaporation-driven vertical colloidal deposition and used to analyze a series of directly deposited polypeptide samples. In this new SLDI method, the required laser fluence for ion detection was equal or less than what was needed for matrix-assisted laser desorption/ionization (MALDI) but the resulting spectra were free of matrix interferences. A silicon microcolumn array-based substrate (a.k.a. black silicon) was developed as a new matrix-free laser desorption ionization surface. When low-resistivity silicon wafers were processed with a 22 ps pulse length 3×ω Nd:YAG laser in air, SF6 or water environment, regularly arranged conical spikes emerged. The radii of the spike tips varied with the processing environment, ranging from approximately 500 nm in water, to ~2 µm in SF6 gas and to ~5 µm in air. Peptide mass spectra directly induced by a nitrogen laser showed the formation of protonated ions of angiotensin I and II, substance P, bradykinin fragment 1-7, synthetic peptide, pro14-arg, and insulin from the processed silicon surfaces but not from the unprocessed areas. Threshold fluences for desorption/ionization were similar to those used in MALDI. Although compared to silicon nanowires the threshold laser pulse energy for ionization is significantly (~10×) higher, the ease of production and robustness of microcolumn arrays offer complementary benefits.

Relativistic equation-of-motion coupled-cluster method using open-shell reference wavefunction: Application to ionization potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pathak, Himadri, E-mail: hmdrpthk@gmail.com; Sasmal, Sudip, E-mail: sudipsasmal.chem@gmail.com; Vaval, Nayana

2016-08-21

The open-shell reference relativistic equation-of-motion coupled-cluster method within its four-component description is successfully implemented with the consideration of single- and double- excitation approximations using the Dirac-Coulomb Hamiltonian. At the first attempt, the implemented method is employed to calculate ionization potential value of heavy atomic (Ag, Cs, Au, Fr, and Lr) and molecular (HgH and PbF) systems, where the effect of relativity does really matter to obtain highly accurate results. Not only the relativistic effect but also the effect of electron correlation is crucial in these heavy atomic and molecular systems. To justify the fact, we have taken two further approximationsmore » in the four-component relativistic equation-of-motion framework to quantify how the effect of electron correlation plays a role in the calculated values at different levels of theory. All these calculated results are compared with the available experimental data as well as with other theoretically calculated values to judge the extent of accuracy obtained in our calculations.« less

Structure and Dynamics of Ionic Block Copolymer Melts: Computational Study

DOE PAGES

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; ...

2017-09-06

Structure and dynamics of melts of copolymers with an ABCBA topology, where C is an ionizable block, have been studied by fully atomistic molecular dynamics (MD) simulations. Introducing an ionizable block for functionality adds a significant element to the coupled set of interactions that determine the structure and dynamics of the macromolecule. The polymer consists of a randomly sulfonated polystyrene C block tethered to a flexible poly(ethylene-r-propylene) bridge B and end-capped with poly(tert-butylstyrene) A. The chemical structure and topology of these polymers constitute a model for incorporation of ionic blocks within a framework that provides tactility and mechanical stability. Heremore » in this paper we resolve the structure and dynamics of a structured polymer on the nanoscale constrained by ionic clusters. We find that the melts form intertwined networks of the A and C blocks independent of the degree of sulfonation of the C block with no long-range order. The cluster cohesiveness and morphology affect both macroscopic translational motion and segmental dynamics of all the blocks.« less

Structure and Dynamics of Ionic Block Copolymer Melts: Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora

Structure and dynamics of melts of copolymers with an ABCBA topology, where C is an ionizable block, have been studied by fully atomistic molecular dynamics (MD) simulations. Introducing an ionizable block for functionality adds a significant element to the coupled set of interactions that determine the structure and dynamics of the macromolecule. The polymer consists of a randomly sulfonated polystyrene C block tethered to a flexible poly(ethylene-r-propylene) bridge B and end-capped with poly(tert-butylstyrene) A. The chemical structure and topology of these polymers constitute a model for incorporation of ionic blocks within a framework that provides tactility and mechanical stability. Heremore » in this paper we resolve the structure and dynamics of a structured polymer on the nanoscale constrained by ionic clusters. We find that the melts form intertwined networks of the A and C blocks independent of the degree of sulfonation of the C block with no long-range order. The cluster cohesiveness and morphology affect both macroscopic translational motion and segmental dynamics of all the blocks.« less

Self-consistent semi-analytic models of the first stars

NASA Astrophysics Data System (ADS)

Visbal, Eli; Haiman, Zoltán; Bryan, Greg L.

2018-04-01

We have developed a semi-analytic framework to model the large-scale evolution of the first Population III (Pop III) stars and the transition to metal-enriched star formation. Our model follows dark matter haloes from cosmological N-body simulations, utilizing their individual merger histories and three-dimensional positions, and applies physically motivated prescriptions for star formation and feedback from Lyman-Werner (LW) radiation, hydrogen ionizing radiation, and external metal enrichment due to supernovae winds. This method is intended to complement analytic studies, which do not include clustering or individual merger histories, and hydrodynamical cosmological simulations, which include detailed physics, but are computationally expensive and have limited dynamic range. Utilizing this technique, we compute the cumulative Pop III and metal-enriched star formation rate density (SFRD) as a function of redshift at z ≥ 20. We find that varying the model parameters leads to significant qualitative changes in the global star formation history. The Pop III star formation efficiency and the delay time between Pop III and subsequent metal-enriched star formation are found to have the largest impact. The effect of clustering (i.e. including the three-dimensional positions of individual haloes) on various feedback mechanisms is also investigated. The impact of clustering on LW and ionization feedback is found to be relatively mild in our fiducial model, but can be larger if external metal enrichment can promote metal-enriched star formation over large distances.

Radiation-Induced Chemical Dynamics in Ar Clusters Exposed to Strong X-Ray Pulses.

PubMed

Kumagai, Yoshiaki; Jurek, Zoltan; Xu, Weiqing; Fukuzawa, Hironobu; Motomura, Koji; Iablonskyi, Denys; Nagaya, Kiyonobu; Wada, Shin-Ichi; Mondal, Subhendu; Tachibana, Tetsuya; Ito, Yuta; Sakai, Tsukasa; Matsunami, Kenji; Nishiyama, Toshiyuki; Umemoto, Takayuki; Nicolas, Christophe; Miron, Catalin; Togashi, Tadashi; Ogawa, Kanade; Owada, Shigeki; Tono, Kensuke; Yabashi, Makina; Son, Sang-Kil; Ziaja, Beata; Santra, Robin; Ueda, Kiyoshi

2018-06-01

We show that electron and ion spectroscopy reveals the details of the oligomer formation in Ar clusters exposed to an x-ray free electron laser (XFEL) pulse, i.e., chemical dynamics triggered by x rays. With guidance from a dedicated molecular dynamics simulation tool, we find that van der Waals bonding, the oligomer formation mechanism, and charge transfer among the cluster constituents significantly affect ionization dynamics induced by an XFEL pulse of moderate fluence. Our results clearly demonstrate that XFEL pulses can be used not only to "damage and destroy" molecular assemblies but also to modify and transform their molecular structure. The accuracy of the predictions obtained makes it possible to apply the cluster spectroscopy, in connection with the respective simulations, for estimation of the XFEL pulse fluence in the fluence regime below single-atom multiple-photon absorption, which is hardly accessible with other diagnostic tools.

Radiation-Induced Chemical Dynamics in Ar Clusters Exposed to Strong X-Ray Pulses

NASA Astrophysics Data System (ADS)

Kumagai, Yoshiaki; Jurek, Zoltan; Xu, Weiqing; Fukuzawa, Hironobu; Motomura, Koji; Iablonskyi, Denys; Nagaya, Kiyonobu; Wada, Shin-ichi; Mondal, Subhendu; Tachibana, Tetsuya; Ito, Yuta; Sakai, Tsukasa; Matsunami, Kenji; Nishiyama, Toshiyuki; Umemoto, Takayuki; Nicolas, Christophe; Miron, Catalin; Togashi, Tadashi; Ogawa, Kanade; Owada, Shigeki; Tono, Kensuke; Yabashi, Makina; Son, Sang-Kil; Ziaja, Beata; Santra, Robin; Ueda, Kiyoshi

2018-06-01

We show that electron and ion spectroscopy reveals the details of the oligomer formation in Ar clusters exposed to an x-ray free electron laser (XFEL) pulse, i.e., chemical dynamics triggered by x rays. With guidance from a dedicated molecular dynamics simulation tool, we find that van der Waals bonding, the oligomer formation mechanism, and charge transfer among the cluster constituents significantly affect ionization dynamics induced by an XFEL pulse of moderate fluence. Our results clearly demonstrate that XFEL pulses can be used not only to "damage and destroy" molecular assemblies but also to modify and transform their molecular structure. The accuracy of the predictions obtained makes it possible to apply the cluster spectroscopy, in connection with the respective simulations, for estimation of the XFEL pulse fluence in the fluence regime below single-atom multiple-photon absorption, which is hardly accessible with other diagnostic tools.

The Gaia-ESO Survey: dynamics of ionized and neutral gas in the Lagoon nebula (M 8)

NASA Astrophysics Data System (ADS)

Damiani, F.; Bonito, R.; Prisinzano, L.; Zwitter, T.; Bayo, A.; Kalari, V.; Jiménez-Esteban, F. M.; Costado, M. T.; Jofré, P.; Randich, S.; Flaccomio, E.; Lanzafame, A. C.; Lardo, C.; Morbidelli, L.; Zaggia, S.

2017-08-01

Aims: We present a spectroscopic study of the dynamics of the ionized and neutral gas throughout the Lagoon nebula (M 8), using VLT-FLAMES data from the Gaia-ESO Survey. The new data permit exploration of the physical connections between the nebular gas and the stellar population of the associated star cluster NGC 6530. Methods: We characterized through spectral fitting emission lines of Hα, [N II] and [S II] doublets, [O III], and absorption lines of sodium D doublet, using data from the FLAMES-Giraffe and UVES spectrographs, on more than 1000 sightlines toward the entire face of the Lagoon nebula. Gas temperatures are derived from line-width comparisons, densities from the [S II] doublet ratio, and ionization parameter from Hα/[N II] ratio. Although doubly-peaked emission profiles are rarely found, line asymmetries often imply multiple velocity components along the same line of sight. This is especially true for the sodium absorption, and for the [O III] lines. Results: Spatial maps for density and ionization are derived, and compared to other known properties of the nebula and of its massive stars 9 Sgr, Herschel 36 and HD 165052 which are confirmed to provide most of the ionizing flux. The detailed velocity fields across the nebula show several expanding shells, related to the cluster NGC 6530, the O stars 9 Sgr and Herschel 36, and the massive protostar M 8East-IR. The origins of kinematical expansion and ionization of the NGC 6530 shell appear to be different. We are able to put constrains on the line-of-sight (relative or absolute) distances between some of these objects and the molecular cloud. The data show that the large obscuring band running through the middle of the nebula is being compressed by both sides, which might explain its enhanced density. We also find an unexplained large-scale velocity gradient across the entire nebula. At larger distances, the transition from ionized to neutral gas is studied using the sodium lines. Based on observations collected with the FLAMES spectrograph at VLT/UT2 telescope (Paranal Observatory, ESO, Chile), for the Gaia-ESO Large Public Survey (program 188.B-3002).Full Tables A.1 and A.2 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/604/A135

A Comparison of Vertical Stiffness Values Calculated from Different Measures of Center of Mass Displacement in Single-Leg Hopping.

PubMed

Mudie, Kurt L; Gupta, Amitabh; Green, Simon; Hobara, Hiroaki; Clothier, Peter J

2017-02-01

This study assessed the agreement between K vert calculated from 4 different methods of estimating vertical displacement of the center of mass (COM) during single-leg hopping. Healthy participants (N = 38) completed a 10-s single-leg hopping effort on a force plate, with 3D motion of the lower limb, pelvis, and trunk captured. Derived variables were calculated for a total of 753 hop cycles using 4 methods, including: double integration of the vertical ground reaction force, law of falling bodies, a marker cluster on the sacrum, and a segmental analysis method. Bland-Altman plots demonstrated that K vert calculated using segmental analysis and double integration methods have a relatively small bias (0.93 kN⋅m -1 ) and 95% limits of agreement (-1.89 to 3.75 kN⋅m -1 ). In contrast, a greater bias was revealed between sacral marker cluster and segmental analysis (-2.32 kN⋅m -1 ), sacral marker cluster and double integration (-3.25 kN⋅m -1 ), and the law of falling bodies compared with all methods (17.26-20.52 kN⋅m -1 ). These findings suggest the segmental analysis and double integration methods can be used interchangeably for the calculation of K vert during single-leg hopping. The authors propose the segmental analysis method to be considered the gold standard for the calculation of K vert during single-leg, on-the-spot hopping.

The Contribution of Ionizing Stars to the Far-Infrared and Radio Emission in the Galaxy

NASA Astrophysics Data System (ADS)

Terebey, S.; Fich, M.; Taylor, R.

1999-12-01

A summary of research activities carried out in this eighth and final progress report. The final report includes: this summary document, copies of three published research papers, plus a draft manuscript of a fourth research paper entitled "The Contribution of Ionizing Stars to the FarInfrared and Radio Emission in the Milky Way; Evidence for a Swept-up Shell and Diffuse Ionized Halo around the W4 Chimney/Supershell." The main activity during the final quarterly reporting period was research on W4, including analysis of the radio and far-infrared images, generation of shell models, a literature search, and preparation of a research manuscript. There will be additional consultation with co-authors prior to submission of the paper to the Astrophysical Journal. The results will be presented at the 4th Tetons Summer Conference on "Galactic Structure, Stars, and the ISM" in May 2000. In this fourth and last paper we show W4 has a swept-up partially ionized shell of gas and dust which is powered by the OCl 352 star cluster. Analysis shows there is dense interstellar material directly below the shell, evidence that that the lower W4 shell "ran into a brick wall" and stalled, whereas the upper W4 shell achieved "breakout" to form a Galactic chimney. An ionized halo is evidence of Lyman continuum leakage which ionizes the WIM (warm ionized medium). It has long been postulated that the strong winds and abundant ionizing photons from massive stars are responsible for much of the large scale structure in the interstellar medium (ISM), including the ISM in other galaxies. However standard HII region theory predicts few photons will escape the local HII region. The significance of W4 and this work is it provides a direct example of how stellar winds power a galactic chimney, which in turn leads to a low density cavity from which ionizing photons can escape to large distances to ionize the WIM.

The Contribution of Ionizing Stars to the Far-Infrared and Radio Emission in the Galaxy

NASA Technical Reports Server (NTRS)

Terebey, S.; Fich, M.; Taylor, R.

1999-01-01

A summary of research activities carried out in this eighth and final progress report. The final report includes: this summary document, copies of three published research papers, plus a draft manuscript of a fourth research paper entitled "The Contribution of Ionizing Stars to the FarInfrared and Radio Emission in the Milky Way; Evidence for a Swept-up Shell and Diffuse Ionized Halo around the W4 Chimney/Supershell." The main activity during the final quarterly reporting period was research on W4, including analysis of the radio and far-infrared images, generation of shell models, a literature search, and preparation of a research manuscript. There will be additional consultation with co-authors prior to submission of the paper to the Astrophysical Journal. The results will be presented at the 4th Tetons Summer Conference on "Galactic Structure, Stars, and the ISM" in May 2000. In this fourth and last paper we show W4 has a swept-up partially ionized shell of gas and dust which is powered by the OCl 352 star cluster. Analysis shows there is dense interstellar material directly below the shell, evidence that that the lower W4 shell "ran into a brick wall" and stalled, whereas the upper W4 shell achieved "breakout" to form a Galactic chimney. An ionized halo is evidence of Lyman continuum leakage which ionizes the WIM (warm ionized medium). It has long been postulated that the strong winds and abundant ionizing photons from massive stars are responsible for much of the large scale structure in the interstellar medium (ISM), including the ISM in other galaxies. However standard HII region theory predicts few photons will escape the local HII region. The significance of W4 and this work is it provides a direct example of how stellar winds power a galactic chimney, which in turn leads to a low density cavity from which ionizing photons can escape to large distances to ionize the WIM.

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Theoretical and Experimental Insights into the Dissociation of 2-Hydroxyethylhydrazinium Nitrate Clusters Formed via Electrospray.

PubMed

Patrick, Amanda L; Vogelhuber, Kristen M; Prince, Benjamin D; Annesley, Christopher J

2018-03-01

Ionic liquids are used for myriad applications, including as catalysts, solvents, and propellants. Specifically, 2-hydroxyethylhydrazinium nitrate (HEHN) has been developed as a chemical propellant for space applications. The gas-phase behavior of HEHN ions and clusters is important in understanding its potential as an electrospray thruster propellant. Here, the unimolecular dissociation pathways of two clusters are experimentally observed, and theoretical modeling of hydrogen bonding and dissociation pathways is used to help rationalize those observations. The cation/deprotonated cation cluster [HEH 2 - H] + , which is observed from electrospray ionization, is calculated to be considerably more stable than the complementary cation/protonated anion adduct, [HEH + HNO 3 ] + , which is not observed experimentally. Upon collisional activation, a larger cluster [(HEHN) 2 HEH] + undergoes dissociation via loss of nitric acid at lower collision energies, as predicted theoretically. At higher collision energies, additional primary and secondary loss pathways open, including deprotonated cation loss, ion-pair loss, and double-nitric-acid loss. Taken together, these experimental and theoretical results contribute to a foundational understanding of the dissociation of protic ionic liquid clusters in the gas phase.

A highly sensitive electron spectrometer for crossed-beam collisional ionization: A retarding-type magnetic bottle analyzer and its application to collision-energy resolved Penning ionization electron spectroscopy

NASA Astrophysics Data System (ADS)

Yamakita, Yoshihiro; Tanaka, Hideyasu; Maruyama, Ryo; Yamakado, Hideo; Misaizu, Fuminori; Ohno, Koichi

2000-08-01

A highly sensitive electron energy analyzer which utilizes a "magnetic bottle" combined with a retarding electrostatic field has been developed for Penning ionization electron spectroscopy. A beam of metastable rare-gas atoms is crossed with a continuous supersonic sample beam in the source region of the analyzer. The emitted electrons are collected by an inhomogeneous magnetic field (the magnetic bottle effect) with a high efficiency of nearly 4π solid angle, which is more than 103 times higher than that of a conventional hemispherical analyzer. The kinetic energy of electrons is analyzed by scanning the retarding field in a flight tube of the analyzer in the presence of a weak magnetic field. The velocity of the metastable atoms can also be resolved by a time-of-flight method in the present instrument. Examples of Penning ionization electron energy spectra as a function of collision energy are presented for Ar and N2 with metastable He*(2 3S) atoms. This instrument has opened the possibility for extensive studies of Penning ionization electron spectroscopy for low-density species, such as clusters, ions, electronically excited species, unstable or transient species, and large molecules with low volatility.

Structure of 2,4-Diaminopyrimidine - Theobromine Alternate Base Pairs

NASA Technical Reports Server (NTRS)

Gengeliczki, Zsolt; Callahan, Michael P.; Kabelac, Martin; Rijs, Anouk M.; deVries, Mattanjah S.

2011-01-01

We report the structure of clusters of 2,4-diaminopyrimidine with 3,7-dimethylxanthine (theobromine) in the gas phase determined by IR-UV double resonance spectroscopy in both the near-IR and mid-IR regions in combination with ab initio computations. These clusters represent potential alternate nucleobase pairs, geometrically equivalent to guanine-cytosine. We have found the four lowest energy structures, which include the Watson-Crick base pairing motif. This Watson-Crick structure has not been observed by resonant two-photon ionization (R2PI) in the gas phase for the canonical DNA base pairs.

Assessment of interaction-strength interpolation formulas for gold and silver clusters

NASA Astrophysics Data System (ADS)

Giarrusso, Sara; Gori-Giorgi, Paola; Della Sala, Fabio; Fabiano, Eduardo

2018-04-01

The performance of functionals based on the idea of interpolating between the weak- and the strong-interaction limits the global adiabatic-connection integrand is carefully studied for the challenging case of noble-metal clusters. Different interpolation formulas are considered and various features of this approach are analyzed. It is found that these functionals, when used as a correlation correction to Hartree-Fock, are quite robust for the description of atomization energies, while performing less well for ionization potentials. Future directions that can be envisaged from this study and a previous one on main group chemistry are discussed.

High-resolution X-ray spectroscopy of M87 with the Einstein observatory - The detection of an O VIII emission line

NASA Technical Reports Server (NTRS)

Canizares, C. R.; Clark, G. W.; Markert, T. H.; Berg, C.; Smedira, M.; Bardas, D.; Schnopper, H.; Kalata, K.

1979-01-01

The paper deals with high-resolution X-ray spectroscopy performed to study the extended source surrounding the giant elliptical galaxy, M87, in the Virgo cluster. From observations carried out with a focal plane crystal spectrometer, L-alpha emission was detected from hydrogenic oxygen (O VIII). Upper limits could be set on lines from intermediate ionization states of iron. The presence of a quantity of cooler matter surrounding M87 was revealed, which has important implications for cluster models and favors a radiatively controlled accretion mechanism.

Sodium dopants in helium clusters: Structure, equilibrium and submersion kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calvo, F.

Alkali impurities bind to helium nanodroplets very differently depending on their size and charge state, large neutral or charged dopants being wetted by the droplet whereas small neutral impurities prefer to reside aside. Using various computational modeling tools such as quantum Monte Carlo and path-integral molecular dynamics simulations, we have revisited some aspects of the physical chemistry of helium droplets interacting with sodium impurities, including the onset of snowball formation in presence of many-body polarization forces, the transition from non-wetted to wetted behavior in larger sodium clusters, and the kinetics of submersion of small dopants after sudden ionization.

Structural, electronic, and magnetic properties of Y(n)O (n=2-14) clusters: Density functional study.

PubMed

Yang, Zhi; Xiong, Shi-Jie

2008-09-28

The geometries stability, electronic properties, and magnetism of Y(n)O clusters up to n=14 are systematically studied with density functional theory. In the lowest-energy structures of Y(n)O clusters, the equilibrium site of the oxygen atom gradually moves from an outer site of the cluster, via a surface site, and finally, to an interior site as the number of the Y atoms increases from 2 to 14. Starting from n=12, the O atom falls into the center of the cluster with the Y atoms forming the outer frame. The results show that clusters with n=2, 4, 8, and 12 are more stable than their respective neighbors, and that the total magnetic moments of Y(n)O clusters are all quite small except Y(12)O cluster. The lowest-energy structure of Y(12)O cluster is a perfect icosahedron with a large magnetic moment 6mu(B). In addition, we find that the total magnetic moments are quenched for n=2, 6, and 8 due to the closed-shell electronic configuration. The calculated ionization potentials and electron affinities are in good agreement with the experimental results, which imply that the present theoretical treatments are satisfactory.

Observable Signatures of Cosmic Reionization and the End of the Dark Ages

NASA Astrophysics Data System (ADS)

Shapiro, Paul R.; Iliev, I. T.; Mellema, G.; Pen, U. L.; McDonald, P.; Bond, J. R.; Alvarez, M.; Ahn, K.

2007-12-01

Reionization exerted a strong feedback effect which left its imprint on all scales and on radiation backgrounds at all wavelengths. When the first stars formed inside minihalos of mass 106 solar masses at z > 20, ionizing radiation heated and expelled the gas inside their minihalos and escaped to create intergalactic H II regions. As these H II regions grew, their ionization fronts encountered other minihalos, which blocked their path and trapped them, causing this minihalo gas, too, to escape in a photoevaporative wind. Further star formation inside minihalos was affected not only by these I-fronts, but also by the rising dissociating background. Eventually, hierarchical clustering formed dwarf galaxies > 108 solar masses, where atomic cooling was effective enough to trigger more star formation, and intergalactic H II regions grew and merged to become 10's of comoving Mpc's in size. Inside these H II regions, gas pressure inhibited gravitational collapse, so the minimum mass of newly-formed galaxies jumped above 109 solar masses. Reionization ended when the intergalactic H II regions finally overlapped everywhere. We have studied this process by a variety of techniques, on a hierarchy of mass- and length-scales. The latter span the range from interiors of minihalos, to giant H II regions produced by the clustered formation of galaxies, to large-scale structure of the patchy distribution of neutral and ionized gas during the epoch of reionization. These results lead to predictions of a fluctuating background of redshifted 21-cm line radiation, temperature and polarization anisotropy of the CMB, gaps in the Gunn-Peterson absorption spectra of high-z quasars, and distortion of the luminosity function and spatial clustering of Lyman alpha emission-line galaxies during this epoch, among other things. I will summarize the latest theoretical developments in this talk. This work supported by NASA grants NNX07AH09G and NNG04GI77G and NSF AST-0708176.

A magnified young galaxy from about 500 million years after the Big Bang.

PubMed

Zheng, Wei; Postman, Marc; Zitrin, Adi; Moustakas, John; Shu, Xinwen; Jouvel, Stephanie; Høst, Ole; Molino, Alberto; Bradley, Larry; Coe, Dan; Moustakas, Leonidas A; Carrasco, Mauricio; Ford, Holland; Benítez, Narciso; Lauer, Tod R; Seitz, Stella; Bouwens, Rychard; Koekemoer, Anton; Medezinski, Elinor; Bartelmann, Matthias; Broadhurst, Tom; Donahue, Megan; Grillo, Claudio; Infante, Leopoldo; Jha, Saurabh W; Kelson, Daniel D; Lahav, Ofer; Lemze, Doron; Melchior, Peter; Meneghetti, Massimo; Merten, Julian; Nonino, Mario; Ogaz, Sara; Rosati, Piero; Umetsu, Keiichi; van der Wel, Arjen

2012-09-20

Re-ionization of the intergalactic medium occurred in the early Universe at redshift z ≈ 6-11, following the formation of the first generation of stars. Those young galaxies (where the bulk of stars formed) at a cosmic age of less than about 500 million years (z ≲ 10) remain largely unexplored because they are at or beyond the sensitivity limits of existing large telescopes. Understanding the properties of these galaxies is critical to identifying the source of the radiation that re-ionized the intergalactic medium. Gravitational lensing by galaxy clusters allows the detection of high-redshift galaxies fainter than what otherwise could be found in the deepest images of the sky. Here we report multiband observations of the cluster MACS J1149+2223 that have revealed (with high probability) a gravitationally magnified galaxy from the early Universe, at a redshift of z = 9.6 ± 0.2 (that is, a cosmic age of 490 ± 15 million years, or 3.6 per cent of the age of the Universe). We estimate that it formed less than 200 million years after the Big Bang (at the 95 per cent confidence level), implying a formation redshift of ≲14. Given the small sky area that our observations cover, faint galaxies seem to be abundant at such a young cosmic age, suggesting that they may be the dominant source for the early re-ionization of the intergalactic medium.

Electrospray ionization mass spectrometry for the hydrolysis complexes of cisplatin: implications for the hydrolysis process of platinum complexes.

PubMed

Feifan, Xie; Pieter, Colin; Jan, Van Bocxlaer

2017-07-01

Non-enzyme-dependent hydrolysis of the drug cisplatin is important for its mode of action and toxicity. However, up until today, the hydrolysis process of cisplatin is still not completely understood. In the present study, the hydrolysis of cisplatin in an aqueous solution was systematically investigated by using electrospray ionization mass spectrometry coupled to liquid chromatography. A variety of previously unreported hydrolysis complexes corresponding to monomeric, dimeric and trimeric species were detected and identified. The characteristics of the Pt-containing complexes were investigated by using collision-induced dissociation (CID). The hydrolysis complexes demonstrate distinctive and correlative CID characteristics, which provides tools for an informative identification. The most frequently observed dissociation mechanism was sequential loss of NH 3 , H 2 O and HCl. Loss of the Pt atom was observed as the final step during the CID process. The formation mechanisms of the observed complexes were explored and experimentally examined. The strongly bound dimeric species, which existed in solution, are assumed to be formed from the clustering of the parent compound and its monohydrated or dihydrated complexes. The role of the electrospray process in the formation of some of the observed ions was also evaluated, and the electrospray ionization-related cold clusters were identified. The previously reported hydrolysis equilibria were tested and subsequently refined via a hydrolysis study resulting in a renewed mechanistic equilibrium system of cisplatin as proposed from our results. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

The ATLAS3D project - X. On the origin of the molecular and ionized gas in early-type galaxies

NASA Astrophysics Data System (ADS)

Davis, Timothy A.; Alatalo, Katherine; Sarzi, Marc; Bureau, Martin; Young, Lisa M.; Blitz, Leo; Serra, Paolo; Crocker, Alison F.; Krajnović, Davor; McDermid, Richard M.; Bois, Maxime; Bournaud, Frédéric; Cappellari, Michele; Davies, Roger L.; Duc, Pierre-Alain; de Zeeuw, P. Tim; Emsellem, Eric; Khochfar, Sadegh; Kuntschner, Harald; Lablanche, Pierre-Yves; Morganti, Raffaella; Naab, Thorsten; Oosterloo, Tom; Scott, Nicholas; Weijmans, Anne-Marie

2011-10-01

We make use of interferometric CO and H I observations, and optical integral-field spectroscopy from the ATLAS3D survey, to probe the origin of the molecular and ionized interstellar medium (ISM) in local early-type galaxies. We find that 36 ± 5 per cent of our sample of fast-rotating early-type galaxies have their ionized gas kinematically misaligned with respect to the stars, setting a strong lower limit on the importance of externally acquired gas (e.g. from mergers and cold accretion). Slow rotators have a flat distribution of misalignments, indicating that the dominant source of gas is external. The molecular, ionized and atomic gas in all the detected galaxies are always kinematically aligned, even when they are misaligned from the stars, suggesting that all these three phases of the ISM share a common origin. In addition, we find that the origin of the cold and warm gas in fast-rotating early-type galaxies is strongly affected by environment, despite the molecular gas detection rate and mass fractions being fairly independent of group/cluster membership. Galaxies in dense groups and the Virgo cluster nearly always have their molecular gas kinematically aligned with the stellar kinematics, consistent with a purely internal origin (presumably stellar mass loss). In the field, however, kinematic misalignments between the stellar and gaseous components indicate that at least 42 ± 5 per cent of local fast-rotating early-type galaxies have their gas supplied from external sources. When one also considers evidence of accretion present in the galaxies' atomic gas distributions, ≳46 per cent of fast-rotating field ETGs are likely to have acquired a detectable amount of ISM from accretion and mergers. We discuss several scenarios which could explain the environmental dichotomy, including preprocessing in galaxy groups/cluster outskirts and the morphological transformation of spiral galaxies, but we find it difficult to simultaneously explain the kinematic misalignment difference and the constant detection rate. Furthermore, our results suggest that galaxy mass may be an important independent factor associated with the origin of the gas, with the most massive fast-rotating galaxies in our sample (MK≲-24 mag; stellar mass of ≈8 × 1010 M⊙) always having kinematically aligned gas. This mass dependence appears to be independent of environment, suggesting it is caused by a separate physical mechanism.

Assessment of electron propagator methods for the simulation of vibrationally-resolved valence and core photoionization spectra

PubMed Central

Baiardi, A.; Paoloni, L.; Barone, V.; Zakrzewski, V.G.; Ortiz, J.V.

2017-01-01

The analysis of photoelectron spectra is usually facilitated by quantum mechanical simulations. Due to the recent improvement of experimental techniques, the resolution of experimental spectra is rapidly increasing, and the inclusion of vibrational effects is usually mandatory to obtain a reliable reproduction of the spectra. With the aim of defining a robust computational protocol, a general time-independent formulation to compute different kinds of vibrationally-resolved electronic spectra has been generalized to support also photoelectron spectroscopy. The electronic structure data underlying the simulation are computed using different electron propagator approaches. In addition to the more standard approaches, a new and robust implementation of the second-order self-energy approximation of the electron propagator based on a transition operator reference (TOEP2) is presented. To validate our implementation, a series of molecules has been used as test cases. The result of the simulations shows that, for ultraviolet photoionization spectra, the more accurate non-diagonal approaches are needed to obtain a reliable reproduction of vertical ionization energies, but diagonal approaches are sufficient for energy gradients and pole strengths. For X-ray photoelectron spectroscopy, the TOEP2 approach, besides being more efficient, is also the most accurate in the reproduction of both vertical ionization energies and vibrationally-resolved bandshapes. PMID:28521087

Clustering of velocities in a GPS network spanning the Sierra Nevada Block, the Northern Walker Lane Belt, and the Central Nevada Seismic Belt, California-Nevada

NASA Astrophysics Data System (ADS)

Savage, J. C.; Simpson, R. W.

2013-09-01

The deformation across the Sierra Nevada Block, the Walker Lane Belt, and the Central Nevada Seismic Belt (CNSB) between 38.5°N and 40.5°N has been analyzed by clustering GPS velocities to identify coherent blocks. Cluster analysis determines the number of clusters required and assigns the GPS stations to the proper clusters. The clusters are shown on a fault map by symbols located at the positions of the GPS stations, each symbol representing the cluster to which the velocity of that GPS station belongs. Fault systems that separate the clusters are readily identified on such a map. Four significant clusters are identified. Those clusters are strips separated by (from west to east) the Mohawk Valley-Genoa fault system, the Pyramid Lake-Wassuk fault system, and the Central Nevada Seismic Belt. The strain rates within the westernmost three clusters approximate simple right-lateral shear (~13 nstrain/a) across vertical planes roughly parallel to the cluster boundaries. Clustering does not recognize the longitudinal segmentation of the Walker Lane Belt into domains dominated by either northwesterly trending, right-lateral faults or northeasterly trending, left-lateral faults.

Clustering of velocities in a GPS network spanning the Sierra Nevada Block, the northern Walker Lane Belt, and the Central Nevada Seismic Belt, California-Nevada

USGS Publications Warehouse

Savage, James C.; Simpson, Robert W.

2013-01-01

The deformation across the Sierra Nevada Block, the Walker Lane Belt, and the Central Nevada Seismic Belt (CNSB) between 38.5°N and 40.5°N has been analyzed by clustering GPS velocities to identify coherent blocks. Cluster analysis determines the number of clusters required and assigns the GPS stations to the proper clusters. The clusters are shown on a fault map by symbols located at the positions of the GPS stations, each symbol representing the cluster to which the velocity of that GPS station belongs. Fault systems that separate the clusters are readily identified on such a map. Four significant clusters are identified. Those clusters are strips separated by (from west to east) the Mohawk Valley-Genoa fault system, the Pyramid Lake-Wassuk fault system, and the Central Nevada Seismic Belt. The strain rates within the westernmost three clusters approximate simple right-lateral shear (~13 nstrain/a) across vertical planes roughly parallel to the cluster boundaries. Clustering does not recognize the longitudinal segmentation of the Walker Lane Belt into domains dominated by either northwesterly trending, right-lateral faults or northeasterly trending, left-lateral faults.

Ab initio Study on Ionization Energies of 3-Amino-1-propanol

NASA Astrophysics Data System (ADS)

Wang, Ke-dong; Jia, Ying-bin; Lai, Zhen-jiang; Liu, Yu-fang

2011-06-01

Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311++G** level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the intramolecular OH···N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molecular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of photoelectron spectra is interpreted.

Photoionization of Benzene and Small Polycyclic Aromatic Hydrocarbons in Ultraviolet-Processed Astrophysical Ices: A Computational Study

NASA Technical Reports Server (NTRS)

Woon, D. E.; Park, J.-Y.

2004-01-01

We employed density functional theory (DFT) calculations to model the photoionization behavior of benzene and small polycyclic aromatic hydrocarbons when they are embedded in a matrix of water ice in order to investigate issues raised by recent experimental work by Gudipati and Allamandola. The ionization energies of benzene, naphthalene, anthracene, and pyrene were found to be lowered by 1.5-2.1 eV in water ice. Low-lying vertical electronic excitation energies were computed with time-dependent DFT for both neutral and ionized species and are found in both cases to be remarkably unaffected by the ice matrix. Chemical behavior in ultraviolet-photoprocessed ices is also discussed, with a focus on electron recombination and pathways leading to phenol and analogous products.

The TIME-Pilot intensity mapping experiment

NASA Astrophysics Data System (ADS)

Crites, A. T.; Bock, J. J.; Bradford, C. M.; Chang, T. C.; Cooray, A. R.; Duband, L.; Gong, Y.; Hailey-Dunsheath, S.; Hunacek, J.; Koch, P. M.; Li, C. T.; O'Brient, R. C.; Prouve, T.; Shirokoff, E.; Silva, M. B.; Staniszewski, Z.; Uzgil, B.; Zemcov, M.

2014-08-01

TIME-Pilot is designed to make measurements from the Epoch of Reionization (EoR), when the first stars and galaxies formed and ionized the intergalactic medium. This will be done via measurements of the redshifted 157.7 um line of singly ionized carbon ([CII]). In particular, TIME-Pilot will produce the first detection of [CII] clustering fluctuations, a signal proportional to the integrated [CII] intensity, summed over all EoR galaxies. TIME-Pilot is thus sensitive to the emission from dwarf galaxies, thought to be responsible for the balance of ionizing UV photons, that will be difficult to detect individually with JWST and ALMA. A detection of [CII] clustering fluctuations would validate current theoretical estimates of the [CII] line as a new cosmological observable, opening the door for a new generation of instruments with advanced technology spectroscopic array focal planes that will map [CII] fluctuations to probe the EoR history of star formation, bubble size, and ionization state. Additionally, TIME-Pilot will produce high signal-to-noise measurements of CO clustering fluctuations, which trace the role of molecular gas in star-forming galaxies at redshifts 0 < z < 2. With its unique atmospheric noise mitigation, TIME-Pilot also significantly improves sensitivity for measuring the kinetic Sunyaev-Zel'dovich (kSZ) effect in galaxy clusters. TIME-Pilot will employ a linear array of spectrometers, each consisting of a parallel-plate diffraction grating. The spectrometer bandwidth covers 185-323 GHz to both probe the entire redshift range of interest and to include channels at the edges of the band for atmospheric noise mitigation. We illuminate the telescope with f/3 horns, which balances the desire to both couple to the sky with the best efficiency per beam, and to pack a large number of horns into the fixed field of view. Feedhorns couple radiation to the waveguide spectrometer gratings. Each spectrometer grating has 190 facets and provides resolving power above 100. At this resolution, the longest dimension of the grating is 31 cm, which allows us to stack gratings in two blocks (one for each polarization) of 16 within a single cryostat, providing a 1x16 array of beams in a 14 arcminute field of view. Direct absorber TES sensors sit at the output of the grating on six linear facets over the output arc, allowing us to package and read out the detectors as arrays in a modular manner. The 1840 detectors will be read out with the NIST time-domain-multiplexing (TDM) scheme and cooled to a base temperature of 250 mK with a 3He sorption refrigerator. We present preliminary designs for the TIME-Pilot cryogenics, spectrometers, bolometers, and optics.

Equilibrium geometries, electronic and magnetic properties of small AunNi- (n = 1-9) clusters

NASA Astrophysics Data System (ADS)

Tang, Cui-Ming; Chen, Xiao-Xu; Yang, Xiang-Dong

2014-05-01

Geometrical, electronic and magnetic properties of small AunNi- (n = 1-9) clusters have been investigated based on density functional theory (DFT) at PW91P86 level. An extensive structural search shows that the relative stable structures of AunNi- (n = 1-9) clusters adopt 2D structure for n = 1-5, 7 and 3D structure for n = 6, 8-9. And the substitution of a Ni atom for an Au atom in the Au-n+1 cluster obviously changes the structure of the host cluster. Moreover, an odd-even alternation phenomenon has been found for HOMO-LUMO energy gaps, indicating that the relative stable structures of the AunNi- clusters with odd-numbered gold atoms have a higher relative stability. Finally, the natural population analysis (NPA) and the vertical detachment energies (VDE) are studied, respectively. The theoretical values of VDE are reported for the first time to our best knowledge.

Radiative transfer calculations of the diffuse ionized gas in disc galaxies with cosmic ray feedback

NASA Astrophysics Data System (ADS)

Vandenbroucke, Bert; Wood, Kenneth; Girichidis, Philipp; Hill, Alex S.; Peters, Thomas

2018-05-01

The large vertical scale heights of the diffuse ionized gas (DIG) in disc galaxies are challenging to model, as hydrodynamical models including only thermal feedback seem to be unable to support gas at these heights. In this paper, we use a three-dimensional Monte Carlo radiation transfer code to post-process disc simulations of the Simulating the Life-Cycle of Molecular Clouds project that include feedback by cosmic rays. We show that the more extended discs in simulations including cosmic ray feedback naturally lead to larger scale heights for the DIG which are more in line with observed scale heights. We also show that including a fiducial cosmic ray heating term in our model can help to increase the temperature as a function of disc scale height, but fails to reproduce observed DIG nitrogen and sulphur forbidden line intensities. We show that, to reproduce these line emissions, we require a heating mechanism that affects gas over a larger density range than is achieved by cosmic ray heating, which can be achieved by fine tuning the total luminosity of ionizing sources to get an appropriate ionizing spectrum as a function of scale height. This result sheds a new light on the relation between forbidden line emissions and temperature profiles for realistic DIG gas distributions.

Chemical analysis of solids with sub-nm depth resolution by using a miniature LIMS system designed for in situ space research

NASA Astrophysics Data System (ADS)

Riedo, Andreas; Grimaudo, Valentine; Moreno-García, Pavel; Brigitte Neuland, Maike; Tulej, Marek; Broekmann, Peter; Wurz, Peter

2015-04-01

Sensitive elemental and isotope analysis of solid samples are of considerable interest in nowadays in situ space research. For context in situ analysis, high spatial resolution is also of substantial importance. While the measurements conducted with high lateral resolution can provide compositional details of the surface of highly heterogeneous materials, depth profiling measurements yield information on compositional details of surface and subsurface. The mass spectrometric analysis with the vertical resolution at sub-µm levels is of special consideration and can deliver important information on processes, which may have modified the surface. Information on space weathering effects can be readily determined when the sample composition of the surface and sub-surface is studied with high vertical resolution. In this contribution we will present vertical depth resolution measurements conducted by our sensitive miniature laser ablation ionization time-of-flight mass spectrometer (160mm x Ø 60mm) designed for in situ space research [1-3]. The mass spectrometer is equipped with a fs-laser system (~190fs pulse width, λ = 775nm), which is used for ablation and ionization of the sample material [2]. Laser radiation is focussed on the target material to a spot size of about 10-20 µm in diameter. Mass spectrometric measurements are conducted with a mass resolution (m/Δm) of about 400-500 (at 56Fe mass peak) and with a superior dynamic range of more than eight orders of magnitude. The depth profiling performance studies were conducted on 10µm thick Cu films that were deposited by an additive-assisted electrochemical procedure on Si-wafers. The presented measurement study will show that the current instrument prototype is able to conduct quantitative chemical (elemental and isotope) analysis of solids with a vertical resolution at sub-nm level. Contaminants, incorporated by using additives (polymers containing e.g. C, N, O, S) and with layer thickness of a few nanometres, can be fully resolved [1]. The current measurement performance, including the sensitivity and the high vertical depth resolution, opens new perspectives for future applications in the laboratory, e.g. measurements of Genesis samples, and new measurement capabilities for in situ space research. References 1)V. Grimaudo, P. Moreno-García, M.B. Neuland, M. Tulej, P. Broekmann, P. Wurz and A. Riedo, "High-resolution chemical depth profiling of solid material using a miniature laser ablation/ionization mass spectrometer", Anal. Chem., 2015, submitted. 2)A. Riedo, M. Neuland, S. Meyer, M. Tulej, and P. Wurz, "Coupling of LMS with a fs-laser ablation ion source: elemental and isotope composition measurements", J. Anal. At. Spectrom., 2013, 28, 1256. 3)Tulej et al. CAMAM: A Miniature Laser Ablation Ionisation Mass Spectrometer and Microscope-Camera System for In Situ Investigation of the Composition and Morphology of Extraterrestrial Materials, Geostand. Geoanal. Res., 2014, doi: 10.1111/j.1751-908X.2014.00302.x

Thermodynamics and Charging of Interstellar Iron Nanoparticles

NASA Astrophysics Data System (ADS)

Hensley, Brandon S.; Draine, B. T.

2017-01-01

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar iron is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.

The epoch of cosmic heating by early sources of X-rays

NASA Astrophysics Data System (ADS)

Eide, Marius B.; Graziani, Luca; Ciardi, Benedetta; Feng, Yu; Kakiichi, Koki; Di Matteo, Tiziana

2018-05-01

Observations of the 21 cm line from neutral hydrogen indicate that an epoch of heating (EoH) might have preceded the later epoch of reionization. Here we study the effects on the ionization state and the thermal history of the intergalactic medium (IGM) during the EoH induced by different assumptions on ionizing sources in the high-redshift Universe: (i) stars; (ii) X-ray binaries (XRBs); (iii) thermal bremsstrahlung of the hot interstellar medium (ISM); and (iv) accreting nuclear black holes (BHs). To this aim, we post-process outputs from the (100 h-1 comoving Mpc)3 hydrodynamical simulation MassiveBlack-II with the cosmological 3D radiative transfer code CRASH, which follows the propagation of ultraviolet and X-ray photons, computing the thermal and ionization state of hydrogen and helium through the EoH. We find that stars determine the fully ionized morphology of the IGM, while the spectrally hard XRBs pave way for efficient subsequent heating and ionization by the spectrally softer ISM. With the seeding prescription in MassiveBlack-II, BHs do not contribute significantly to either ionization or heating. With only stars, most of the IGM remains in a cold state (with a median T = 11 K at z = 10), however, the presence of more energetic sources raises the temperature of regions around the brightest and more clustered sources above that of the cosmic microwave background, opening the possibility to observing the 21 cm signal in emission.

X-ray ionization of the intergalactic medium by quasars

NASA Astrophysics Data System (ADS)

Graziani, Luca; Ciardi, B.; Glatzle, M.

2018-06-01

We investigate the impact of quasars on the ionization of the surrounding intergalactic medium (IGM) with the radiative transfer code CRASH4, now accounting for X-rays and secondary electrons. After comparing with analytic solutions, we post-process a cosmic volume (≈1.5 × 104 Mpc3h-3) containing a ULAS J1120+0641-like quasar (QSO) hosted by a 5 × 1011M⊙h-1 dark matter (DM) halo. We find that: (i) the average HII region (R ˜ 3.2 pMpc in a lifetime tf = 107 yrs) is mainly set by UV flux, in agreement with semi-analytic scaling relations; (ii) a largely neutral (xHII < 0.001), warm (T ˜ 103 K) tail extends up to few Mpc beyond the ionization front, as a result of the X-ray flux; (iii) LyC-opaque inhomogeneities induce a line of sight (LOS) scatter in R as high as few physical Mpc, consistent with the DLA scenario proposed to explain the anomalous size of the ULAS J1120+0641 ionized region. On the other hand, with an ionization rate \\dot{N}_{γ ,0} ˜ 10^{57} s-1, the assumed DLA clustering and gas opacity, only one LOS shows an HII region compatible with the observed one. We deduce that either the ionization rate of the QSO is at least one order of magnitude lower or the ULAS J1120+0641 bright phase is shorter than 107 yrs.

Dense clumps of ionized gas near Pi Scorpii, as revealed by the fine-structure excitation of N II

NASA Technical Reports Server (NTRS)

Bertoldi, Frank; Jenkins, Edward B.

1992-01-01

The column density and the emission of the ionized gas along the line of sight toward the B1 V + B2 V binary star Pi Sco are measured on the basis of the fine-structure absorption lines of the ground state N II. It is found that the bulk of this ionized gas must be clumped on a length scale of 0.025 pc, which is far smaller than the observed size of the diffuse H II region surrounding Pi Sco of about 6 pc. The observed column density of S III toward Pi Sco yields an upper limit on the distance of the absorbing, clumped gas from the star of less than about 0.02 pc, assuming that both the N II and S III absorption arise from the same gas. The possibility that the ionized gas originates from a photoevaporating circumstellar disk directly surrounding Pi Sco is excluded, since such a disk would have an unusual size of order 0.025 pc and would have had to survive for the estimated age of Pi Sco of 5-8 Myr. The derived mean density of the clumped gas is of order 40/cu cm, so that the gas is at a pressure that far exceeds the mean pressure in the H II region. It is concluded that the ionized gas could originate from evaporation flows off a cluster of compact neutral objects that evaporate due to the ionizing radiation of Pi Sco.

Analysis of model Titan atmospheric components using ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Kojiro, D. R.; Cohen, M. J.; Wernlund, R. F.; Stimac, R. M.; Humphry, D. E.; Takeuchi, N.

1991-01-01

The Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS) was proposed as an analytical technique for the analysis of Titan's atmosphere during the Cassini Mission. The IMS is an atmospheric pressure, chemical detector that produces an identifying spectrum of each chemical species measured. When the IMS is combined with a GC as a GC-IMS, the GC is used to separate the sample into its individual components, or perhaps small groups of components. The IMS is then used to detect, quantify, and identify each sample component. Conventional IMS detection and identification of sample components depends upon a source of energetic radiation, such as beta radiation, which ionizes the atmospheric pressure host gas. This primary ionization initiates a sequence of ion-molecule reactions leading to the formation of sufficiently energetic positive or negative ions, which in turn ionize most constituents in the sample. In conventional IMS, this reaction sequence is dominated by the water cluster ion. However, many of the light hydrocarbons expected in Titan's atmosphere cannot be analyzed by IMS using this mechanism at the concentrations expected. Research at NASA Ames and PCP Inc., has demonstrated IMS analysis of expected Titan atmospheric components, including saturated aliphatic hydrocarbons, using two alternate sample ionizations mechanisms. The sensitivity of the IMS to hydrocarbons such as propane and butane was increased by several orders of magnitude. Both ultra dry (waterless) IMS sample ionization and metastable ionization were successfully used to analyze a model Titan atmospheric gas mixture.

Reticulate classification of mosaic microbial genomes using NeAT website.

PubMed

Lima-Mendez, Gipsi

2012-01-01

The tree of life is the classical representation of the evolutionary relationships between existent species. A tree is appropriate to display the divergence of species through mutation, i.e., by vertical descent. However, lateral gene transfer (LGT) is excluded from such representations. When LGT contribution to genome evolution cannot be neglected (e.g., for prokaryotes and mobile genetic elements), the tree becomes misleading. Networks appear as an intuitive way to represent both vertical and horizontal relationships, while overlapping groups within such graphs are more suitable for their classification. Here, we describe a method to represent both vertical and horizontal relationships. We start with a set of genomes whose coded proteins have been grouped into families based on sequence similarity. Next, all pairs of genomes are compared, counting the number of proteins classified into the same family. From this comparison, we derive a weighted graph where genomes with a significant number of similar proteins are linked. Finally, we apply a two-step clustering of this graph to produce a classification where nodes can be assigned to multiple clusters. The procedure can be performed using the Network Analysis Tools (NeAT) website.

Phase Transition for the Large-Dimensional Contact Process with Random Recovery Rates on Open Clusters

NASA Astrophysics Data System (ADS)

Xue, Xiaofeng

2016-12-01

In this paper we are concerned with the contact process with random recovery rates on open clusters of bond percolation on Z^d. Let ξ be a random variable such that P(ξ ≥ 1)=1, which ensures E1/ξ <+∞, then we assign i. i. d. copies of ξ on the vertices as the random recovery rates. Assuming that each edge is open with probability p and the infection can only spread through the open edges, then we obtain that limsup _{d→ +∞}λ _d≤ λ _c=1/pE{1}/{ξ}, where λ _d is the critical value of the process on Z^d, i.e., the maximum of the infection rates with which the infection dies out with probability one when only the origin is infected at t=0. To prove the above main result, we show that the following phase transition occurs. Assuming that lceil log drceil vertices are infected at t=0, where these vertices can be located anywhere, then when the infection rate λ >λ _c, the process survives with high probability as d→ +∞ while when λ <λ _c, the process dies out at time O(log d) with high probability.

Preparing transition-metal clusters in known structural forms: the mass-analyzed threshold ionization spectrum of V3.

PubMed

Ford, Mark S; Mackenzie, Stuart R

2005-08-22

The first results are presented of a new experiment designed both to generate and characterize spectroscopically individual isomers of transition-metal cluster cations. As a proof of concept the one-photon mass-analyzed threshold ionization (MATI) spectrum of V3 has been recorded in the region of 44,000-45,000 cm-1. This study extends the range of a previous zero-kinetic-energy (ZEKE) photoelectron study of Yang et al. [Chem. Phys. Lett. 231, 177 (1994)] with which the current results are compared. The MATI spectra reported here exhibit surprisingly high resolution (0.2 cm-1) for this technique despite the use of large discrimination and extraction fields. Analysis of the rotational profile of the origin band allows assignment of the V3 ground state as and the V3+ ground state as , both with D3h geometry, in agreement with the density-functional theory study of the V3 ZEKE spectrum by Calaminici et al. [J. Chem. Phys. 114, 4036 (2001)]. There is also some evidence in the spectrum of transitions to the low-lying excited state of the ion. The vibrational structure observed in the MATI spectrum is, however, significantly different to and less extensive than that predicted in the density-functional theory study. Possible reasons for the discrepancies are discussed and an alternative assignment is proposed which results in revised values for the vibrational wave numbers of both the neutral and ionic states. These studies demonstrate the efficient generation of cluster ions in known structural (isomeric) forms and pave the way for the study of cluster reactivity as a function of geometrical structure.

Some characteristics of matrix-assisted UV laser desorption/ionization mass spectrometric analysis of large proteins

NASA Astrophysics Data System (ADS)

Perera, I. K.; Kantartzoglou, S.; Dyer, P. E.

1996-12-01

We have performed experiments to explore the characteristics of the matrix-assisted laser desorption/ionization (MALDI) process and to ascertain optimal operational conditions for observing intact molecular ions of large proteins. In this study, several methods have been adopted for the preparation of analyte samples. Of these, the samples prepared with the simple dried-droplet method were found to be the most suitable for the generation of the large molecular clusters, while the near-uniform spin-coated samples were observed to produce highly reproducible molecular ion signals of relatively high mass resolutions. A resulting mass spectrum which illustrates the formation of cluster ions up to the 26-mer [26M+H]+ of bovine insulin corresponding to a mass of about 150,000 Da, is presented. The effect of fluence on the extent of clustering of protein molecules has been studied, the results revealing the existence of an optimum fluence for detecting the large cluster ions. Investigations have also indicated that the use of polyethylene-coated metallic substrates as sample supports can considerably reduce the fragmentation of the matrix/analyte molecular ions and the desorption of "neat" MALDI matrices deposited on these polyethylene-coated sample probes enhance their aggregation, forming up to the heptamer [7M+H]+ of the matrix, ferulic acid. The dependence of the mass resolution on the applied acceleration voltage and the desorption fluence has been examined and the results obtained are discussed in terms of a simple analysis of the linear time-of-flight mass spectrometer. A spectrum of chicken egg lysozyme (M~14,306) displaying the high mass resolutions (M/[Delta]M~690) that can be attained when the mass spectrometer is operated in the reflectron mode is also presented.

Ionized Gas Motions and the Structure of Feedback near a Forming Globular Cluster in NGC 5253

NASA Astrophysics Data System (ADS)

Cohen, Daniel P.; Turner, Jean L.; Consiglio, S. Michelle; Martin, Emily C.; Beck, Sara C.

2018-06-01

We observed Brackett α 4.05 μm emission toward the supernebula in NGC 5253 with NIRSPEC on Keck II in adaptive optics mode, NIRSPAO, to probe feedback from its exciting embedded super star cluster (SSC). NIRSPEC's Slit-viewing Camera was simultaneously used to image the K-band continuum at ∼0.″1 resolution. We register the IR continuum with HST imaging, and find that the visible clusters are offset from the K-band peak, which coincides with the Brα peak of the supernebula and its associated molecular cloud. The spectra of the supernebula exhibit Brα emission with a strong, narrow core. The linewidths are 65–76 km s‑1, FWHM, comparable to those around individual ultra-compact H II regions within our Galaxy. A weak, broad (FWHM ≃ 150–175 km s‑1) component is detected on the base of the line, which could trace a population of sources with high-velocity winds. The core velocity of Brα emission shifts by +13 km s‑1 from NE to SW across the supernebula, possibly indicating a bipolar outflow from an embedded object or a link to a foreground redshifted gas filament. The results can be explained if the supernebula comprises thousands of ionized wind regions around individual massive stars, stalled in their expansion due to critical radiative cooling and unable to merge to drive a coherent cluster wind. Based on the absence of an outflow with large mass loss, we conclude that feedback is currently ineffective at dispersing gas, and the SSC retains enriched material out of which it may continue to form stars.

Elimination-Fusion Self-Assembly of a Nanometer-Scale 72-Nucleus Silver Cluster Caging a Pair of [EuW10 O36 ]9- Polyoxometalates.

PubMed

Zhang, Shan-Shan; Su, Hai-Feng; Wang, Zhi; Wang, Xing-Po; Chen, Wen-Xian; Zhao, Quan-Qin; Tung, Chen-Ho; Sun, Di; Zheng, Lan-Sun

2018-02-06

The largest known polyoxometalate (POM)-templated silver-alkynyl cluster, [(EuW 10 O 36 ) 2 @Ag 72 (tBuC≡C) 48 Cl 2 ⋅4 BF 4 ] (SD/Ag20), was isolated under solvothermal conditions and structurally characterized. It was confirmed by single-crystal X-ray diffraction (SCXRD) as a {EuW 10 } 2 -in-{Ag 72 } clusters-in-cluster rod-like compound. The high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) shows that such a double anion-templated cluster is assembled from a crucial single anion-templated Ag 42 intermediate in the solution. The crystallization of Ag 42 species (SD/Ag21), followed by SCXRD, gave an important clue about the assembly route of SD/Ag20 in solution: the Ag 42 cluster eliminates six silver atoms laterally, then fuses together at the vacant face to form the final Ag 72 cluster (elimination-fusion mechanism). The characteristic emission of [EuW 10 O 36 ] 9- is well maintained in SD/Ag20. This work not only provides a new method for the synthesis of larger silver clusters as well as the functional integration of the silver cluster and POMs, but also gives deep insights about the high-nuclear silver cluster assembly mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of bulk properties of tropical cloud clusters from large scale heat and moisture budgets, appendix B

NASA Technical Reports Server (NTRS)

Yanai, M.; Esbensen, S.; Chu, J.

1972-01-01

The bulk properties of tropical cloud clusters, as the vertical mass flux, the excess temperature, and moisture and the liquid water content of the clouds, are determined from a combination of the observed large-scale heat and moisture budgets over an area covering the cloud cluster, and a model of a cumulus ensemble which exchanges mass, heat, vapor and liquid water with the environment through entrainment and detrainment. The method also provides an understanding of how the environmental air is heated and moistened by the cumulus convection. An estimate of the average cloud cluster properties and the heat and moisture balance of the environment, obtained from 1956 Marshall Islands data, is presented.

Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2014-05-14

This paper's objective is to create a "consistent" mean-field based Kohn-Sham (KS) density functional theory (DFT) meaning the functional should not only provide good total energy properties, but also the corresponding KS eigenvalues should be accurate approximations to the vertical ionization potentials (VIPs) of the molecule, as the latter condition attests to the viability of the exchange-correlation potential (VXC). None of the prominently used DFT approaches show these properties: the optimized effective potential VXC based ab initio dft does. A local, range-separated hybrid potential cam-QTP-00 is introduced as the basis for a "consistent" KS DFT approach. The computed VIPs as the negative of KS eigenvalue have a mean absolute error of 0.8 eV for an extensive set of molecule's electron ionizations, including the core. Barrier heights, equilibrium geometries, and magnetic properties obtained from the potential are in good agreement with experiment. A similar accuracy with less computational efforts can be achieved by using a non-variational global hybrid variant of the QTP-00 approach.

Structure of the San Andreas Fault Zone in the Salton Trough Region of Southern California: A Comparison with San Andreas Fault Structure in the Loma Prieta Area of Central California

NASA Astrophysics Data System (ADS)

Fuis, G. S.; Catchings, R.; Scheirer, D. S.; Goldman, M.; Zhang, E.; Bauer, K.

2016-12-01

The San Andreas fault (SAF) in the northern Salton Trough, or Coachella Valley, in southern California, appears non-vertical and non-planar. In cross section, it consists of a steeply dipping segment (75 deg dip NE) from the surface to 6- to 9-km depth, and a moderately dipping segment below 6- to 9-km depth (50-55 deg dip NE). It also appears to branch upward into a flower-like structure beginning below about 10-km depth. Images of the SAF zone in the Coachella Valley have been obtained from analysis of steep reflections, earthquakes, modeling of potential-field data, and P-wave tomography. Review of seismological and geodetic research on the 1989 M 6.9 Loma Prieta earthquake, in central California (e.g., U.S. Geological Survey Professional Paper 1550), shows several features of SAF zone structure similar to those seen in the northern Salton Trough. Aftershocks in the Loma Prieta epicentral area form two chief clusters, a tabular zone extending from 18- to 9-km depth and a complex cluster above 5-km depth. The deeper cluster has been interpreted to surround the chief rupture plane, which dips 65-70 deg SW. When double-difference earthquake locations are plotted, the shallower cluster contains tabular subclusters that appear to connect the main rupture with the surface traces of the Sargent and Berrocal faults. In addition, a diffuse cluster may surround a steep to vertical fault connecting the main rupture to the surface trace of the SAF. These interpreted fault connections from the main rupture to surface fault traces appear to define a flower-like structure, not unlike that seen above the moderately dipping segment of the SAF in the Coachella Valley. But importantly, the SAF, interpreted here to include the main rupture plane, appears segmented, as in the Coachella Valley, with a moderately dipping segment below 9-km depth and a steep to vertical segment above that depth. We hope to clarify fault-zone structure in the Loma Prieta area by reanalyzing active-source data collected after the earthquake for steep reflections.

Photoelectron Angular Distributions of Transition Metal Dioxide Anions - a joint experimental and theoretical study

NASA Astrophysics Data System (ADS)

Iordanov, Ivan; Gunaratne, Dasitha; Harmon, Christopher; Sofo, Jorge; Castleman, A. W., Jr.

2012-02-01

Angular-resolved photoelectron spectroscopy (PES) studies of the MO2- (M=Ti, Zr, Hf, Co, Rh) clusters are presented for the first time along with theoretical calculations of their properties. We confirm previously reported non-angular PES results for the vertical detachment energies (VDE), vibrational energies and geometric structures of these clusters and further explore the effect of the 'lanthanide contraction' on the MO2- clusters by comparing the electronic spectra of 4d and 5d transition metal dioxides. Angular-resolved PES provides the angular momentum contributions to the HOMO of these clusters and we use theoretical calculations to examine the HOMO and compare to our experimental results. First-principles calculations are done using both density functional theory (DFT) and the coupled-cluster, singles, doubles and triples (CCSD(T)) methods.

A Model for Protostellar Cluster Luminosities and the Impact on the CO–H2 Conversion Factor

NASA Astrophysics Data System (ADS)

Gaches, Brandt A. L.; Offner, Stella S. R.

2018-02-01

We construct a semianalytic model to study the effect of far-ultraviolet (FUV) radiation on gas chemistry from embedded protostars. We use the protostellar luminosity function (PLF) formalism of Offner & McKee to calculate the total, FUV, and ionizing cluster luminosity for various protostellar accretion histories and cluster sizes. We2 compare the model predictions with surveys of Gould Belt star-forming regions and find that the tapered turbulent core model matches best the mean luminosities and the spread in the data. We combine the cluster model with the photodissociation region astrochemistry code, 3D-PDR, to compute the impact of the FUV luminosity from embedded protostars on the CO-to-H2 conversion factor, X CO, as a function of cluster size, gas mass, and star formation efficiency. We find that X CO has a weak dependence on the FUV radiation from embedded sources for large clusters owing to high cloud optical depths. In smaller and more efficient clusters the embedded FUV increases X CO to levels consistent with the average Milky Way values. The internal physical and chemical structures of the cloud are significantly altered, and X CO depends strongly on the protostellar cluster mass for small efficient clouds.

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

PubMed

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

Classical plasma dynamics of Mie-oscillations in atomic clusters

NASA Astrophysics Data System (ADS)

Kull, H.-J.; El-Khawaldeh, A.

2018-04-01

Mie plasmons are of basic importance for the absorption of laser light by atomic clusters. In this work we first review the classical Rayleigh-theory of a dielectric sphere in an external electric field and Thomson’s plum-pudding model applied to atomic clusters. Both approaches allow for elementary discussions of Mie oscillations, however, they also indicate deficiencies in describing the damping mechanisms by electrons crossing the cluster surface. Nonlinear oscillator models have been widely studied to gain an understanding of damping and absorption by outer ionization of the cluster. In the present work, we attempt to address the issue of plasmon relaxation in atomic clusters in more detail based on classical particle simulations. In particular, we wish to study the role of thermal motion on plasmon relaxation, thereby extending nonlinear models of collective single-electron motion. Our simulations are particularly adopted to the regime of classical kinetics in weakly coupled plasmas and to cluster sizes extending the Debye-screening length. It will be illustrated how surface scattering leads to the relaxation of Mie oscillations in the presence of thermal motion and of electron spill-out at the cluster surface. This work is intended to give, from a classical perspective, further insight into recent work on plasmon relaxation in quantum plasmas [1].

Structures of small Pd Pt bimetallic clusters by Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Cheng, Daojian; Huang, Shiping; Wang, Wenchuan

2006-11-01

Segregation phenomena of Pd-Pt bimetallic clusters with icosahedral and decahedral structures are investigated by using Monte Carlo method based on the second-moment approximation of the tight-binding (TB-SMA) potentials. The simulation results indicate that the Pd atoms generally lie on the surface of the smaller clusters. The three-shell onion-like structures are observed in 55-atom Pd-Pt bimetallic clusters, in which a single Pd atom is located in the center, and the Pt atoms are in the middle shell, while the Pd atoms are enriched on the surface. With the increase of Pd mole fraction in 55-atom Pd-Pt bimetallic clusters, the Pd atoms occupy the vertices of clusters first, then edge and center sites, and finally the interior shell. It is noticed that some decahedral structures can be transformed into the icosahedron-like structure at 300 and 500 K. Comparisons are made with previous experiments and theoretical studies of Pd-Pt bimetallic clusters.

Archetypal TRMM Radar Profiles Identified Through Cluster Analysis

NASA Technical Reports Server (NTRS)

Boccippio, Dennis J.

2003-01-01

It is widely held that identifiable 'convective regimes' exist in nature, although precise definitions of these are elusive. Examples include land / Ocean distinctions, break / monsoon beahvior, seasonal differences in the Amazon (SON vs DJF), etc. These regimes are often described by differences in the realized local convective spectra, and measured by various metrics of convective intensity, depth, areal coverage and rainfall amount. Objective regime identification may be valuable in several ways: regimes may serve as natural 'branch points' in satellite retrieval algorithms or data assimilation efforts; one example might be objective identification of regions that 'should' share a similar 2-R relationship. Similarly, objectively defined regimes may provide guidance on optimal siting of ground validation efforts. Objectively defined regimes could also serve as natural (rather than arbitrary geographic) domain 'controls' in studies of convective response to environmental forcing. Quantification of convective vertical structure has traditionally involved parametric study of prescribed quantities thought to be important to convective dynamics: maximum radar reflectivity, cloud top height, 30-35 dBZ echo top height, rain rate, etc. Individually, these parameters are somewhat deficient as their interpretation is often nonunique (the same metric value may signify different physics in different storm realizations). Individual metrics also fail to capture the coherence and interrelationships between vertical levels available in full 3-D radar datasets. An alternative approach is discovery of natural partitions of vertical structure in a globally representative dataset, or 'archetypal' reflectivity profiles. In this study, this is accomplished through cluster analysis of a very large sample (0[107) of TRMM-PR reflectivity columns. Once achieved, the rainconditional and unconditional 'mix' of archetypal profile types in a given location and/or season provides a description of the local convective spectrum which retains vertical structure information. A further cluster analysis of these 'mixes' can identify recurrent convective spectra. These are a first step towards objective identification of convective regimes, and towards answering the question: 'What are the most convectively similar locations in the world?'

A simple way to model nebulae with distributed ionizing stars

NASA Astrophysics Data System (ADS)

Jamet, L.; Morisset, C.

2008-04-01

Aims: This work is a follow-up of a recent article by Ercolano et al. that shows that, in some cases, the spatial dispersion of the ionizing stars in a given nebula may significantly affect its emission spectrum. The authors found that the dispersion of the ionizing stars is accompanied by a decrease in the ionization parameter, which at least partly explains the variations in the nebular spectrum. However, they did not research how other effects associated to the dispersion of the stars may contribute to those variations. Furthermore, they made use of a unique and simplified set of stellar populations. The scope of the present article is to assess whether the variation in the ionization parameter is the dominant effect in the dependence of the nebular spectrum on the distribution of its ionizing stars. We examined this possibility for various regimes of metallicity and age. We also investigated a way to model the distribution of the ionizing sources so as to bypass expensive calculations. Methods: We wrote a code able to generate random stellar populations and to compute the emission spectra of their associated nebulae through the widespread photoionization code cloudy. This code can process two kinds of spatial distributions of the stars: one where all the stars are concentrated at one point, and one where their separation is such that their Strömgren spheres do not overlap. Results: We found that, in most regimes of stellar population ages and gas metallicities, the dependence of the ionization parameter on the distribution of the stars is the dominant factor in the variation of the main nebular diagnostics with this distribution. We derived a method to mimic those effects with a single calculation that makes use of the common assumptions of a central source and a spherical nebula, in the case of constant density objects. This represents a computation time saving by a factor of at least several dozen in the case of H ii regions ionized by massive clusters.

The kinematics of the diffuse ionized gas in NGC 4666

NASA Astrophysics Data System (ADS)

Voigtländer, P.; Kamphuis, P.; Marcelin, M.; Bomans, D. J.; Dettmar, R.-J.

2013-06-01

Context. The global properties of the interstellar medium with processes such as infall and outflow of gas and a large scale circulation of matter and its consequences for star formation and chemical enrichment are important for the understanding of galaxy evolution. Aims: In this paper we studied the kinematics and morphology of the diffuse ionized gas (DIG) in the disk and in the halo of the star forming spiral galaxy NGC 4666 to derive information about its kinematical properties. Especially, we searched for infalling and outflowing ionized gas. Methods: We determined surface brightness, radial velocity, and velocity dispersion of the warm ionized gas via high spectral resolution (R ≈ 9000) Fabry-Pérot interferometry. This allows the determination of the global velocity field and the detection of local deviations from this velocity field. We calculated models of the DIG distribution and its kinematics for comparison with the measured data. In this way we determined fundamental parameters such as the inclination and the scale height of NGC 4666, and established the need for an additional gas component to fit our observed data. Results: We found individual areas, especially along the minor axis, with gas components reaching into the halo which we interpret as an outflowing component of the DIG. As the main result of our study, we were able to determine that the vertical structure of the DIG distribution in NGC 4666 is best modeled with two components of ionized gas, a thick and a thin disk with 0.8 kpc and 0.2 kpc scale height, respectively. Therefore, the enhanced star formation in NGC 4666 drives an outflow and also maintains a thick ionized gas layer reminiscent of the Reynold's layer in the Milky Way.

SOLAR HARD X-RAY SOURCE SIZES IN A BEAM-HEATED AND IONIZED CHROMOSPHERE

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Flannagain, Aidan M.; Gallagher, Peter T.; Brown, John C.

2015-02-01

Solar flare hard X-rays (HXRs) are produced as bremsstrahlung when an accelerated population of electrons interacts with the dense chromospheric plasma. HXR observations presented by Kontar et al. using the Ramaty High-Energy Solar Spectroscopic Imager have shown that HXR source sizes are three to six times more extended in height than those predicted by the standard collisional thick target model (CTTM). Several possible explanations have been put forward including the multi-threaded nature of flare loops, pitch-angle scattering, and magnetic mirroring. However, the nonuniform ionization (NUI) structure along the path of the electron beam has not been fully explored as amore » solution to this problem. Ionized plasma is known to be less effective at producing nonthermal bremsstrahlung HXRs when compared to neutral plasma. If the peak HXR emission was produced in a locally ionized region within the chromosphere, the intensity of emission will be preferentially reduced around this peak, resulting in a more extended source. Due to this effect, along with the associated density enhancement in the upper chromosphere, injection of a beam of electrons into a partially ionized plasma should result in an HXR source that is substantially more vertically extended relative to that for a neutral target. Here we present the results of a modification to the CTTM, which takes into account both a localized form of chromospheric NUI and an increased target density. We find 50 keV HXR source widths, with and without the inclusion of a locally ionized region, of ∼3 Mm and ∼0.7 Mm, respectively. This helps to provide a theoretical solution to the currently open question of overly extended HXR sources.« less

Probing the SEB Sensitive Depth of a Power MOSFET Using a Two-Photon Absorption Laser Method

NASA Technical Reports Server (NTRS)

Lauenstein, Jean-Marie; Liu, Sandra; Titus, Jeffrey L.; McMorrow, Dale; Casey, Megan C.; Buchner, Stephen P.; Warner, Jeffrey; Phan, Anthony M.; Topper, Alyson D.; Kim, Hak S.;

The ROSAT Brightest Cluster Sample - III. Optical spectra of the central cluster galaxies

NASA Astrophysics Data System (ADS)

Crawford, C. S.; Allen, S. W.; Ebeling, H.; Edge, A. C.; Fabian, A. C.

1999-07-01

We present new spectra of dominant galaxies in X-ray-selected clusters of galaxies, which combine with our previously published spectra to form a sample of 256 dominant galaxies in 215 clusters. 177 of the clusters are members of the ROSAT Brightest Cluster Sample (BCS; Ebeling et al.), and 17 have no previous measured redshift. This is the first paper in a series correlating the properties of brightest cluster galaxies and their host clusters in the radio, optical and X-ray wavebands. 27 per cent of the central dominant galaxies have emission-line spectra, all but five with line intensity ratios typical of cooling flow nebulae. A further 6 per cent show only [N ii]lambdalambda6548,6584 with Hα in absorption. We find no evidence for an increase in the frequency of line emission with X-ray luminosity. Purely X-ray-selected clusters at low redshift have a higher probability of containing line emission. The projected separation between the optical position of the dominant galaxy and its host cluster X-ray centroid is less for the line-emitting galaxies than for those without line emission, consistent with a closer association of the central galaxy and the gravitational centre in cooling flow clusters. The more Hα-luminous galaxies have larger emission-line regions and show a higher ratio of Balmer to forbidden line emission, although there is a continuous trend of ionization behaviour across four decades in Hα luminosity. Galaxies with the more luminous line emission [L(Hα)> 10^41ergs^-1] show a significantly bluer continuum, whereas lower luminosity and [N ii]-only line emitters have continua that differ little from those of non-line-emitting dominant galaxies. Values of the Balmer decrement in the more luminous systems commonly imply intrinsic reddening of E(B-V)~0.3 and, when this is corrected for, the excess blue light can be characterized by a population of massive young stars. Several of the galaxies require a large population of O stars, which also provide sufficient photoionization to produce the observed Hα luminosity. The large number of lower mass stars relative to the O-star population suggests that this anomalous population is caused by a series of starbursts in the central galaxy. The lower Hα-luminosity systems show a higher ionization state and few massive stars, requiring instead the introduction of a harder source of photoionization, such as turbulent mixing layers, or low-level nuclear activity. The line emission from the systems showing only [N ii] is very similar to low-level LINER activity commonly found in many normal elliptical galaxies.

Externally Induced Evaporation of Young Stellar Disks: The Case for HST 10 in Orion's Trapezium.

NASA Astrophysics Data System (ADS)

Johnstone, D.; Hollenbach, D.; Storzer, H.; Bally, J.; Sutherland, R.

1996-12-01

The Trapezium region in Orion is composed of a few high-mass stars, responsible for the ionization of the surrounding gas, and a plethora of low-mass stars with disks. Observations at infrared, optical, and radio wavelengths have led to the discovery of extended ionized envelopes around many of the young low-mass stars requiring evaporation rates dot M ~ 10(-7) Modot/yr. In this poster we explain these observations through a model for the evaporation of disks around young low-mass stars by an external source of high energy photons. In particular, the externally produced ultraviolet continuum longward of the Lyman limit is used to heat the disk surface and produce a warm neutral flow. The model results in an offset ionization front, where the neutral flow encounters Lyman continuum radiation, and a mass-loss rate which is fixed due to the self-regulating nature of FUV heating. Applying this model to the Trapezium region evaporating objects, particularly HST 10, produces a satisfactory solution to both the mass-loss rate and the size of the ionized envelopes. The resulting short destruction times for these disks constrain the gestation period for planet embryos around stars in dense clusters.

Uncovering multiple Wolf-Rayet star clusters and the ionized ISM in Mrk 178: the closest metal-poor Wolf-Rayet H II galaxy

NASA Astrophysics Data System (ADS)

Kehrig, C.; Pérez-Montero, E.; Vílchez, J. M.; Brinchmann, J.; Kunth, D.; García-Benito, R.; Crowther, P. A.; Hernández-Fernández, J.; Durret, F.; Contini, T.; Fernández-Martín, A.; James, B. L.

2013-07-01

New integral field spectroscopy (IFS) has been obtained for the nearby metal-poor Wolf-Rayet (WR) galaxy Mrk 178 to examine the spatial correlation between its WR stars and the neighbouring ionized interstellar medium (ISM). The strength of the broad WR features and its low metallicity make Mrk 178 an intriguing object. We have detected the blue and red WR bumps in different locations across the field of view (˜300 pc × 230 pc) in Mrk 178. The study of the WR content has been extended, for the first time, beyond its brightest star-forming knot uncovering new WR star clusters. Using Large/Small Magellanic Cloud-template WR stars, we empirically estimate a minimum of ˜20 WR stars within the region sampled. Maps of the spatial distribution of the emission lines and of the physical-chemical properties of the ionized ISM have been created and analysed. Here, we refine the statistical methodology by Pérez-Montero et al. (2011) to probe the presence of variations in the ISM properties. An error-weighted mean of 12+log(O/H) = 7.72 ± 0.01 is taken as the representative oxygen abundance for Mrk 178. A localized N and He enrichment, spatially correlated with WR stars, is suggested by this analysis. Nebular He II λ4686 emission is shown to be spatially extended reaching well beyond the location of the WR stars. This spatial offset between WRs and He II emission can be explained based on the mechanical energy input into the ISM by the WR star winds, and does not rule out WR stars as the He II ionization source. We study systematic aperture effects on the detection and measurement of the WR features, using Sloan Digital Sky Survey spectra combined with the power of IFS. In this regard, the importance of targeting low metallicity nearby systems is discussed.