Calculations of acceptor ionization energies in GaN

NASA Astrophysics Data System (ADS)

Wang, H.; Chen, A.-B.

2001-03-01

The k.p Hamiltonian and a model potential are used to deduce the acceptor ionization energies in GaN from a systematic study of the chemical trend in GaAs, GaP, and InP. The acceptors studied include Be, Mg, Ca, Zn, and Cd on the cation sites and C, Si, and Ge on the anion sites. Our calculated acceptor ionization energies are estimated to be accurate to better than 10% across the board. The ionization energies of C and Be (152 and 187 meV, respectively) in wurtzite GaN are found to be lower than that of Mg (224 meV). The C was found to behave like the hydrogenic acceptor in all systems and it has the smallest ionization energy among all the acceptors studied.

Efficient G0W0 using localized basis sets: a benchmark for molecules

NASA Astrophysics Data System (ADS)

Koval, Petr; Per Ljungberg, Mathias; Sanchez-Portal, Daniel

Electronic structure calculations within Hedin's GW approximation are becoming increasingly accessible to the community. In particular, as it has been shown earlier and we confirm by calculations using our MBPT_LCAO package, the computational cost of the so-called G0W0 can be made comparable to the cost of a regular Hartree-Fock calculation. In this work, we study the performance of our new implementation of G0W0 to reproduce the ionization potentials of all 117 closed-shell molecules belonging to the G2/97 test set, using a pseudo-potential starting point provided by the popular density-functional package SIESTA. Moreover, the ionization potentials and electron affinities of a set of 24 acceptor molecules are compared to experiment and to reference all-electron calculations. PK: Guipuzcoa Fellow; PK,ML,DSP: Deutsche Forschungsgemeinschaft (SFB1083); PK,DSP: MINECO MAT2013-46593-C6-2-P.

Ionization-potential depression and dynamical structure factor in dense plasmas

NASA Astrophysics Data System (ADS)

Lin, Chengliang; Röpke, Gerd; Kraeft, Wolf-Dietrich; Reinholz, Heidi

2017-07-01

The properties of a bound electron system immersed in a plasma environment are strongly modified by the surrounding plasma. The modification of an essential quantity, the ionization energy, is described by the electronic and ionic self-energies, including dynamical screening within the framework of the quantum statistical theory. Introducing the ionic dynamical structure factor as the indicator for the ionic microfield, we demonstrate that ionic correlations and fluctuations play a critical role in determining the ionization potential depression. This is, in particular, true for mixtures of different ions with large mass and charge asymmetry. The ionization potential depression is calculated for dense aluminum plasmas as well as for a CH plasma and compared to the experimental data and more phenomenological approaches used so far.

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

Singh, Suvam; Naghma, Rahla; Kaur, Jaspreet

The total and ionization cross sections for electron scattering by benzene, halobenzenes, toluene, aniline, and phenol are reported over a wide energy domain. The multi-scattering centre spherical complex optical potential method has been employed to find the total elastic and inelastic cross sections. The total ionization cross section is estimated from total inelastic cross section using the complex scattering potential-ionization contribution method. In the present article, the first theoretical calculations for electron impact total and ionization cross section have been performed for most of the targets having numerous practical applications. A reasonable agreement is obtained compared to existing experimental observationsmore » for all the targets reported here, especially for the total cross section.« less

Optical potential approach to the electron-atom impact ionization threshold problem

NASA Technical Reports Server (NTRS)

Temkin, A.; Hahn, Y.

1973-01-01

The problem of the threshold law for electron-atom impact ionization is reconsidered as an extrapolation of inelastic cross sections through the ionization threshold. The cross sections are evaluated from a distorted wave matrix element, the final state of which describes the scattering from the Nth excited state of the target atom. The actual calculation is carried for the e-H system, and a model is introduced which is shown to preserve the essential properties of the problem while at the same time reducing the dimensionability of the Schrodinger equation. Nevertheless, the scattering equation is still very complex. It is dominated by the optical potential which is expanded in terms of eigen-spectrum of QHQ. It is shown by actual calculation that the lower eigenvalues of this spectrum descend below the relevant inelastic thresholds; it follows rigorously that the optical potential contains repulsive terms. Analytical solutions of the final state wave function are obtained with several approximations of the optical potential.

Ionization potential depression and optical spectra in a Debye plasma model

NASA Astrophysics Data System (ADS)

Lin, Chengliang; Röpke, Gerd; Reinholz, Heidi; Kraeft, Wolf-Dietrich

2017-11-01

We show how optical spectra in dense plasmas are determined by the shift of energy levels as well as the broadening owing to collisions with the plasma particles. In lowest approximation, the interaction with the plasma particles is described by the RPA dielectric function, leading to the Debye shift of the continuum edge. The bound states remain nearly un-shifted, their broadening is calculated in Born approximation. The role of ionization potential depression as well as the Inglis-Teller effect are shown. The model calculations have to be improved going beyond the lowest (RPA) approximation when applying to WDM spectra.

Potential Energy Curves and Collisions Integrals of Air Components. 2; Interactions Involving Ionized Atoms

NASA Technical Reports Server (NTRS)

Stallcop, James R.; Partridge, Harry; Levin, Eugene; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

Collision integrals are fundamental quantities required to determine the transport properties of the environment surrounding aerospace vehicles in the upper atmosphere. These collision integrals can be determined as a function of temperature from the potential energy curves describing the atomic and molecular collisions. Ab initio calculations provide a practical method of computing the required interaction potentials. In this work we will discuss recent advances in scattering calculations with an emphasis on the accuracy that is obtainable. Results for interactions of the atoms and ionized atoms of nitrogen and oxygen will be reviewed and their application to the determination of transport properties, such as diffusion and viscosity coefficients, will be examined.

Time-dependent density-functional theory with optimized effective potential and self-interaction correction and derivative discontinuity for the treatment of double ionization of He and Be atoms in intense laser fields

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

2013-05-01

We present a self-interaction-free time-dependent density-functional theory (TDDFT) for the treatment of double-ionization processes of many-electron systems. The method is based on the extension of the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed three-dimensional (3D) calculations of double ionization of He and Be atoms by intense near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double-ionization process. We found that a proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the total particle number (TPN). The results for the intensity-dependent rates of double ionization of He and Be atoms are presented.

Reduction of the ionization energy for 1s-electrons in dense aluminum plasmas

NASA Astrophysics Data System (ADS)

Lin, C.; Reinholz, H.; Röpke, G.

2017-02-01

The properties of a bound multi-electron system immersed in a plasma environment are strongly modified by the surrounding plasma. In particular, the modification of the ionization energy is described by the electronic self-energy within the framework of the quantum statistical theory. We present the energy shift of the eigenstates and the lowering of the continuum edge of free electrons in a plasma. The reduction of the ionization potential is determined by their difference. This ionization potential depression for the 1s-levels in dense aluminum plasmas is calculated. Comparisons with other theories and the experimental data are shown for aluminum plasma at solid density 2.7 g/cm3.

Orientation dependent ionization potential of In2O3: a natural source for inhomogeneous barrier formation at electrode interfaces in organic electronics.

PubMed

Hohmann, Mareike V; Ágoston, Péter; Wachau, André; Bayer, Thorsten J M; Brötz, Joachim; Albe, Karsten; Klein, Andreas

2011-08-24

The ionization potentials of In(2)O(3) films grown epitaxially by magnetron sputtering on Y-stabilized ZrO(2) substrates with (100) and (111) surface orientation are determined using photoelectron spectroscopy. Epitaxial growth is verified using x-ray diffraction. The observed ionization potentials, which directly affect the work functions, are in good agreement with ab initio calculations using density functional theory. While the (111) surface exhibits a stable surface termination with an ionization potential of ∼ 7.0 eV, the surface termination and the ionization potential of the (100) surface depend strongly on the oxygen chemical potential. With the given deposition conditions an ionization potential of ∼ 7.7 eV is obtained, which is attributed to a surface termination stabilized by oxygen dimers. This orientation dependence also explains the lower ionization potentials observed for In(2)O(3) compared to Sn-doped In(2)O(3) (ITO) (Klein et al 2009 Thin Solid Films 518 1197-203). Due to the orientation dependent ionization potential, a polycrystalline ITO film will exhibit a laterally varying work function, which results in an inhomogeneous charge injection into organic semiconductors when used as electrode material. The variation of work function will become even more pronounced when oxygen plasma or UV-ozone treatments are performed, as an oxidation of the surface is only possible for the (100) surface. The influence of the deposition technique on the formation of stable surface terminations is also discussed. © 2011 IOP Publishing Ltd

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.

Differential cross sections for the electron impact ionization of Ar (3 p) atoms for equal energy final state electrons

NASA Astrophysics Data System (ADS)

Purohit, Ghanshyam; Singh, Prithvi

2017-06-01

The electron-impact ionization of inert gases for asymmetric final state energy sharing conditions has been studied in detail. However, there have been relatively few studies examining equal energy final state electrons. We report in this communication the results of triple differential cross sections (TDCSs) for electron impact ionization of Ar (3 p) for equal energy sharing of the outgoing electrons. We calculate TDCS in the modified distorted wave Born approximation (DWBA) formalism including post collision interaction (PCI) and polarization potential. We compare the results of our calculation with available measurements [Phys. Rev. A 87, 022712 (2013)]. We study the effect of PCI, target polarization on the trends of TDCS for the single ionization of Ar (3 p) targets.

Trajectory calculations of two-dimensional Penning ionization electron spectra of N 2 in collision with metastable He* 2 3S atoms

NASA Astrophysics Data System (ADS)

Ohno, Koichi; Yamazaki, Masakazu; Kishimoto, Naoki; Ogawa, Tetsuji; Takeshita, Kouichi

2000-12-01

Ionization cross-sections of N 2 in collision with He* 2 3S as functions of the collision energy and the ejected electron kinetic energy (two-dimensional Penning ionization electron spectra, 2D-PIES) have been evaluated by trajectory calculations based on quantum chemical potential surfaces of both entrance and exit channels as well as on the transition widths for producing X, A, and B states of N 2+. The present approach using a Li atom for He * and an overlap approximation for Γ has given theoretical 2D-PIES in good agreement with the observation and a promise for its application to the study of dynamics in collisional ionization involving highly anisotropic target systems.

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

Using the charge-stabilization technique in the double ionization potential equation-of-motion calculations with dianion references.

PubMed

Kuś, Tomasz; Krylov, Anna I

2011-08-28

The charge-stabilization method is applied to double ionization potential equation-of-motion (EOM-DIP) calculations to stabilize unstable dianion reference functions. The auto-ionizing character of the dianionic reference states spoils the numeric performance of EOM-DIP limiting applications of this method. We demonstrate that reliable excitation energies can be computed by EOM-DIP using a stabilized resonance wave function instead of the lowest energy solution corresponding to the neutral + free electron(s) state of the system. The details of charge-stabilization procedure are discussed and illustrated by examples. The choice of optimal stabilizing Coulomb potential, which is strong enough to stabilize the dianion reference, yet, minimally perturbs the target states of the neutral, is the crux of the approach. Two algorithms of choosing optimal parameters of the stabilization potential are presented. One is based on the orbital energies, and another--on the basis set dependence of the total Hartree-Fock energy of the reference. Our benchmark calculations of the singlet-triplet energy gaps in several diradicals show a remarkable improvement of the EOM-DIP accuracy in problematic cases. Overall, the excitation energies in diradicals computed using the stabilized EOM-DIP are within 0.2 eV from the reference EOM spin-flip values. © 2011 American Institute of Physics

Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

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

Bross, David H.; Parmar, Payal; Peterson, Kirk A., E-mail: kipeters@wsu.edu

The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set limit using new all-electron correlation consistent basis sets. The latter was carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons has been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. The final ionizationmore » potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV) and thus more reliable than the current experimental values of IP{sub 3} through IP{sub 6}.« less

Application of Effective Fragment Potential Methos to the Redox Potential of Green Fluorescent Protein

NASA Astrophysics Data System (ADS)

Ghosh, Debashree; Krylov, Anna I.

2011-06-01

Green fluorescent proteins (GFP) can be considered as a model for flurogenic dyes and are of importance in photovoltaic materials. It exhibits bright green fluorescence when exposed to blue light and has been an extremely powerful tool as non-invasive marker in living cells and extensibly used in molecular and cell biology. The understanding of the underlying electronic structure of these proteins and its chromophore is therefore crucial to the understanding of the mechanism for its optical properties. The chromophore of the GFP is p-hydroxybenzylidene-imidazolinone (HBDI) and is embedded in the center of the β barrel of the GFP. Calculating redox potential of this chromophore is a challenging problem, especially in diverse solvents and protein environment. It is possible to carry out high-level accurate ab-initio calculation of ionization potential or electron affinity of the microsolvated chromophore or the bare chromophore. But, it is not possible to extend these calculations to bulk solvents due to the high computational cost. Effective fragment potential (EFP)[1,2] method gives us a convenient tool to understand such systems. In our work, we have benchmarked the ionization energy and electron affinity of the microsolvated GFP chromophore calculated by combined EOM-IP-CCSD/EFP and EOM-EA-CCSD/EFP with the EOM-IP-CCSD and EOM-EA-CCSD calculations of the oxidized and reduced forms. We have carried out similar EFP-EOM-IP-CCSD and EFP-EOM-EA-CCSD calculations of ionization potential and electron affinity of GFP choromophore in bulk solvent generated by ab-initio molecular dynamics simulations. [1] M. S. Gordon, L. Slipchenko, H. Li, J. H. Jensen, Annual Reports in Computational Chemistry, Volume 3, 177 (2007). [2] D. Ghosh, D. Kosenkov, V. Vanovschi, C.F. Williams, J.M. Herbert, M.S. Gordon, M.W. Schmidt, L.V. Slipchenko, and A.I. Krylov, J. Phys. Chem. A 114, 12739 (2010).

Second Order Born Effects in the Perpendicular Plane Ionization of Xe (5p) Atoms

NASA Astrophysics Data System (ADS)

Purohit, G.; Singh, Prithvi; Patidar, Vinod

We report triple differential cross section (TDCS) results for the perpendicular plane ionization of xenon atoms at incident electron energies 5, 10, 20, 30, and 40 eV above ionization potential. The TDCS calculation have been preformed within the modified distorted wave Born approximation formalism including the second order Born (SBA) amplitude. We compare the (e, 2e) TDCS result of our calculation with the very recent measurements of Nixon and Murray [Phys. Rev. A 85, 022716 (2012)] and relativistic DWBA-G results of Illarionov and Stauffer [J. Phys. B: At. Mol. Opt. Phys. 45, 225202 (2012)] and discuss the process contributing to structure seen in the differential cross section.

Ionizing Collisions of Electrons with Radical Species OH, H2 O2 and HO2; Theoretical Calculations

NASA Astrophysics Data System (ADS)

Joshipura, K. N.; Pandya, S. H.; Vaishnav, B. G.; Patel, U. R.

2016-05-01

In this paper we present our calculated total ionization cross sections (TICS) of electron impact on radical targets OH, H2 O2 and HO2 at energies from threshold to 2000 eV. Reactive species such as these pose difficulties in measurements of electron scattering cross sections. No measured data have been reported in this regard except an isolated TICS measurement on OH radical, and hence the present work on the title radicals hold significance. These radical species are present in an environment in which water molecules undergo dissociation (neutral or ionic) in interactions with photons or electrons. The embedding environments could be quite diverse, ranging from our atmosphere to membranes of living cells. Ionization of OH, H2 O2 or HO2 can give rise to further chemistry in the relevant bulk medium. Therefore, it is appropriate and meaningful to examine electron impact ionization of these radicals in comparison with that of water molecules, for which accurate da are available. For the OH target single-centre scattering calculations are performed by starting with a 4-term complex potential, that describes simultaneous elastic plus inelastic scattering. TICS are obtained from the total inelastic cross sections in the complex scattering potential - ionization contribution formalism , a well established method. For H2 O2 and HO2 targets, we employ the additivity rule with overlap or screening corrections. Detailed results will be presented in the Conference.

Stark parameter dependence of the rest core charge of the emitters for multiply charged ions spectral lines

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

Šćepanović, M., E-mail: mara.scepanovic@gmail.com; Purić, J.

2016-03-25

Stark width and shift simultaneous dependence on the upper level ionization potential and rest core charge of the emitter has been evaluated and discussed. It has been verified that the found relations, connecting Stark broadening parameters with upper level ionization potential and rest core charge of the emitters for particular electron temperature and density, can be used for prediction of Stark line width and shift data in case of ions for which observed data, or more detailed calculations, are not yet available. Stark widths and shifts published data are used to demonstrate the existence of other kinds of regularities withinmore » similar spectra of different elements and their ionization stages. The emphasis is on the Stark parameter dependence on the upper level ionization potential and on the rest core charge for the lines from similar spectra of multiply charged ions. The found relations connecting Stark widths and shift parameters with upper level ionization potential, rest core charge and electron temperature were used for a prediction of new Stark broadening data, thus avoiding much more complicated procedures.« less

Study of elastic and inelastic cross sections by positron impact on inert gases

NASA Astrophysics Data System (ADS)

Singh, Suvam; Naghma, Rahla; Kaur, Jaspreet; Antony, Bobby

2018-04-01

In this article, a modified computational method recently introduced is used for the calculation of total, positronium (Ps) formation and ionization cross sections including direct and total ionization cross sections for positron scattering from noble gases. The incident positron is assumed to have energies over a wide range from 5 eV to 5 keV. The positron-atom interaction potential is developed under an optical potential framework and the computations of cross sections for each process are performed by introducing appropriate absorption thresholds. The calculated results obtained by employing this modified approach are found to be in reasonably good agreement with most of the existing data.

QTAIM electron density study of natural chalcones

NASA Astrophysics Data System (ADS)

González Moa, María J.; Mandado, Marcos; Cordeiro, M. Natália D. S.; Mosquera, Ricardo A.

2007-09-01

QTAIM atomic and bond properties, ionization potential, and O-H bond dissociation energies calculated at the B3LYP/6-311++G(2d,2p) level indicate the natural chalcones bear a significant radical scavenging activity. However, their ionization potentials indicate they decrease the electron-transfer rate between antioxidant and oxygen that yields the pro-oxidative cations less than other natural antioxidants. Rings A and B display slight and similar positive charges, whereas ring B is involved in exocycle delocalization at a larger extension.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

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

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

Band-edge positions in G W : Effects of starting point and self-consistency

NASA Astrophysics Data System (ADS)

Chen, Wei; Pasquarello, Alfredo

2014-10-01

We study the effect of starting point and self-consistency within G W on the band-edge positions of semiconductors and insulators. Compared to calculations based on a semilocal starting point, the use of a hybrid-functional starting point shows a larger quasiparticle correction for both band-edge states. When the self-consistent treatment is employed, the band-gap opening is found to result mostly from a shift of the valence-band edge. Within the non-self-consistent methods, we analyse the performance of empirical and nonempirical schemes in which the starting point is optimally tuned. We further assess the accuracy of the band-edge positions through the calculation of ionization potentials of surfaces. The ionization potentials for most systems are reasonably well described by one-shot calculations. However, in the case of TiO2, we find that the use of self-consistency is critical to obtain a good agreement with experiment.

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

Calculations with the quasirelativistic local-spin-density-functional theory for high-Z atoms

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

Guo, Y.; Whitehead, M.A.

1988-10-01

The generalized-exchange local-spin-density-functional theory (LSD-GX) with relativistic corrections of the mass velocity and Darwin terms has been used to calculate statistical total energies for the neutral atoms, the positive ions, and the negative ions for high-Z elements. The effect of the correlation and relaxation correction on the statistical total energy is discussed. Comparing the calculated results for the ionization potentials and electron affinities for the atoms (atomic number Z from 37 to 56 and 72 to 80) with experiment, shows that for the atoms rubidium to barium both the LSD-GX and the quasirelativistic LSD-GX, with self-interaction correction, Gopinathan, Whitehead, andmore » Bogdanovic's Fermi-hole parameters (Phys. Rev. A 14, 1 (1976)), and Vosko, Wilk, and Nusair's correlation correction (Can. J. Phys. 58, 1200 (1980)), are very good methods for calculating ionization potentials and electron affinities. For the atoms hafnium to mercury the relativistic effect has to be considered.« less

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

Nuclear Fission Investigation with Twin Ionization Chamber

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

Zeynalova, O.; Zeynalov, Sh.; Nazarenko, M.

2011-11-29

The purpose of the present paper was to report the recent results, obtained in development of digital pulse processing mathematics for prompt fission neutron (PFN) investigation using twin ionization chamber (TIC) along with fast neutron time-of-flight detector (ND). Due to well known ambiguities in literature (see refs. [4, 6, 9 and 11]), concerning a pulse induction on TIC electrodes by FF ionization, we first presented detailed mathematical analysis of fission fragment (FF) signal formation on TIC anode. The analysis was done using Ramo-Shockley theorem, which gives relation between charged particle motion between TIC electrodes and so called weighting potential. Weightingmore » potential was calculated by direct numerical solution of Laplace equation (neglecting space charge) for the TIC geometry and ionization, caused by FF. Formulae for grid inefficiency (GI) correction and digital pulse processing algorithms for PFN time-of-flight measurements and pulse shape analysis are presented and discussed.« less

Computational Calculation Of The Ionization Energies Of The Human Prion Protein By The Coarse-grain Method

NASA Astrophysics Data System (ADS)

Lyu, Justin; Andrianarijaona, V. M.

2016-05-01

The causes of the misfolding of prion protein -i.e. the transformation of PrPC to PrPSc - have not been clearly elucidated. Many studies have focused on identifying possible chemical conditions, such as pH, temperature and chemical denaturation, that may trigger the pathological transformation of prion proteins (Weiwei Tao, Gwonchan Yoon, Penghui Cao, `` β-sheet-like formation during the mechanical unfolding of prion protein'', The Journal of Chemical Physics, 2015, 143, 125101). Here, we attempt to calculate the ionization energies of the prion protein, which will be able to shed light onto the possible causes of the misfolding. We plan on using the coarse-grain method which allows for a more feasible calculation time by means of approximation. We believe that by being able to approximate the ionization potential, particularly that of the regions known to form stable β-strands of the PrPSc form, the possible sources of denaturation, be it chemical or mechanical, may be narrowed down.

Compact modeling of total ionizing dose and aging effects in MOS technologies

DOE PAGES

Esqueda, Ivan S.; Barnaby, Hugh J.; King, Michael Patrick

2015-06-18

This paper presents a physics-based compact modeling approach that incorporates the impact of total ionizing dose (TID) and stress-induced defects into simulations of metal-oxide-semiconductor (MOS) devices and integrated circuits (ICs). This approach utilizes calculations of surface potential (ψs) to capture the charge contribution from oxide trapped charge and interface traps and to describe their impact on MOS electrostatics and device operating characteristics as a function of ionizing radiation exposure and aging effects. The modeling approach is demonstrated for bulk and silicon-on-insulator (SOI) MOS device. The formulation is verified using TCAD simulations and through the comparison of model calculations and experimentalmore » I-V characteristics from irradiated devices. The presented approach is suitable for modeling TID and aging effects in advanced MOS devices and ICs.« less

Experimental and theoretical study of the microsolvation of sodium atoms in methanol clusters: differences and similarities to sodium-water and sodium-ammonia.

PubMed

Dauster, Ingo; Suhm, Martin A; Buck, Udo; Zeuch, Thomas

2008-01-07

Methanol clusters are generated in a continuous He-seeded supersonic expansion and doped with sodium atoms in a pick-up cell. By this method, clusters of the type Na(CH(3)OH)(n) are formed and subsequently photoionized by applying a tunable dye-laser system. The microsolvation process of the Na 3s electron is studied by determining the ionization potentials (IPs) of these clusters size-selectively for n = 2-40. A decrease is found from n = 2 to 6 and a constant value of 3.19 +/- 0.07 eV for n = 6-40. The experimentally-determined ionization potentials are compared with ionization potentials derived from quantum-chemical calculations, assuming limiting vertical and adiabatic processes. In the first case, energy differences are calculated between the neutral and the ionized cationic clusters of the same geometry. In the second case, the ionized clusters are used in their optimized relaxed geometry. These energy differences and relative stabilities of isomeric clusters vary significantly with the applied quantum-chemical method (B3LYP or MP2). The comparison with the experiment for n = 2-7 reveals strong variations of the ionization potential with the cluster structure indicating that structural diversity and non-vertical pathways give significant signal contributions at the threshold. Based on these findings, a possible explanation for the remarkable difference in IP evolutions of methanol or water and ammonia is presented: for methanol and water a rather localized surface or semi-internal Na 3s electron is excited to either high Rydberg or more localized states below the vertical ionization threshold. This excitation is followed by a local structural relaxation that couples to an autoionization process. For small clusters with n < 6 for methanol and n < 4 for water the addition of solvent molecules leads to larger solvent-metal-ion interaction energies, which consequently lead to lower ionization thresholds. For n = 6 (methanol) and n = 4 (water) this effect comes to a halt, which may be connected with the completion of the first cationic solvation shell limiting the release of local relaxation energy. For Na(NH(3))(n), a largely delocalized and internal electron is excited to autoionizing electronic states, a process that is no longer local and consequently may depend on cluster size up to very large n.

Acceptor Ionization Energies in GaN*

NASA Astrophysics Data System (ADS)

Wang, Hao; Ban Chen, An

2001-03-01

The k.p Hamiltonian and a model potential are used to deduce the acceptor ionization energies in GaN from a systematic study of the chemical trend in GaAs, GaP, and InP. The acceptors studied include Be, Mg, Ca, Zn, and Cd on the cation sites and C, Si, and Ge on the anion sites. Our calculated acceptor ionization energies are estimated to be accurate to better than ten percent across the board. The ionization energies of C and Be (152 and 187 meV respectively) in wurtzite GaN are found to be lower than that of Mg (224 meV). The C was found to behave like the hydrogenic acceptor in all systems and it has the smallest ionization energy among all the acceptors studied.

Ionization waves of arbitrary velocity driven by a flying focus

NASA Astrophysics Data System (ADS)

Palastro, J. P.; Turnbull, D.; Bahk, S.-W.; Follett, R. K.; Shaw, J. L.; Haberberger, D.; Bromage, J.; Froula, D. H.

2018-03-01

A chirped laser pulse focused by a chromatic lens exhibits a dynamic, or flying, focus in which the trajectory of the peak intensity decouples from the group velocity. In a medium, the flying focus can trigger an ionization front that follows this trajectory. By adjusting the chirp, the ionization front can be made to travel at an arbitrary velocity along the optical axis. We present analytical calculations and simulations describing the propagation of the flying focus pulse, the self-similar form of its intensity profile, and ionization wave formation. The ability to control the speed of the ionization wave and, in conjunction, mitigate plasma refraction has the potential to advance several laser-based applications, including Raman amplification, photon acceleration, high-order-harmonic generation, and THz generation.

Size-dependent error of the density functional theory ionization potential in vacuum and solution

DOE PAGES

Sosa Vazquez, Xochitl A.; Isborn, Christine M.

2015-12-22

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. As a result, in vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less

Size-dependent error of the density functional theory ionization potential in vacuum and solution

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

Sosa Vazquez, Xochitl A.; Isborn, Christine M., E-mail: cisborn@ucmerced.edu

2015-12-28

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. In vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less

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.

Ionization Cross Sections and Dissociation Channels of DNA Bases by Electron Collisions

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Dateo, Christopher E.; Fletcher, Graham D.

2004-01-01

Free secondary electrons are the most abundant secondary species in ionizing radiation. Their role in DNA damage, both direct and indirect, is an active area of research. While indirect damage by free radicals, particularly by the hydroxyl radical generated by electron collision with water. is relatively well studied, damage by direct electron collision with DNA is less well understood. Only recently Boudaiffa et al. demonstrated that electrons at energies well below ionization thresholds can induce substantial yields of single- and double-strand breaks in DNA by a resonant, dissociative attachment process. This study attracted renewed interest in electron collisions with DNA, especially in the low energy region. At higher energies ionization becomes important. While Monte Carlo track simulations of radiation damage always include ionization, the probability of dissociative ionization, i.e., simultaneous ionization and dissociation, is ignored. Just like dissociative attachment, dissociative ionization may be an important contributor to double-strand breaks since the radicals and ions produced by dissociative ionization, located in the vicinity of the DNA coil, can readily interact with other parts of the DNA. Using the improved binary-encounter dipole (iBED) formulation, we calculated the ionization cross sections of the four DNA bases, adenine, cytosine, guanine, and thymine, by electrons at energies from threshold to 1 KeV. The present calculation gives cross sections approximately 20% lower than the results by Bemhardt and Paretzke using the Deutsch-Mark and Binary-Encounter-Bethe (BEB) formalisms. The difference is most likely due to the lack of a shielding term in the dipole potential used in the Deutsch-Mark and BEB formalisms. The dissociation channels of ionization for the bases are currently being studied.

Effect of an InxGa1-xAs-GaAs blocking heterocathode metal contact on the GaAs TED operation

NASA Astrophysics Data System (ADS)

Arkusha, Yu. V.; Prokhorov, E. D.; Storozhenko, I. P.

2004-09-01

The frequency dependence of the generation efficiency of an mm- -nn:In:InxGaGa1-1-xAs- As-nn:GaAs-:GaAs-nn++:GaAs TED with the 2.5-mm long active region is calculated. The optimum values - which yield the diode maximum generation efficiency - for the :GaAs TED with the 2.5-mm long active region is calculated. The optimum values - which yield the diode maximum generation efficiency - for the nn:In:InxGaGa1-1-xAs cathode length, the cathode concentration of ionized impurities, and the height of the potential barrier on metal contact are determined.As cathode length, the cathode concentration of ionized impurities, and the height of the potential barrier on metal contact are determined.

Electrostatic Return of Contaminants

NASA Technical Reports Server (NTRS)

Rantanen, R.; Gordon, T.

2003-01-01

A Model has been developed capable of calculating the electrostatic return of spacecraft-emitted molecules that are ionized and attracted back to the spacecraft by the spacecraft electric potential on its surfaces. The return of ionized contaminant molecules to charged spacecraft surfaces is very important to all altitudes. It is especially important at geosynchronous and interplanetary environments, since it may be the only mechanism by which contaminants can degrade a surface. This model is applicable to all altitudes and spacecraft geometries. In addition to results of the model will be completed to cover a wide range of potential space systems.

Photo-ionization cross-section of donor-related in (In,Ga)N/GaN core/shell under hydrostatic pressure and electric field effects

NASA Astrophysics Data System (ADS)

El Ghazi, Haddou; John Peter, A.

2017-04-01

Hydrogenic-like donor-impurity related self and induced polarizations, bending energy and photo-ionization cross section in spherical core/shell zinc blende (In,Ga)N/GaN are computed. Based on the variational approach and within effective-mass and one parabolic approximations, the calculations are made under finite potential barrier taking into account of the discontinuity of the effective-mass and the constant dielectric. The photo-ionization cross section is studied according to the photon incident energy considering the effects of hydrostatic pressure, applied electric field, structure's radius, impurity's position and indium composition in the core. It is obtained that the influences mentioned above lead to either blue shifts or redshifts of the resonant peak of the photo-ionization cross section spectrum. The unusual behavior related to the structure radius is discussed which is as a consequence of the finite potential confinement. We have shown that the photo-ionization cross section can be controlled with adjusting the internal and external factors. These properties can be useful for producing some device applications such as quantum dot infrared photodetectors.

A comparative study on carbon, boron-nitride, boron-phosphide and silicon-carbide nanotubes based on surface electrostatic potentials and average local ionization energies.

PubMed

Esrafili, Mehdi D; Behzadi, Hadi

2013-06-01

A density functional theory study was carried out to predict the electrostatic potentials as well as average local ionization energies on both the outer and the inner surfaces of carbon, boron-nitride (BN), boron-phosphide (BP) and silicon-carbide (SiC) single-walled nanotubes. For each nanotube, the effect of tube radius on the surface potentials and calculated average local ionization energies was investigated. It is found that SiC and BN nanotubes have much stronger and more variable surface potentials than do carbon and BP nanotubes. For the SiC, BN and BP nanotubes, there are characteristic patterns of positive and negative sites on the outer lateral surfaces. On the other hand, a general feature of all of the systems studied is that stronger potentials are associated with regions of higher curvature. According to the evaluated surface electrostatic potentials, it is concluded that, for the narrowest tubes, the water solubility of BN tubes is slightly greater than that of SiC followed by carbon and BP nanotubes.

Molecular frame photoelectron angular distributions for core ionization of ethane, carbon tetrafluoride and 1,1-difluoroethylene

DOE PAGES

Menssen, A.; Trevisan, C. S.; Schöffler, M. S.; ...

2016-02-15

Molecular frame photoelectron angular distributions (MFPADs) are measured in this paper in electron–ion momentum imaging experiments and compared with complex Kohn variational calculations for carbon K-shell ionization of carbon tetrafluoride (CF 4), ethane (C 2H 6) and 1,1-difluoroethylene (C 2H 2F 2). While in ethane the polarization averaged MFPADs show a tendency at low energies for the photoelectron to be emitted in the directions of the bonds, the opposite effect is seen in CF 4. A combination of these behaviors is seen in difluoroethylene where ionization from the two carbons can be distinguished experimentally because of their different K-shell ionizationmore » potentials. Excellent agreement is found between experiment and simple static-exchange or coupled two-channel theoretical calculations. Finally, however, simple electrostatics do not provide an adequate explanation of the suggestively simple angular distributions at low electron ejection energies.« less

Determination of structure parameters in strong-field tunneling ionization theory of molecules

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

Zhao Songfeng; Jin Cheng; College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou, Gansu 730070

2010-03-15

In the strong field molecular tunneling ionization theory of Tong et al. [Phys. Rev. A 66, 033402 (2002)], the ionization rate depends on the asymptotic wave function of the molecular orbital from which the electron is removed. The orbital wave functions obtained from standard quantum chemistry packages in general are not good enough in the asymptotic region. Here we construct a one-electron model potential for several linear molecules using density functional theory. We show that the asymptotic wave function can be improved with an iteration method and after one iteration accurate asymptotic wave functions and structure parameters are determined. Withmore » the new parameters we examine the alignment-dependent tunneling ionization probabilities for several molecules and compare with other calculations and with recent measurements, including ionization from inner molecular orbitals.« less

Thermophysics Characterization of Multiply Ionized Air Plasma Absorption of Laser Radiation

NASA Technical Reports Server (NTRS)

Wang, Ten-See; Rhodes, Robert; Turner, Jim (Technical Monitor)

2002-01-01

The impact of multiple ionization of air plasma on the inverse Bremsstrahlung absorption of laser radiation is investigated for air breathing laser propulsion. Thermochemical properties of multiply ionized air plasma species are computed for temperatures up to 200,000 deg K, using hydrogenic approximation of the electronic partition function; And those for neutral air molecules are also updated for temperatures up to 50,000 deg K, using available literature data. Three formulas for absorption are calculated and a general formula is recommended for multiple ionization absorption calculation. The plasma composition required for absorption calculation is obtained by increasing the degree of ionization sequentially, up to quadruple ionization, with a series of thermal equilibrium computations. The calculated second ionization absorption coefficient agrees reasonably well with that of available data. The importance of multiple ionization modeling is demonstrated with the finding that area under the quadruple ionization curve of absorption is found to be twice that of single ionization. The effort of this work is beneficial to the computational plasma aerodynamics modeling of laser lightcraft performance.

A generalized any particle propagator theory: Assessment of nuclear quantum effects on electron propagator calculations

NASA Astrophysics Data System (ADS)

Romero, Jonathan; Posada, Edwin; Flores-Moreno, Roberto; Reyes, Andrés

2012-08-01

In this work we propose an extended propagator theory for electrons and other types of quantum particles. This new approach has been implemented in the LOWDIN package and applied to sample calculations of atomic and small molecular systems to determine its accuracy and performance. As a first application of the method we have studied the nuclear quantum effects on electron ionization energies. We have observed that ionization energies of atoms are similar to those obtained with the electron propagator approach. However, for molecular systems containing hydrogen atoms there are improvements in the quality of the results with the inclusion of nuclear quantum effects. An energy term analysis has allowed us to conclude that nuclear quantum effects are important for zero order energies whereas propagator results correct the electron and electron-nuclear correlation terms. Results presented for a series of n-alkanes have revealed the potential of this method for the accurate calculation of ionization energies of a wide variety of molecular systems containing hydrogen nuclei. The proposed methodology will also be applicable to exotic molecular systems containing positrons or muons.

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

Conformational properties and electronic structure of tetrahydrotetrazines studied by photoelectron spectroscopy and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Muchall, Heidi M.; Rademacher, Paul

1997-11-01

The photoelectron (PE) spectra of tetrahydro-1,2,3,4-tetrazines 1 and 2 and tetrahydro-1,2,4,5-tetrazines 3-5 have been recorded and their conformations have been investigated by ab initio SCF calculations. While v-tetrazine 2 is planar, tetrazines 1 and 3-5 each possess two low-energy conformations, according to ab initio HF and Becke3LYP methods. Attempts to assign ionization potentials to molecular orbitals obtained by semiempirical PM3 calculations indicate that this method is not suited for the compounds studied. Best results were obtained when the ab initio hybrid method Becke3LYP of the density functional theory was employed. Two conformers of 1 and 3-5 are present in the gas phase and their PE spectra are superimposed one upon the other. For v-tetrazine 1, ionizations arising from half-chair and unsymmetrical boat conformers have similar energies and cannot be separated in the PE spectrum. For s-tetrazine 3, on the other hand, the spectrum clearly shows different ionizations of both half-chairs, 3ee and 3ae.

Decay, excitation, and ionization of lithium Rydberg states by blackbody radiation

NASA Astrophysics Data System (ADS)

Ovsiannikov, V. D.; Glukhov, I. L.

2010-09-01

Details of interaction between the blackbody radiation and neutral lithium atoms were studied in the temperature ranges T = 100-2000 K. The rates of thermally induced decays, excitations and ionization were calculated for S-, P- and D-series of Rydberg states in the Fues' model potential approach. The quantitative regularities for the states of the maximal rates of blackbody-radiation-induced processes were determined. Approximation formulas were proposed for analytical representation of the depopulation rates.

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.

Density functional theory calculations of continuum lowering in strongly coupled plasmas.

PubMed

Vinko, S M; Ciricosta, O; Wark, J S

2014-03-24

An accurate description of the ionization potential depression of ions in plasmas due to their interaction with the environment is a fundamental problem in plasma physics, playing a key role in determining the ionization balance, charge state distribution, opacity and plasma equation of state. Here we present a method to study the structure and position of the continuum of highly ionized dense plasmas using finite-temperature density functional theory in combination with excited-state projector augmented-wave potentials. The method is applied to aluminium plasmas created by intense X-ray irradiation, and shows excellent agreement with recently obtained experimental results. We find that the continuum lowering for ions in dense plasmas at intermediate temperatures is larger than predicted by standard plasma models and explain this effect through the electronic structure of the valence states in these strong-coupling conditions.

An evaluation of ionizing radiation emitted by high power microwave generators

NASA Astrophysics Data System (ADS)

Lovell, C. David; Bolch, W. Emmett

1992-02-01

Ionizing radiation emitted by electron-beam driven high power microwave (HPM) generators were measured in the near and far-field using lithium fluoride (LiF) thermoluminescent dosimeters (TLD's). Simplified photon energy spectra were determined by measuring radiation transmission, at electron beam energies of 300 to 650 keV, through various thicknesses of steel and lead attenuators. These data were used to calculate the effective energy of the x-rays produced by interactions between the electrons and the walls or other structures of the HPM generators. Operators were polled to determine locations of burn marks or other visible damage to locate potential ionizing radiation source regions.

Two- and three-photon ionization in the noble gases

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

McGuire, E.J.

1981-08-01

By using a characteristic Green's function for an exactly solvable Schroedinger equation with an approximation to the central potential of Hermann and Skillman, the cross section for nonresonant two- and three-photon ionization of Ne, Ar, Kr, and Xe were calculated in jl coupling. Expressions for cross sections in jl coupling are given. Comparison with the Ar two-photon cross section of Pindzola and Kelly, calculated using the many-body theory, the dipole-length approximation, and LS coupling shows a disagreement of as much as a factor of 2. The disagreement appears to arise from distortion introduced by shifting the Green's-function resonances to experimentalmore » values.« less

Potential of mean force for electrical conductivity of dense plasmas

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

Starrett, C. E.

The electrical conductivity in dense plasmas can be calculated with the relaxation-time approximation provided that the interaction potential between the scattering electron and the ion is known. To date there has been considerable uncertainty as to the best way to define this interaction potential so that it correctly includes the effects of ionic structure, screening by electrons and partial ionization. The current approximations lead to significantly different results with varying levels of agreement when compared to bench-mark calculations and experiments. Here, we present a new way to define this potential, drawing on ideas from classical fluid theory to define amore » potential of mean force. This new potential results in significantly improved agreement with experiments and bench-mark calculations, and includes all the aforementioned physics self-consistently.« less

Potential of mean force for electrical conductivity of dense plasmas

DOE PAGES

Starrett, C. E.

2017-09-28

The electrical conductivity in dense plasmas can be calculated with the relaxation-time approximation provided that the interaction potential between the scattering electron and the ion is known. To date there has been considerable uncertainty as to the best way to define this interaction potential so that it correctly includes the effects of ionic structure, screening by electrons and partial ionization. The current approximations lead to significantly different results with varying levels of agreement when compared to bench-mark calculations and experiments. Here, we present a new way to define this potential, drawing on ideas from classical fluid theory to define amore » potential of mean force. This new potential results in significantly improved agreement with experiments and bench-mark calculations, and includes all the aforementioned physics self-consistently.« less

Potential of mean force for electrical conductivity of dense plasmas

NASA Astrophysics Data System (ADS)

Starrett, C. E.

2017-12-01

The electrical conductivity in dense plasmas can be calculated with the relaxation-time approximation provided that the interaction potential between the scattering electron and the ion is known. To date there has been considerable uncertainty as to the best way to define this interaction potential so that it correctly includes the effects of ionic structure, screening by electrons and partial ionization. Current approximations lead to significantly different results with varying levels of agreement when compared to bench-mark calculations and experiments. We present a new way to define this potential, drawing on ideas from classical fluid theory to define a potential of mean force. This new potential results in significantly improved agreement with experiments and bench-mark calculations, and includes all the aforementioned physics self-consistently.

Dynamics of ionization of H2 by Ne*(3P) investigated by electron spectroscopy

NASA Astrophysics Data System (ADS)

Noroski, Joseph H.; Siska, P. E.

2006-10-01

The Penning ionization reaction Ne*(2p53sP3)+H2→[NeH2]++e- has been studied in crossed supersonic molecular beams with electron-energy analysis at four collision energies E =1.83, 2.50, 3.16, and 3.89kcal/mol. The electron kinetic-energy spectra, which directly reflect the ionizing transition region, show resolved peaks assignable to v'=0-4 of H2+. The vibrational populations deviate systematically from Franck-Condon behavior, suggesting that the discrete-continuum coupling increases with H2 bond stretching. Each peak displays both increasing breadth and increasing blueshift with increasing E, and the blueshift also increases with increasing v'. The first two properties are consistent with a predominantly repulsive excited-state potential-energy surface, while the last is speculated to be a reflection of the rHH dependence of the ionic surface. Quantum scattering calculations based on ab initio potential surfaces for the excited and ionic states in spherical and infinite-order-sudden rigid rotor approximations are in semiquantitative agreement with the measurements. Discrepancies suggest changes in the imaginary, absorptive part of the excited surface, which probably can be best effected by multiproperty fitting calculations.

Collisional Ionization Equilibrium for Optically Thin Plasmas

NASA Technical Reports Server (NTRS)

Bryans, P.; Mitthumsiri, W.; Savin, D. W.; Badnell, N. R.; Gorczyca, T. W.; Laming, J. M.

2006-01-01

Reliably interpreting spectra from electron-ionized cosmic plasmas requires accurate ionization balance calculations for the plasma in question. However, much of the atomic data needed for these calculations have not been generated using modern theoretical methods and their reliability are often highly suspect. We have utilized state-of-the-art calculations of dielectronic recombination (DR) rate coefficients for the hydrogenic through Na-like ions of all elements from He to Zn. We have also utilized state-of-the-art radiative recombination (RR) rate coefficient calculations for the bare through Na-like ions of all elements from H to Zn. Using our data and the recommended electron impact ionization data of Mazzotta et al. (1998), we have calculated improved collisional ionization equilibrium calculations. We compare our calculated fractional ionic abundances using these data with those presented by Mazzotta et al. (1998) for all elements from H to Ni, and with the fractional abundances derived from the modern DR and RR calculations of Gu (2003a,b, 2004) for Mg, Si, S, Ar, Ca, Fe, and Ni.

Density, Velocity and Ionization Structure in Accretion-Disc Winds

NASA Technical Reports Server (NTRS)

Sonneborn, George (Technical Monitor); Long, Knox

2004-01-01

This was a project to exploit the unique capabilities of FUSE to monitor variations in the wind- formed spectral lines of the luminous, low-inclination, cataclysmic variables(CV) -- RW Sex. (The original proposal contained two additional objects but these were not approved.) These observations were intended to allow us to determine the relative roles of density and ionization state changes in the outflow and to search for spectroscopic signatures of stochastic small-scale structure and shocked gas. By monitoring the temporal behavior of blue-ward extended absorption lines with a wide range of ionization potentials and excitation energies, we proposed to track the changing physical conditions in the outflow. We planned to use a new Monte Carlo code to calculate the ionization structure of and radiative transfer through the CV wind. The analysis therefore was intended to establish the wind geometry, kinematics and ionization state, both in a time-averaged sense and as a function of time.

Feasibility of Ionization-Mediated Pathway for Ultraviolet-Induced Melanin Damage.

PubMed

Mandal, Mukunda; Das, Tamal; Grewal, Baljinder K; Ghosh, Debashree

2015-10-22

Melanin is the pigment found in human skin that is responsible for both photoprotection and photodamage. Recently there have been reports that greater photodamage of DNA occurs when cells containing melanin are irradiated with ultraviolet (UV) radiation, thus suggesting that the photoproducts of melanin cause DNA damage. Photoionization processes have also been implicated in the photodegradation of melanin. However, not much is known about the oxidation potential of melanin and its monomers. In this work we calculate the ionization energies of monomers, dimers, and few oligomers of eumelanin to estimate the threshold energy required for the ionization of eumelanin. We find that this threshold is within the UV-B region for eumelanin. We also look at the charge and spin distributions of the various ionized states of the monomers that are formed to understand which of the ionization channels might favor monomerization from a covalent dimer.

Stochastic treatment of electron multiplication without scattering in dielectrics

NASA Technical Reports Server (NTRS)

Lin, D. L.; Beers, B. L.

1981-01-01

By treating the emission of optical phonons as a Markov process, a simple analytic method is developed for calculating the electronic ionization rate per unit length for dielectrics. The effects of scattering from acoustic and optical phonons are neglected. The treatment obtains universal functions in recursive form, the theory depending on only two dimensionless energy ratios. A comparison of the present work with other numerical approaches indicates that the effect of scattering becomes important only when the electric potential energy drop in a mean free path for optical-phonon emission is less than about 25% of the ionization potential. A comparison with Monte Carlo results is also given for Teflon.

Calculation of H2-He Flow with Nonequilibrium Ionization and Radiation: an Interim Report

NASA Technical Reports Server (NTRS)

Furudate, Michiko; Chang, Keun-Shik

2005-01-01

The nonequilibrium ionization process in hydrogen-helium mixture behind a strong shock wave is studied numerically using the detailed ionization rate model developed recently by Park which accounts for emission and absorption of Lyman lines. The study finds that, once the avalanche ionization is started, the Lyman line is self-absorbed. The intensity variation of the radiation at 5145 Angstroms found by Leibowitz in a shock tube experiment can be numerically reproduced by assuming that ionization behind the shock wave prior to the onset of avalanche ionization is 1.3%. Because 1.3% initial ionization is highly unlikely, Leibowitz s experimental data is deemed questionable. By varying the initial electron density value in the calculation, the calculated ionization equilibration time is shown to increase approximately as inverse square-root of the initial electron density value. The true ionization equilibration time is most likely much longer than the value found by Leibowitz.

The classical equation of state of fully ionized plasmas

NASA Astrophysics Data System (ADS)

Eisa, Dalia Ahmed

2011-03-01

The aim of this paper is to calculate the analytical form of the equation of state until the third virial coefficient of a classical system interacting via an effective potential of fully Ionized Plasmas. The excess osmotic pressure is represented in the forms of a convergent series expansions in terms of the plasma Parameter μ _{ab} = {{{e_a e_b χ } over {DKT}}}, where χ2 is the square of the inverse Debye radius. We consider only the thermal equilibrium plasma.

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

Ionization potential depression in an atomic-solid-plasma picture

NASA Astrophysics Data System (ADS)

Rosmej, F. B.

2018-05-01

Exotic solid density matter such as heated hollow crystals allow extended material studies while their physical properties and models such as the famous ionization potential depression are presently under renewed controversial discussion. Here we develop an atomic-solid-plasma (ASP) model that permits ionization potential depression studies also for single and multiple core hole states. Numerical calculations show very good agreement with recently available data not only in absolute values but also for Z-scaled properties while currently employed methods fail. For much above solid density compression, the ASP model predicts increased K-edge energies that are related to a Fermi surface rising. This is in good agreement with recent quantum molecular dynamics simulations. For hot dense matter a quantum number dependent optical electron finite temperature ion sphere model is developed that fits well with line shift and line disappearance data from dense laser produced plasma experiments. Finally, the physical transparency of the ASP picture allows a critical discussion of current methods.

Coupled Cluster Studies of Ionization Potentials and Electron Affinities of Single-Walled Carbon Nanotubes

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

Peng, Bo; Govind, Niranjan; Aprà, Edoardo

In this paper we apply equation-of-motion coupled cluster (EOMCC) methods in studies of vertical ionization potentials (IP) and electron affinities (EA) for sin- gled walled carbon nanotubes. EOMCC formulations for ionization potentials and electron affinities employing excitation manifolds spanned by single and double ex- citations (IP/EA-EOMCCSD) are used to study IPs and EAs of nanotubes as a function of nanotube length. Several armchair nanotubes corresponding to C20nH20 models with n = 2 - 6 have been used in benchmark calculations. In agreement with previous studies, we demonstrate that the electronegativity of C20nH20 systems remains, to a large extent, independent ofmore » nanotube length. We also compare IP/EA- EOMCCSD results with those obtained with the coupled cluster models with single and double excitations corrected by perturbative triples, CCSD(T), and density func- tional theory (DFT) using global and range-separated hybrid exchange-correlation functionals.« less

Zero kinetic energy spectroscopy: mass-analyzed threshold ionization spectra of chromium sandwich complexes with alkylbenzenes, (η(6)-RPh)(2)Cr (R = Me, Et, i-Pr, t-Bu).

PubMed

Ketkov, Sergey Y; Selzle, Heinrich L; Cloke, F Geoffrey N; Markin, Gennady V; Shevelev, Yury A; Domrachev, Georgy A; Schlag, Edward W

2010-10-28

For over 25 years zero kinetic energy (ZEKE) spectroscopy has yielded a rich foundation of high-resolution results of molecular ions. This was based on the discovery in the late 60's of long-lived ion states throughout the ionization continuum of molecular ions. Here, an example is chosen from another fundamental system pioneered at this university. The mass-analyzed threshold ionization (MATI) spectra of jet-cooled chromium bisarene complexes (η(6)-RPh)(2)Cr (R = Me (1), Et (2), i-Pr (3), and t-Bu (4)) have been measured and interpreted on the basis of DFT calculations. The MATI spectra of complexes 1 and 2 appear to reveal features arising from ionizations of the isomers formed by the rotation of one arene ring relative to the other. The 1 and 2 MATI spectra show two intense peaks corresponding to the 0(0)(0) ionizations with inverse intensity ratios. As indicated by the DFT calculations, the intensity ratio change on going from 1 to 2 results from different isomers contributing to each MATI peak. The ionization energies corresponding to the 0(0)(0) peaks are 42746 ± 5 and 42809 ± 5 cm(-1) for compound 1 and 42379 ± 5 and 42463 ± 5 cm(-1) for complex 2. The 1 and 2 spectra show also the weaker features representing transitions to the vibrationally excited cationic levels, the signals of individual rotamers being detected and assigned on the basis of calculated vibrational frequencies. The MATI spectra of compounds 3 and 4 reveal only one strong peak because of close ionization potentials of the isomers contributing to the MATI signal. The 3 and 4 ionization energies are 42104 ± 5 and 41917 ± 5 cm(-1), respectively. The precise values of ionization energies obtained from the MATI spectra reveal a nonlinear dependence of the IE on the number of Me groups in the alkyl substituents of (η(6)-RPh)(2)Cr. This can be explained by an increase in the molecular zero point energies on methylation of the substituents.

The lowest ionization potentials of Al2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Barnes, Leslie A.; Taylor, Peter R.

1988-01-01

Potential curves for the lowest two electronic states (X 2 sigma g + and A 2 pi u) of Al2(+) were computed using complete active space SCF/multireference CI wave functions and large Gaussian basis sets. The lowest observable vertical ionization potential (to Al2(+) X 2 sigma g +) of the Al2 X 3 pi u ground state is calculated to occur around 6.1 eV, in excellent agreement with the experimental range of 6.0 to 6.42 eV obtained in recent cluster ionization studies by Cox and co-workers. The second vertical ionization potential (to Al2(+) A 2 pi u) occurs near 6.4 eV, also within the experimental range. The adiabatic IP of 5.90 eV is in good agreement with the value of 5.8 to 6.1 eV deduced by Hanley and co-workers from the difference in thresholds between collision induced dissociation processes of Al3(+). The computed IP values are somewhat larger than those deduced from branching ratios in cluster fragmentation experiments by Jarrold and co-workers. The observation of an ionization threshold below 6.42 eV is shown to be incompatible with an Al2 ground electronic state assignment of 3 sigma g -, but the separation between the two lowest states of Al2 is so small that it is likely that both are populated in the experiments, so that this does not provide unambiguous support for the recent theoretical assignment of the ground state as 3 pi u.

Investigation on the absolute and relative photoionization cross sections of 3 potential propargylic fuels.

PubMed

Winfough, Matthew; Meloni, Giovanni

2017-12-01

Absolute photoionization cross sections for 2 potential propargylic fuels (propargylamine and dipropargyl ether) along with the partial ionization cross sections for their dissociative fragments are measured and presented for the first time via synchrotron photoionization mass spectrometry. The experimental setup consists of a multiplexed orthogonal time-of-flight mass spectrometer and is located at the Advanced Light Source facility of the Lawrence Berkeley National Laboratory in Berkeley, California. Data for a third propargylic compound (propargyl alcohol) were taken; however, because of its low signal, due to its weakly bound cation, only the dissociative ionization fragment from the H-loss channel is observed and presented. Suggested pathways leading to formation of dissociative photoionization fragments along with CBS-QB3 calculated adiabatic ionization energies and appearance energies for the dissociative fragments are also presented. Copyright © 2017 John Wiley & Sons, Ltd.

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

Photoionisation study of Xe.CF{sub 4} and Kr.CF{sub 4} van-der-Waals molecules

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

Alekseev, V. A., E-mail: alekseev@va3474.spb.edu; Kevorkyants, R.; Garcia, G. A.

2016-05-14

We report on photoionization studies of Xe.CF{sub 4} and Kr.CF{sub 4} van-der-Waals complexes produced in a supersonic expansion and detected using synchrotron radiation and photoelectron-photoion coincidence techniques. The ionization potential of CF{sub 4} is larger than those of the Xe and Kr atoms and the ground state of the Rg.CF{sub 4}{sup +} ion correlates with Rg{sup +} ({sup 2}P{sub 3/2}) + CF{sub 4}. The onset of the Rg.CF{sub 4}{sup +} signals was found to be only ∼0.2 eV below the Rg ionization potential. In agreement with experiment, complementary ab initio calculations show that vertical transitions originating from the potential minimummore » of the ground state of Rg.CF{sub 4} terminate at a part of the potential energy surfaces of Rg.CF{sub 4}{sup +}, which are approximately 0.05 eV below the Rg{sup +} ({sup 2}P{sub 3/2}) + CF{sub 4} dissociation limit. In contrast to the neutral complexes, which are most stable in the face geometry, for the Rg.CF{sub 4}{sup +} ions, the calculations show that the minimum of the potential energy surface is in the vertex geometry. Experiments which have been performed only with Xe.CF{sub 4} revealed no Xe.CF{sub 4}{sup +} signal above the first ionization threshold of Xe, suggesting that the Rg.CF{sub 4}{sup +} ions are not stable above the first dissociation limit.« less

Ion time-of-flight determinations of doubly to singly ionized mercury ion ratios from a mercury electron bombardment discharge

NASA Technical Reports Server (NTRS)

Sellen, J. M., Jr.; Kemp, R. F.; Hall, D. F.

1973-01-01

Doubly to singly charged mercury ion ratios in electron bombardment ion thruster exhaust beams have been determined as functions of bombardment discharge potential, thrust beam current, thrust beam radial position, acceleration-deceleration voltage ratio, and propellant utilization fraction. A mathematical model for two-step ionization processes has been derived, and calculated ion ratios are compared to observed ratios. Production of Hg(++) appears to result primarily from sequential ionization of Hg(+) in the discharge. Experimental and analytical results are presented, and design, construction, and operation features of an electrostatic deflection ion time-of-flight analyzer for the determination of the above-mentioned ratios are reviewed.

Absolute photoionization cross sections of two cyclic ketones: cyclopentanone and cyclohexanone.

PubMed

Price, Chelsea; Fathi, Yasmin; Meloni, Giovanni

2017-05-01

Absolute photoionization cross sections for cyclopentanone and cyclohexanone, as well as partial ionization cross sections for the dissociative ionized fragments, are presented in this investigation. Experiments are performed via a multiplexed photoionization mass spectrometer utilizing vacuum ultraviolet (VUV) synchrotron radiation supplied by the Advanced Light Source of Lawrence Berkeley National Laboratory. These results allow the quantification of these species that is relevant to investigate the kinetics and combustion reactions of potential biofuels. The CBS-QB3 calculated values for the adiabatic ionization energies agree well with the experimental values, and the identification of possible dissociative fragments is discussed for both systems. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Thermal ionization of Cs Rydberg states

NASA Astrophysics Data System (ADS)

Glukhov, I. L.; Ovsiannikov, V. D.

2009-01-01

Rates Pnl of photoionization from Rydberg ns-, np-, nd-states of a valence electron in Cs, induced by black-body radiation, were calculated on the basis of the modified Fues model potential method. The numerical data were approximated with a three-term expression which reproduces in a simple analytical form the dependence of Pnl on the ambient temperature T and on the principal quantum number n. The comparison between approximate and exactly calculated values of the thermal ionization rate demonstrates the applicability of the proposed approximation for highly excited states with n from 20 to 100 in a wide temperature range of T from 100 to 10,000 K. We present coefficients of this approximation for the s-, p- and d-series of Rydberg states.

Analytical solutions for avalanche-breakdown voltages of single-diffused Gaussian junctions

NASA Astrophysics Data System (ADS)

Shenai, K.; Lin, H. C.

1983-03-01

Closed-form solutions of the potential difference between the two edges of the depletion layer of a single diffused Gaussian p-n junction are obtained by integrating Poisson's equation and equating the magnitudes of the positive and negative charges in the depletion layer. By using the closed form solution of the static Poisson's equation and Fulop's average ionization coefficient, the ionization integral in the depletion layer is computed, which yields the correct values of avalanche breakdown voltage, depletion layer thickness at breakdown, and the peak electric field as a function of junction depth. Newton's method is used for rapid convergence. A flowchart to perform the calculations with a programmable hand-held calculator, such as the TI-59, is shown.

Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3

DOE PAGES

Cooper, Jason K.; Grant, Christian D.; Zhang, Jin Z.

2012-07-20

The vertical and adiabatic ionization potential (IP V and IP A) and vertical electron affinity (EA V) for six explosives (RDX, HMX, TNT, PETN, HMTD, and TATP) have been studied by ab initio computational methods. The IPV was calculated using MP2 and CBS-QB3 while the IP A was calculated with B3LYP, CAM-B3LYP, ω B97XD, B2PLYP, and MP2. RDX and TNT IP A’s were also reported using CBS -QB3. Excluding results by CBS-QB3, B3LYP and B2PLYPD provided superior and more consistent results for calculating the IP. The EA V were calculated using the same methods however B3LYP performed the worst inmore » this case with MP2 and B2PLYPD predicting values closest to those made by CBS-QB3, which was used a reference due to lacking experimental data. Basis set effects were evaluated using 6- 31+G(d,p), 6-311+G(d,p), and 6-311+(3df,2p) for both IP and EA. 6-31+G(d,p) gave satisfactory results for calculating both IP however 6-311+G(3df,2p) had improved results in calculating the EA. The four nitro containing compounds had exothermic reduction potentials while the peroxides were unfavorable. Additionally, it was seen that RDX, HMX, TATP and HMTD were unstable in their reduced forms. Results are aimed to assist detection and screening methods.« less

Local thermodynamic equilibrium in rapidly heated high energy density plasmas

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

Aslanyan, V.; Tallents, G. J.

Emission spectra and the dynamics of high energy density plasmas created by optical and Free Electron Lasers (FELs) depend on the populations of atomic levels. Calculations of plasma emission and ionization may be simplified by assuming Local Thermodynamic Equilibrium (LTE), where populations are given by the Saha-Boltzmann equation. LTE can be achieved at high densities when collisional processes are much more significant than radiative processes, but may not be valid if plasma conditions change rapidly. A collisional-radiative model has been used to calculate the times taken by carbon and iron plasmas to reach LTE at varying densities and heating rates.more » The effect of different energy deposition methods, as well as Ionization Potential Depression are explored. This work shows regimes in rapidly changing plasmas, such as those created by optical lasers and FELs, where the use of LTE is justified, because timescales for plasma changes are significantly longer than the times needed to achieve an LTE ionization balance.« less

Indirect dark matter signatures in the cosmic dark ages. II. Ionization, heating, and photon production from arbitrary energy injections

NASA Astrophysics Data System (ADS)

Slatyer, Tracy R.

2016-01-01

Any injection of electromagnetically interacting particles during the cosmic dark ages will lead to increased ionization, heating, production of Lyman-α photons and distortions to the energy spectrum of the cosmic microwave background, with potentially observable consequences. In this paper we describe numerical results for the low-energy electrons and photons produced by the cooling of particles injected at energies from keV to multi-TeV scales, at arbitrary injection redshifts (but focusing on the post-recombination epoch). We use these data, combined with existing calculations modeling the cooling of these low-energy particles, to estimate the resulting contributions to ionization, excitation and heating of the gas, and production of low-energy photons below the threshold for excitation and ionization. We compute corrected deposition-efficiency curves for annihilating dark matter, and demonstrate how to compute equivalent curves for arbitrary energy-injection histories. These calculations provide the necessary inputs for the limits on dark matter annihilation presented in the accompanying paper I, but also have potential applications in the context of dark matter decay or deexcitation, decay of other metastable species, or similar energy injections from new physics. We make our full results publicly available at http://nebel.rc.fas.harvard.edu/epsilon, to facilitate further independent studies. In particular, we provide the full low-energy electron and photon spectra, to allow matching onto more detailed codes that describe the cooling of such particles at low energies.

Ionization waves of arbitrary velocity driven by a flying focus

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

Palastro, J. P.; Turnbull, D.; Bahk, S. -W.

A chirped laser pulse focused by a chromatic lens exhibits a dynamic, or flying, focus in which the trajectory of the peak intensity decouples from the group velocity. In a medium, the flying focus can trigger an ionization front that follows this trajectory. By adjusting the chirp, the ionization front can be made to travel at an arbitrary velocity along the optical axis. For this study, we present analytical calculations and simulations describing the propagation of the flying focus pulse, the self-similar form of its intensity profile, and ionization wave formation. The ability to control the speed of the ionizationmore » wave and, in conjunction, mitigate plasma refraction has the potential to advance several laser-based applications, including Raman amplification, photon acceleration, high-order-harmonic generation, and THz generation.« less

Ionization waves of arbitrary velocity driven by a flying focus

DOE PAGES

Palastro, J. P.; Turnbull, D.; Bahk, S. -W.; ...

2018-03-01

A chirped laser pulse focused by a chromatic lens exhibits a dynamic, or flying, focus in which the trajectory of the peak intensity decouples from the group velocity. In a medium, the flying focus can trigger an ionization front that follows this trajectory. By adjusting the chirp, the ionization front can be made to travel at an arbitrary velocity along the optical axis. For this study, we present analytical calculations and simulations describing the propagation of the flying focus pulse, the self-similar form of its intensity profile, and ionization wave formation. The ability to control the speed of the ionizationmore » wave and, in conjunction, mitigate plasma refraction has the potential to advance several laser-based applications, including Raman amplification, photon acceleration, high-order-harmonic generation, and THz generation.« 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

Charge transfer and ionization in collisions of Si3+ with H from low to high energy

NASA Astrophysics Data System (ADS)

Wang, J. G.; He, B.; Ning, Y.; Liu, C. L.; Yan, J.; Stancil, P. C.; Schultz, D. R.

2006-11-01

Charge transfer processes due to collisions of ground state Si3+(3sS1) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) and classical-trajectory Monte Carlo (CTMC) methods. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial coupling matrix elements obtained from Herrero [J. Phys. B 29, 5583 (1996)] which were calculated with a full configuration-interaction method. Total and state-selective single-electron capture cross sections are obtained for collision energies from 0.01eV/u to 1MeV/u . Total and state-selective rate coefficients are also presented for temperatures from 2×103K to 107K . Comparison with existing data reveals that the total CTMC cross sections are in good agreement with the experimental measurements at the higher considered energies and that previous Landau-Zener calculations underestimate the total rate coefficients by a factor of up to two. The CTMC calculations of target ionization are presented for high energies.

NLTE opacity calculations: C-Si and C-Ge mixtures

NASA Astrophysics Data System (ADS)

Jarrah, W.; Benredjem, D.; Pain, J.-C.; Dubau, J.

2017-09-01

The opacity is an important issue in the knowledge of the radiative properties of ICF and astrophysical plasmas. We present the opacity of dopants (silicon, germanium) embedded in the ablator of some ICF capsules. In recent works, Hill and Rose calculated the opacity of silicon in LTE and non-LTE plasmas, while Minguez and co-workers focused on the opacity of carbon. We have used the Cowan code to calculate the atomic structure of carbon, silicon and germanium in various ionic stages. The cross-sections of atomic processes (collisional excitation, collisional ionization) are obtained by fitting the values given by the code FAC to the Van Regemorter-like formulas of Sampson and Zhang. A corrected Gaunt factor is then obtained. A collisional-radiative code was developed in order to obtain the ionic populations, the level populations and the opacity. Line broadening and line shift are taken into account. The ionization potential depression is included in our calculations. The effect of a radiation field on the opacity is examined.

Time-dependent spin-density-functional-theory description of He+-He collisions

NASA Astrophysics Data System (ADS)

Baxter, Matthew; Kirchner, Tom; Engel, Eberhard

2017-09-01

Theoretical total cross-section results for all ionization and capture processes in the He+-He collision system are presented in the approximate impact energy range of 10-1000 keV/amu. Calculations were performed within the framework of time-dependent spin-density functional theory. The Krieger-Li-Iafrate approximation was used to determine an accurate exchange-correlation potential in the exchange-only limit. The results of two models, one where electron translation factors in the orbitals used to calculate the potential are ignored and another where partial electron translation factors are included, are compared with available experimental data as well as a selection of previous theoretical calculations.

Calculation of photoionization cross section near auto-ionizing lines and magnesium photoionization cross section near threshold

NASA Technical Reports Server (NTRS)

Moore, E. N.; Altick, P. L.

1972-01-01

The research performed is briefly reviewed. A simple method was developed for the calculation of continuum states of atoms when autoionization is present. The method was employed to give the first theoretical cross section for beryllium and magnesium; the results indicate that the values used previously at threshold were sometimes seriously in error. These threshold values have potential applications in astrophysical abundance estimates.

Dissociative Ionization of Benzene by Electron Impact

NASA Technical Reports Server (NTRS)

Huo, Winifred; Dateo, Christopher; Kwak, Dochan (Technical Monitor)

2002-01-01

We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.

Ultrafast multiphoton ionization dynamics and control of NaK molecules

NASA Astrophysics Data System (ADS)

Davidsson, Jan; Hansson, Tony; Mukhtar, Emad

1998-12-01

The multiphoton ionization dynamics of NaK molecules is investigated experimentally using one-color pump-probe femtosecond spectroscopy at 795 nm and intermediate laser field strengths (about 10 GW/cm2). Both NaK+ and Na+ ions are detected as a function of pulse separation time, pulse intensities, and strong pulse-weak pulse order. To aid in the analysis, the potential energy curves of the two lowest electronic states of NaK+ and the electronic transition dipole moment between them are calculated by the GAUSSIAN94 UCIS method. Different ionization pathways are identified by Franck-Condon analysis, and vibrational dynamics in the A 1Σ+ and 3 1Π states, as well as in the ground state, is observed. Further, the existence of a highly excited (above the adiabatic ionization limit) neutral state of NaK is proposed. By changing the strong pulse-weak pulse order of the pulses, the ionization pathways for production of both ions can be varied and thus controlled.

Identification of four rotamers of m-methoxystyrene by resonant two-photon ionization and mass analyzed threshold ionization spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Yanqi; Tzeng, Sheng Yuan; Shivatare, Vidya; Takahashi, Kaito; Zhang, Bing; Tzeng, Wen Bih

2015-03-01

We report the vibronic and cation spectra of four rotamers of m-methoxystyrene, recorded by using the two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques. The excitation energies of the S1← S0 electronic transition are found to be 32 767, 32 907, 33 222, and 33 281 cm-1, and the corresponding adiabatic ionization energies are 65 391, 64 977, 65 114, and 64 525 cm-1 for these isomeric species. Most of the observed active vibrations in the electronically excited S1 and cationic ground D0 states involve in-plane ring deformation and substituent-sensitive bending motions. It is found that the relative orientation of the methoxyl with respect to the vinyl group does not influence the vibrational frequencies of the ring-substituent bending modes. The two dimensional potential energy surface calculations support our experimental finding that the isomerization is restricted in the S1 and D0 states.

Calculation of the Ionization Coefficient in the Townsend Discharge in the Mixture of Argon and Mercury Vapors with Temperature-Dependent Composition

NASA Astrophysics Data System (ADS)

Bondarenko, G. G.; Dubinina, M. S.; Fisher, M. R.; Kristya, V. I.

2018-04-01

For a hybrid model of the low-current discharge considering, along with direct ionization of the mixture components by electrons, the Penning ionization of mercury atoms by metastable argon atoms, the ionization coefficient in the argon-mercury mixture used in illuminating lamps is calculated. The analytical approximation formula describing the dependence of the ionization coefficient of the mixture on the reduced electric field strength and temperature is obtained for sufficiently wide ranges of their variations, and its accuracy is estimated. It is demonstrated that the discharge ignition voltage calculated using this formula is in agreement with the results of simulation and the available experimental data.

An optically stimulated luminescence system to measure dose profiles in x-ray computed tomography

NASA Astrophysics Data System (ADS)

Yukihara, E. G.; Ruan, C.; Gasparian, P. B. R.; Clouse, W. J.; Kalavagunta, C.; Ahmad, S.

2009-10-01

This paper describes an LED-based optically stimulated luminescence (OSL) system for dose profile measurements using OSL detector strips and investigates its performance in x-ray computed tomography (CT) dosimetry. To compensate for the energy response of the Al2O3:C OSL detectors, which have an effective atomic number of 11.28, field-specific energy correction factors were determined using two methods: (a) comparing the OSL profiles with ionization chamber point measurements (0.3 cm3 ionization chamber) and (b) comparing the OSL profiles integrated over a 100 mm length with 100 mm long pencil ionization chamber measurements. These correction factors were obtained for the CT body and head phantoms, central and peripheral positions and three x-ray tube potential differences (100 kVp, 120 kVp and 140 kVp). The OSL dose profiles corrected by the energy dependence agreed with the ionization chamber point measurements over the entire length of the phantom (300 mm). For 120 kVp x-ray tube potential difference, the CTDI100 values calculated using the OSL dose profiles corrected for the energy dependence and those obtained from an independent measurement with a 100 mm long pencil ionization chamber also agreed within ±5%.

Absolute photoionization cross sections of furanic fuels: 2-ethylfuran, 2-acetylfuran and furfural.

PubMed

Smith, Audrey R; Meloni, Giovanni

2015-11-01

Absolute photoionization cross sections of the molecules 2-ethylfuran, 2-acetylfuran and furfural, including partial ionization cross sections for the dissociative ionized fragments, are measured for the first time. These measurements are important because they allow fuel quantification via photoionization mass spectrometry and the development of quantitative kinetic modeling for the complex combustion of potential fuels. The experiments are carried out using synchrotron photoionization mass spectrometry with an orthogonal time-of-flight spectrometer used for mass analysis at the Advanced Light Source of Lawrence Berkeley National Laboratory. The CBS-QB3 calculations of adiabatic ionization energies and appearance energies agree well with the experimental results. Several bond dissociation energies are also derived and presented. Copyright © 2015 John Wiley & Sons, Ltd.

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.

Calculation of multiphoton ionization processes

NASA Technical Reports Server (NTRS)

Chang, T. N.; Poe, R. T.

1976-01-01

We propose an accurate and efficient procedure in the calculation of multiphoton ionization processes. In addition to the calculational advantage, this procedure also enables us to study the relative contributions of the resonant and nonresonant intermediate states.

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

Selected cis- and trans-3-fluorostyrene rotamers studied by two-color resonant two-photon mass-analyzed threshold ionization spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Pei Ying; Tzeng, Wen Bih

2015-10-01

We applied two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques to record the vibronic, photoionization efficiency, and cation spectra of the selected rotamers of 3-fluorostyrene. The adiabatic ionization energies of cis- and trans-3-fluorostyrene were determined to be 69 960 ± 5 and 69 856 ± 5 cm-1, respectively. Cation vibrations 10a, 15, 6b, and 12 of both rotamers have been found to have frequencies of 218, 404, 452, and 971 cm-1, respectively. This finding shows that the relative orientation of the vinyl group with respect to the F atom does not affect these vibrations of the 3-fluorostyrene cation. Our one-dimensional potential energy surface calculations support that the cis-trans isomerization of 3-fluorostyrene does not occur under the present experimental conditions.

Central-cell corrections and shallow donor states in strong magnetic fields

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

Jayam, Sr. Gerardin; Navaneethakrishnan, K.

2001-06-01

Ionization energies and the central-cell corrections have been calculated for a few shallow donors in Si, GaP, and GaAs. We have assumed a short range potential with two parameters for the strength and the range for each donor, representing the central-cell effects. These parameters are fixed using the experimentally available ionization energies for each donor in a semiconductor. In the presence of a magnetic field the donor ionization energies are estimated using a variational procedure. Our results show that the ionization energies and the central-cell corrections increase with magnetic field. Our results are compared for GaAs with the recent workmore » by Heron et al. [R. J. Heron, R. A. Lewis, P. E. Simmonds, R. P. Starret, A. V. Skougarevsky, R. G. Clark, and C. R. Stanley, J. Appl. Phys. 85, 893 (1999)]. {copyright} 2001 American Institute of Physics.« less

Theoretical Studies of Group IVA and Group IVB Chemistry

DTIC Science & Technology

2012-01-13

novel ionic liquids . We have performed very high level CCSD(T) calculations on one such species, Al13- to predict its ionization potential in nearly...Precursors. Polyhedral oligomeric silsesquioxanes (POSS) are three- dimensional Si-O cage compounds that have many uses, because of their resistance

Direct computation of general chemical energy differences: Application to ionization potentials, excitation, and bond energies.

PubMed

Beste, A; Harrison, R J; Yanai, T

2006-08-21

Chemists are mainly interested in energy differences. In contrast, most quantum chemical methods yield the total energy which is a large number compared to the difference and has therefore to be computed to a higher relative precision than would be necessary for the difference alone. Hence, it is desirable to compute energy differences directly, thereby avoiding the precision problem. Whenever it is possible to find a parameter which transforms smoothly from an initial to a final state, the energy difference can be obtained by integrating the energy derivative with respect to that parameter (cf. thermodynamic integration or adiabatic connection methods). If the dependence on the parameter is predominantly linear, accurate results can be obtained by single-point integration. In density functional theory and Hartree-Fock, we applied the formalism to ionization potentials, excitation energies, and chemical bond breaking. Example calculations for ionization potentials and excitation energies showed that accurate results could be obtained with a linear estimate. For breaking bonds, we introduce a nongeometrical parameter which gradually turns the interaction between two fragments of a molecule on. The interaction changes the potentials used to determine the orbitals as well as the constraint on the orbitals to be orthogonal.

Photon-assisted Beam Probes for Low Temperature Plasmas and Installation of Neutral Beam Probe in Helimak

NASA Astrophysics Data System (ADS)

Garcia de Gorordo, Alvaro; Hallock, Gary A.; Kandadai, Nirmala

2008-11-01

The Heavy Ion Beam Probe (HIBP) diagnostic has successfully measured the electric potential in a number of major plasma devices in the fusion community. In contrast to a Langmuir probe, the HIBP measures the exact electric potential rather than the floating potential. It is also has the advantage of being a very nonperturbing diagnostic. We propose a new photon-assisted beam probe technique that would extend the HIBP type of diagnostics into the low temperature plasma regime. We expect this method to probe plasmas colder than 10 eV. The novelty of the proposed diagnostic is a VUV laser that ionizes the probing particle. Excimer lasers produce the pulsed VUV radiation needed. The lasers on the market don't have a short enough wavelength too ionize any ion directly and so we calculate the population density of excited states in a NLTE plasma. These new photo-ionization techniques can take an instantaneous one-dimensional potential measurement of a plasma and are ideal for nonmagnitized plasmas where continuous time resolution is not required. Also the status of the Neutral Beam Probe installation on the Helimak experiment will be presented.

Determination of adiabatic ionization potentials and electron affinities of energetic molecules with the Gaussian-4 method

NASA Astrophysics Data System (ADS)

Manaa, M. Riad

2017-06-01

Adiabatic ionization potentials (IPad) and electron affinities (EAad) are determined with the Gaussian-4 (G4) method for the energetic molecules PETN, RDX, β-δ-HMX, CL-17, TNB, TNT, CL-14, DADNE, TNA, and TATB. The IPad and EAad values are in the range of 8.43-11.73 and 0.74-2.86 eV, respectively. Variations are due to substitutional effects of electron withdrawing and donating functional groups. Enthalpies of formation are also determined for several of these molecules to augment the list of recently reported G4 values. The calculated IPad and EAad provide quantitative assessment of such molecular properties as chemical hardness, molecular electronegativity, and "intrinsic" molecular physical hardness.

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

Komppula, J., E-mail: jani.komppula@jyu.fi; Tarvainen, O.

A theoretical framework for power dissipation in low temperature plasmas in corona equilibrium is developed. The framework is based on fundamental conservation laws and reaction cross sections and is only weakly sensitive to plasma parameters, e.g., electron temperature and density. The theory is applied to low temperature atomic and molecular hydrogen laboratory plasmas for which the plasma heating power dissipation to photon emission, ionization, and chemical potential is calculated. The calculated photon emission is compared to recent experimental results.

Energetics of short hydrogen bonds in photoactive yellow protein.

PubMed

Saito, Keisuke; Ishikita, Hiroshi

2012-01-03

Recent neutron diffraction studies of photoactive yellow protein (PYP) proposed that the H bond between protonated Glu46 and the chromophore [ionized p-coumaric acid (pCA)] was a low-barrier H bond (LBHB). Using the atomic coordinates of the high-resolution crystal structure, we analyzed the energetics of the short H bond by two independent methods: electrostatic pK(a) calculations and a quantum mechanical/molecular mechanical (QM/MM) approach. (i) In the QM/MM optimized geometry, we reproduced the two short H-bond distances of the crystal structure: Tyr42-pCA (2.50 Å) and Glu46-pCA (2.57 Å). However, the H atoms obviously belonged to the Tyr or Glu moieties, and were not near the midpoint of the donor and acceptor atoms. (ii) The potential-energy curves of the two H bonds resembled those of standard asymmetric double-well potentials, which differ from those of LBHB. (iii) The calculated pK(a) values for Glu46 and pCA were 8.6 and 5.4, respectively. The pK(a) difference was unlikely to satisfy the prerequisite for LBHB. (iv) The LBHB in PYP was originally proposed to stabilize the ionized pCA because deprotonated Arg52 cannot stabilize it. However, the calculated pK(a) of Arg52 and QM/MM optimized geometry suggested that Arg52 was protonated on the protein surface. The short H bond between Glu46 and ionized pCA in the PYP ground state could be simply explained by electrostatic stabilization without invoking LBHB.

Low-energy electron elastic scattering and impact ionization with hydrogenlike helium in Debye plasmas

NASA Astrophysics Data System (ADS)

Li, Jun; Zhang, Song Bin; Ye, Bang Jiao; Wang, Jian Guo; Janev, R. K.

2017-09-01

Low-energy electron elastic scattering and impact ionization with hydrogenlike helium in Debye plasmas have been investigated by employing the exterior complex scaling method. The interactions between charged particles in the plasmas have been represented by Debye-Hückel potentials. The 1 s -1 s elastic collision strengths below the n =2 excitation threshold of He+ dominated by resonance structures are calculated for different screening lengths. As the screening strength increases, the resonance peaks studied [2(1,0) 2 +1Se,3Po,1De , and 2(0,1) 2 +1Po] exhibit blueshifts and then redshifts with a further increase of the screening strength, which results in dramatic changes of the collision strengths. It is found that these dynamic variation features of the resonances are related to the changes of energy levels of He+ in the screened potential and geometric configurations of resonances. Triple-differential-ionization cross sections in coplanar geometries at 6-Ry incident electron energy are also reported, significant changes are observed with varying screening length.

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).

Electron propagator calculations on the ionization energies of CrH -, MnH - and FeH -

NASA Astrophysics Data System (ADS)

Lin, Jyh-Shing; Ortiz, J. V.

1990-08-01

Electron propagator calculations with unrestricted Hartree-Fock reference states yield the ionization energies of the title anions. Spin contamination in the anionic reference state is small, enabling the use of second-and third-order self-energies in the Dyson equation. Feynman-Dyson amplitudes for these ionizations are essentially identical to canonical spin-orbitals. For most of the final states, these consist of an antibonding combination of an sp metal hybrid, polarized away from the hydrogen, and hydroegen s functions. In one case, the Feynman-Dyson amplitude consists of nonbonding d functions. Calculated ionization energies are within 0.5 eV of experiment.

Continuum Lowering and Fermi-Surface Rising in Strongly Coupled and Degenerate Plasmas

NASA Astrophysics Data System (ADS)

Hu, S. X.

2017-08-01

Continuum lowering is a well known and important physics concept that describes the ionization potential depression (IPD) in plasmas caused by thermal- or pressure-induced ionization of outer-shell electrons. The existing IPD models are often used to characterize plasma conditions and to gauge opacity calculations. Recent precision measurements have revealed deficits in our understanding of continuum lowering in dense hot plasmas. However, these investigations have so far been limited to IPD in strongly coupled but nondegenerate plasmas. Here, we report a first-principles study of the K -edge shifting in both strongly coupled and fully degenerate carbon plasmas, with quantum molecular dynamics calculations based on the all-electron density-functional theory. The resulting K -edge shifting versus plasma density, as a probe to the continuum lowering and the Fermi-surface rising, is found to be significantly different from predictions of existing IPD models. In contrast, a simple model of "single-atom-in-box," developed in this work, accurately predicts K -edge locations as ab initio calculations provide.

Total Electron-Impact Ionization Cross-Sections of CFx and NFx (x = 1 - 3)

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Tarnovsky, Vladimir; Becker, Kurt H.; Kwak, Dochan (Technical Monitor)

2001-01-01

The discrepancy between experimental and theoretical total electron-impact ionization cross sections for a group of fluorides, CFx, and NFx, (x = 1 - 3), is attributed to the inadequacies in previous theoretical models. Cross-sections calculated using a recently developed siBED (simulation Binary-Encounter-Dipole) model that takes into account the shielding of the long-range dipole potential between the scattering electron and target are in agreement with experimentation. The present study also carefully reanalyzed the previously reported experimental data to account for the possibility of incomplete collection of fragment ions and the presence of ion-pair formation channels. For NF3, our experimental and theoretical cross-sections compare well with the total ionization cross-sections recently reported by Haaland et al. in the region below dication formation.

A model of electron collecting plasma contractors

NASA Technical Reports Server (NTRS)

Davis, V. A.; Katz, I.; Mandell, M. J.; Parks, D. E.

1989-01-01

A model of plasma contractors is being developed, which can be used to describe electron collection in a laboratory test tank and in the space environment. To validate the model development, laboratory experiments are conducted in which the source plasma is separated from the background plasma by a double layer. Model calculations show that an increase in ionization rate with potential produces a steep rise in collected current with increasing potential.

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.

Electron ionization and dissociation of aliphatic amino acids

NASA Astrophysics Data System (ADS)

Papp, P.; Shchukin, P.; Kočíšek, J.; Matejčík, Š.

2012-09-01

We present experimental and theoretical study of electron ionization and dissociative ionization to the gas phase amino acids valine, leucine, and isoleucine. A crossed electron/molecular beams technique equipped with quadrupole mass analyzer has been applied to measure mass spectra and ion efficiency curves for formation of particular ions. From experimental data the ionization energies of the molecules and the appearance energies of the fragment ions were determined. Ab initio calculations (Density Functional Theory and G3MP2 methods) were performed in order to calculate the fragmentation paths and interpret the experimental data. The experimental ionization energies of parent molecules [P]+ 8.91 ± 0.05, 8.85 ± 0.05, and 8.79 ± 0.05 eV and G3MP2 ionization energies (adiabatic) of 8.89, 8.88, and 8.81 eV were determined for valine, leucine, and isoleucine, respectively, as well as the experimental and theoretical threshold energies for dissociative ionization channels. The comparison of experimental data with calculations resulted in identification of the ions as well as the neutral fragments formed in the dissociative reactions. Around 15 mass/charge ratio fragments were identified from the mass spectra by comparison of experimental appearance energies with calculated reaction enthalpies for particular dissociative reactions.

Kα resonance fluorescence in Al, Ti, Cu and potential applications for X-ray sources

NASA Astrophysics Data System (ADS)

Nahar, Sultana N.; Pradhan, Anil K.

2015-04-01

The Kα resonance fluorescence (RFL) effect via photoabsorptions of inner shell electrons as the element goes through multiple ionization states is studied. We demonstrate that the resonances observed recently in Kα (1s-2p) fluorescence in aluminum plasmas by using a high-intensity X-ray free-electron laser [1] are basically K-shell resonances in hollow atoms going through multiple ionization states at resonant energies as predicted earlier for gold and iron ions [2]. These resonances are formed below the K-shell ionization edge and shift toward higher energies with ionization states, as observed. Fluorescence emission intensities depend on transition probabilities for each ionization stage of the given element for all possible Kα (1 s → 2 p) transition arrays. The present calculations for resonant photoabsorptions of Kα photons in Al have reproduced experimentally observed features. Resonant cross sections and absorption coefficients are presented for possible observation of Kα RFL in the resonant energy ranges of 4.5-5.0 keV for Ti ions and 8.0-8.7 keV for Cu ions respectively. We suggest that theoretically the Kα RFL process may be driven to enhance the Auger cycle by a twin-beam monochromatic X-ray source, tuned to the K-edge and Kα energies, with potential applications such as the development of narrow-band biomedical X-ray devices.

Toxicity of un-ionized ammonia, nitrite, and nitrate to juvenile bay scallops, Argopecten irradians irradians.

PubMed

Widman, James C; Meseck, Shannon L; Sennefelder, George; Veilleux, David J

2008-04-01

Juvenile bay scallops (7.2-26.4 mm) were exposed for 72 h to different concentrations of un-ionized ammonia, nitrite, or nitrate. Using the Trimmed Spearman Karber method, 50% lethal concentrations (LC(50)) and 95% confidence limits were calculated individually for each. Un-ionized ammonia concentrations above 1.0 mg N-NH(3)/L resulted in 100% scallop mortality within 72 h. The 72-h LC(50) for un-ionized ammonia was calculated at 0.43 mg N/L. At nitrite concentrations of 800 mg N/L or higher 100% mortality was observed. The 72-h LC(50) for nitrite was calculated at 345 mg N/L. Nitrate was the least toxic, with 100% mortality observed at a concentration of 5000 mg N/L. The calculated nitrate 72-h LC(50) was 4453 mg N/L. Our results indicate that un-ionized ammonia is the most lethal nitrogenous waste component to bay scallops.

Low-energy electron-impact single ionization of helium

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

Colgan, J.; Pindzola, M. S.; Childers, G.

2006-04-15

A study is made of low-energy electron-impact single ionization of ground-state helium. The time-dependent close-coupling method is used to calculate total integral, single differential, double differential, and triple differential ionization cross sections for impact electron energies ranging from 32 to 45 eV. For all quantities, the calculated cross sections are found to be in very good agreement with experiment, and for the triple differential cross sections, good agreement is also found with calculations made using the convergent close-coupling technique.

Theory of electron-impact ionization of atoms

NASA Astrophysics Data System (ADS)

Kadyrov, A. S.; Mukhamedzhanov, A. M.; Stelbovics, A. T.; Bray, I.

2004-12-01

The existing formulations of electron-impact ionization of a hydrogenic target suffer from a number of formal problems including an ambiguous and phase-divergent definition of the ionization amplitude. An alternative formulation of the theory is given. An integral representation for the ionization amplitude which is free of ambiguity and divergence problems is derived and is shown to have four alternative, but equivalent, forms well suited for practical calculations. The extension to amplitudes of all possible scattering processes taking place in an arbitrary three-body system follows. A well-defined conventional post form of the breakup amplitude valid for arbitrary potentials including the long-range Coulomb interaction is given. Practical approaches are based on partial-wave expansions, so the formulation is also recast in terms of partial waves and partial-wave expansions of the asymptotic wave functions are presented. In particular, expansions of the asymptotic forms of the total scattering wave function, developed from both the initial and the final state, for electron-impact ionization of hydrogen are given. Finally, the utility of the present formulation is demonstrated on some well-known model problems.

Relativistic features and time delay of laser-induced tunnel ionization

NASA Astrophysics Data System (ADS)

Yakaboylu, Enderalp; Klaiber, Michael; Bauke, Heiko; Hatsagortsyan, Karen Z.; Keitel, Christoph H.

2013-12-01

The electron dynamics in the classically forbidden region during relativistic tunnel ionization is investigated. The classical forbidden region in the relativistic regime is identified by defining a gauge-invariant total-energy operator. Introducing position-dependent energy levels inside the tunneling barrier, we demonstrate that the relativistic tunnel ionization can be well described by a one-dimensional intuitive picture. This picture predicts that, in contrast to the well-known nonrelativistic regime, the ionized electron wave packet arises with a momentum shift along the laser's propagation direction. This is compatible with results from a strong-field approximation calculation where the binding potential is assumed to be zero ranged. Further, the tunneling time delay, stemming from Wigner's definition, is investigated for model configurations of tunneling and compared with results obtained from the exact propagator. By adapting Wigner's time delay definition to the ionization process, the tunneling time is investigated in the deep-tunneling and in the near-threshold-tunneling regimes. It is shown that while in the deep-tunneling regime signatures of the tunneling time delay are not measurable at remote distance, they are detectable, however, in the latter regime.

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.

Direct Delta-MBPT(2) method for ionization potentials, electron affinities, and excitation energies using fractional occupation numbers

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

Beste, Ariana; Vazquez-Mayagoitia, Alvaro; Ortiz, J. Vincent

2013-01-01

A direct method (D-Delta-MBPT(2)) to calculate second-order ionization potentials (IPs), electron affinities (EAs), and excitation energies is developed. The Delta-MBPT(2) method is defined as the correlated extension of the Delta-HF method. Energy differences are obtained by integrating the energy derivative with respect to occupation numbers over the appropriate parameter range. This is made possible by writing the second-order energy as a function of the occupation numbers. Relaxation effects are fully included at the SCF level. This is in contrast to linear response theory, which makes the D-Delta-MBPT(2) applicable not only to single excited but also higher excited states. We showmore » the relationship of the D-Delta-MBPT(2) method for IPs and EAs to a second-order approximation of the effective Fock-space coupled-cluster Hamiltonian and a second-order electron propagator method. We also discuss the connection between the D-Delta-MBPT(2) method for excitation energies and the CIS-MP2 method. Finally, as a proof of principle, we apply our method to calculate ionization potentials and excitation energies of some small molecules. For IPs, the Delta-MBPT(2) results compare well to the second-order solution of the Dyson equation. For excitation energies, the deviation from EOM-CCSD increases when correlation becomes more important. When using the numerical integration technique, we encounter difficulties that prevented us from reaching the Delta-MBPT(2) values. Most importantly, relaxation beyond the Hartree Fock level is significant and needs to be included in future research.« less

TSAR, a new graph-theoretical approach to computational modeling of protein side-chain flexibility: modeling of ionization properties of proteins.

PubMed

Stroganov, Oleg V; Novikov, Fedor N; Zeifman, Alexey A; Stroylov, Viktor S; Chilov, Ghermes G

2011-09-01

A new graph-theoretical approach called thermodynamic sampling of amino acid residues (TSAR) has been elaborated to explicitly account for the protein side chain flexibility in modeling conformation-dependent protein properties. In TSAR, a protein is viewed as a graph whose nodes correspond to structurally independent groups and whose edges connect the interacting groups. Each node has its set of states describing conformation and ionization of the group, and each edge is assigned an array of pairwise interaction potentials between the adjacent groups. By treating the obtained graph as a belief-network-a well-established mathematical abstraction-the partition function of each node is found. In the current work we used TSAR to calculate partition functions of the ionized forms of protein residues. A simplified version of a semi-empirical molecular mechanical scoring function, borrowed from our Lead Finder docking software, was used for energy calculations. The accuracy of the resulting model was validated on a set of 486 experimentally determined pK(a) values of protein residues. The average correlation coefficient (R) between calculated and experimental pK(a) values was 0.80, ranging from 0.95 (for Tyr) to 0.61 (for Lys). It appeared that the hydrogen bond interactions and the exhaustiveness of side chain sampling made the most significant contribution to the accuracy of pK(a) calculations. Copyright © 2011 Wiley-Liss, Inc.

Argentate(i) and (iii) complexes as intermediates in silver-mediated cross-coupling reactions.

PubMed

Weske, Sebastian; Hardin, Richard A; Auth, Thomas; O'Hair, Richard A J; Koszinowski, Konrad; Ogle, Craig A

2018-04-30

Despite the potential of silver to mediate synthetically valuable cross-coupling reactions, the operating mechanisms have remained unknown. Here, we use a combination of rapid-injection NMR spectroscopy, electrospray-ionization mass spectrometry, and quantum chemical calculations to demonstrate that these transformations involve argentate(i) and (iii) complexes as key intermediates.

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.

Chemical trend of acceptor levels of Be, Mg, Zn, and Cd in GaAs, GaP, InP and GaN

NASA Astrophysics Data System (ADS)

Wang, Hao; Chen, An-Ban

2000-03-01

We are investigating the “shallow” acceptor levels in the III-nitride semiconductors theoretically. The k·p Hamiltonians and a model central-cell impurity potential have been used to evaluate the ordering of the ionization energies of impurities Be, Mg, Zn, and Cd in GaN. The impurity potential parameters were obtained from studying the same set of impurities in GaAs. These parameters were then transferred to the calculation for other hosts, leaving only one adjustable screening parameter for each host. This procedure was tested in GaP and InP and remarkably good results were obtained. When applied to GaN, this procedure produced a consistent set of acceptor levels with different k·p Hamiltonians. The calculated ionization energies for Be, Mg, Zn and Cd acceptors in GaN are respectively145, 156, 192, and 312 meV for the zincblende structure, and 229, 250, 320, and 510 meV for the wurtzite structure. These and other results will be discussed.

The collapse of a molecular cloud core to stellar densities using radiation non-ideal magnetohydrodynamics

NASA Astrophysics Data System (ADS)

Wurster, James; Bate, Matthew R.; Price, Daniel J.

2018-04-01

We present results from radiation non-ideal magnetohydrodynamics (MHD) calculations that follow the collapse of rotating, magnetized, molecular cloud cores to stellar densities. These are the first such calculations to include all three non-ideal effects: ambipolar diffusion, Ohmic resistivity, and the Hall effect. We employ an ionization model in which cosmic ray ionization dominates at low temperatures and thermal ionization takes over at high temperatures. We explore the effects of varying the cosmic ray ionization rate from ζcr = 10-10 to 10-16 s-1. Models with ionization rates ≳10-12 s-1 produce results that are indistinguishable from ideal MHD. Decreasing the cosmic ray ionization rate extends the lifetime of the first hydrostatic core up to a factor of 2, but the lifetimes are still substantially shorter than those obtained without magnetic fields. Outflows from the first hydrostatic core phase are launched in all models, but the outflows become broader and slower as the ionization rate is reduced. The outflow morphology following stellar core formation is complex and strongly dependent on the cosmic ray ionization rate. Calculations with high ionization rates quickly produce a fast (≈14 km s-1) bipolar outflow that is distinct from the first core outflow, but with the lowest ionization rate, a slower (≈3-4 km s-1) conical outflow develops gradually and seamlessly merges into the first core outflow.

Effect of the dynamic core-electron polarization of CO molecules on high-order harmonic generation

NASA Astrophysics Data System (ADS)

Le, Cam-Tu; Hoang, Van-Hung; Tran, Lan-Phuong; Le, Van-Hoang

2018-04-01

We theoretically investigate the influence of dynamic core-electron polarization (DCeP) of CO molecules on high-order harmonic generation (HHG) by solving the time-dependent Schrödinger equation (TDSE) within the single-active-electron (SAE) approximation. The effect of DCeP is shown to depend strongly on the molecular orientation angle θ . Particularly, compared to the calculations without DCeP, the inclusion of this effect gives rise to an enhancement of harmonic intensity at θ =0° when the electric field aligns along the O-C direction and to a suppression at θ =180° when the field heads in the opposite direction. Meanwhile, when the electric field is perpendicular to the molecular axis, the effect is almost insignificant. The phenomenon is thought to be linked to the ionization process. However, this picture is not completed yet. By solving the TDSE within the SAE approximation and conducting a classical simulation, we are able to obtain the ionization probability as well as the ionization rate and prove that HHG, in fact, receives a major contribution from electrons ionized at only a certain time interval, rather than throughout the whole pulse propagation. Including DCeP, the variation of the ionization rate in this interval highly correlates to that of the HHG intensity. To better demonstrate the origin of this manifestation, we also show the alternation DCeP makes on the effective potential that corresponds to the observed change in the ionization rate and consequently the HHG intensity. Our results confirm previous studies' observations and, more importantly, provide the missing physical explanation. With the role of DCeP now better understood for the entire range of the orientation angle, this effect can be handled more conveniently for calculating the HHG of other targets.

Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations

NASA Astrophysics Data System (ADS)

Vennila, P.; Govindaraju, M.; Venkatesh, G.; Kamal, C.

2016-05-01

Fourier transform - Infra red (FT-IR) and Fourier transform - Raman (FT-Raman) spectroscopic techniques have been carried out to analyze O-methoxy benzaldehyde (OMB) molecule. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT). The vibrational analysis of stable isomer of OMB has been carried out by FT-IR and FT-Raman in combination with theoretical method simultaneously. The first-order hyperpolarizability and the anisotropy polarizability invariant were computed by DFT method. The atomic charges, hardness, softness, ionization potential, electronegativity, HOMO-LUMO energies, and electrophilicity index have been calculated. The 13C and 1H Nuclear magnetic resonance (NMR) have also been obtained by GIAO method. Molecular electronic potential (MEP) has been calculated by the DFT calculation method. Electronic excitation energies, oscillator strength and excited states characteristics were computed by the closed-shell singlet calculation method.

Electron affinities and ionization energies of Cu and Ag delafossite compounds: A hybrid functional study

NASA Astrophysics Data System (ADS)

Miao, Mao-Sheng; Yarbro, Sam; Barton, Phillip T.; Seshadri, Ram

2014-01-01

Using density functional theory with a hybrid functional, we calculate the ionization energies and electron affinities of a series of delafossite compounds (AMO2: A =Cu, Ag; M =B, Al, Ga, In, Sc). The alignments of the valence band maximum and the conduction band minimum, which directly relate to the ionization energies and electron affinities, were obtained by calculations of supercell slab models constructed in a nonpolar orientation. Our calculations reveal that the ionization energy decreases with an increasing atomic number of group-III elements, and thus suggest an improved p-type doping propensity for heavier compounds. For keeping both a low ionization energy and a band gap of sufficient size, CuScO2 is superior to the Cu-based group-III delafossites. By analyzing the electronic structures, we demonstrate that the compositional trend of the ionization energies and electron affinities is the result of a combined effect of d-band broadening due to Cu(Ag)-Cu(Ag) coupling and a repositioning of the d-band center.

Runge-Lenz wave packet in multichannel Stark photoionization

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

Texier, F.

2005-01-01

In a previous slow photoionization experiment, modulations of ionization rings were manifested for Xe in a constant electric field. The present quantum calculation reveals that the modulation is an effect of the multichannel core scattering and of tunneling waves through the Coulomb-Stark potential barrier: the barrier reduces the number of oscillations that is observed relatively to the number of oscillations of the short range wave functions, and the nonhydrogenic core phase shifts modify the position of the ionization rings. We find a hidden difference, in the ionization process, for two close values of the energy depending on the resonance withmore » the barrier. The ionization intensity is interpreted as a Runge-Lenz wave packet; thus, we can relate the quantum modulation to the classical Coulomb-Stark trajectories. The Runge-Lenz wave packet differs from a usual temporal wave packet because its components are eigenstates of the Runge-Lenz vector z projection and its evolution is not temporal but spatial.« less

Observation of anisotropic interactions between metastable atoms and target molecules by two-dimensional collisional ionization electron spectroscopy

NASA Astrophysics Data System (ADS)

Kishimoto, Naoki; Ohno, Koichi

Excited metastable atoms colliding with target molecules can sensitively probe outer properties of molecules by chemi-ionization (Penning ionization) from molecular orbitals in the outer region, since metastable atoms cannot penetrate into the repulsive interaction wall around the molecules. By means of two-dimensional measurements using kinetic energy analysis of electrons combined with a velocity-resolved metastable beam, one can obtain information on the anisotropic interaction between the colliding particles without any control of orientation or alignment of target molecules. We have developed a classical trajectory method to calculate the collision energy dependence of partial ionization cross-sections (CEDPICS) on the anisotropic interaction potential energy surface, which has enabled us to study stereodynamics between metastable atoms and target molecules as well as the spatial distribution of molecular orbitals and electron ejection functions which have a relation with entrance and exit channels of the reaction. Based on the individual CEDPICS, the electronic structure of molecules can also be elucidated.

Distance geometry protocol to generate conformations of natural products to structurally interpret ion mobility-mass spectrometry collision cross sections.

PubMed

Stow, Sarah M; Goodwin, Cody R; Kliman, Michal; Bachmann, Brian O; McLean, John A; Lybrand, Terry P

2014-12-04

Ion mobility-mass spectrometry (IM-MS) allows the separation of ionized molecules based on their charge-to-surface area (IM) and mass-to-charge ratio (MS), respectively. The IM drift time data that is obtained is used to calculate the ion-neutral collision cross section (CCS) of the ionized molecule with the neutral drift gas, which is directly related to the ion conformation and hence molecular size and shape. Studying the conformational landscape of these ionized molecules computationally provides interpretation to delineate the potential structures that these CCS values could represent, or conversely, structural motifs not consistent with the IM data. A challenge in the IM-MS community is the ability to rapidly compute conformations to interpret natural product data, a class of molecules exhibiting a broad range of biological activity. The diversity of biological activity is, in part, related to the unique structural characteristics often observed for natural products. Contemporary approaches to structurally interpret IM-MS data for peptides and proteins typically utilize molecular dynamics (MD) simulations to sample conformational space. However, MD calculations are computationally expensive, they require a force field that accurately describes the molecule of interest, and there is no simple metric that indicates when sufficient conformational sampling has been achieved. Distance geometry is a computationally inexpensive approach that creates conformations based on sampling different pairwise distances between the atoms within the molecule and therefore does not require a force field. Progressively larger distance bounds can be used in distance geometry calculations, providing in principle a strategy to assess when all plausible conformations have been sampled. Our results suggest that distance geometry is a computationally efficient and potentially superior strategy for conformational analysis of natural products to interpret gas-phase CCS data.

Distance Geometry Protocol to Generate Conformations of Natural Products to Structurally Interpret Ion Mobility-Mass Spectrometry Collision Cross Sections

PubMed Central

2015-01-01

Ion mobility-mass spectrometry (IM-MS) allows the separation of ionized molecules based on their charge-to-surface area (IM) and mass-to-charge ratio (MS), respectively. The IM drift time data that is obtained is used to calculate the ion-neutral collision cross section (CCS) of the ionized molecule with the neutral drift gas, which is directly related to the ion conformation and hence molecular size and shape. Studying the conformational landscape of these ionized molecules computationally provides interpretation to delineate the potential structures that these CCS values could represent, or conversely, structural motifs not consistent with the IM data. A challenge in the IM-MS community is the ability to rapidly compute conformations to interpret natural product data, a class of molecules exhibiting a broad range of biological activity. The diversity of biological activity is, in part, related to the unique structural characteristics often observed for natural products. Contemporary approaches to structurally interpret IM-MS data for peptides and proteins typically utilize molecular dynamics (MD) simulations to sample conformational space. However, MD calculations are computationally expensive, they require a force field that accurately describes the molecule of interest, and there is no simple metric that indicates when sufficient conformational sampling has been achieved. Distance geometry is a computationally inexpensive approach that creates conformations based on sampling different pairwise distances between the atoms within the molecule and therefore does not require a force field. Progressively larger distance bounds can be used in distance geometry calculations, providing in principle a strategy to assess when all plausible conformations have been sampled. Our results suggest that distance geometry is a computationally efficient and potentially superior strategy for conformational analysis of natural products to interpret gas-phase CCS data. PMID:25360896

Electron impact ionization of metastable 2P-state hydrogen atoms in the coplanar geometry

NASA Astrophysics Data System (ADS)

Dhar, S.; Nahar, N.

Triple differential cross sections (TDCS) for the ionization of metastable 2P-state hydrogen atoms by electrons are calculated for various kinematic conditions in the asymmetric coplanar geometry. In this calculation, the final state is described by a multiple-scattering theory for ionization of hydrogen atoms by electrons. Results show qualitative agreement with the available experimental data and those of other theoretical computational results for ionization of hydrogen atoms from ground state, and our first Born results. There is no available other theoretical results and experimental data for ionization of hydrogen atoms from the 2P state. The present study offers a wide scope for the experimental study for ionization of hydrogen atoms from the metastable 2P state.

Coronal Element Abundances of the Post-Common Envelope Binary V471 Tauri with ASCA

NASA Technical Reports Server (NTRS)

Still, Martin; Hussain, Gaitee; White, Nicholas E. (Technical Monitor)

2002-01-01

We report on ASCA observations of the coronally active companion star in the post-common envelope binary V471 Tau. While it would be prudent to check the following results with grating spectroscopy, we find that a single-temperature plasma model does not fit the data. Two temperature models with variable abundances indicate that Fe is underabundant compared to the Hyades photospheric mean, whereas, the high first ionization potential element Ne is overabundant. This is indicative of the inverse first ionization effect, believed to result from the fractionation of ionized material by the magnetic field in the upper atmosphere of the star. Evolutionary calculations indicate that there should be no peculiar abundances on the companion star resulting from the common envelope epoch. Indeed, we find no evidence for peculiar abundances, although uncertainties are high.

Equations of state and transport properties of mixtures in the warm dense regime

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

Hou, Yong; Dai, Jiayu; Kang, Dongdong

2015-02-15

We have performed average-atom molecular dynamics to simulate the CH and LiH mixtures in the warm dense regime, and obtained equations of state and the ionic transport properties. The electronic structures are calculated by using the modified average-atom model, which have included the broadening of energy levels, and the ion-ion pair potentials of mixtures are constructed based on the temperature-dependent density functional theory. The ionic transport properties, such as ionic diffusion and shear viscosity, are obtained through the ionic velocity correlation functions. The equations of state and transport properties for carbon, hydrogen and lithium, hydrogen mixtures in a wide regionmore » of density and temperature are calculated. Through our computing the average ionization degree, average ion-sphere diameter and transition properties in the mixture, it is shown that transport properties depend not only on the ionic mass but also on the average ionization degree.« less

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.

Solar irradiance changes and photobiological effects at earth's surface following astrophysical ionizing radiation events.

PubMed

Thomas, Brian C; Neale, Patrick J; Snyder, Brock R

2015-03-01

Astrophysical ionizing radiation events have been recognized as a potential threat to life on Earth, primarily through depletion of stratospheric ozone and subsequent increase in surface-level solar ultraviolet radiation. Simulations of the atmospheric effects of a variety of events (such as supernovae, gamma-ray bursts, and solar proton events) have been previously published, along with estimates of biological damage at Earth's surface. In this work, we employed the Tropospheric Ultraviolet and Visible (TUV) radiative transfer model to expand and improve calculations of surface-level irradiance and biological impacts following an ionizing radiation event. We considered changes in surface-level UVB, UVA, and photosynthetically active radiation (visible light) for clear-sky conditions and fixed aerosol parameter values. We also considered a wide range of biological effects on organisms ranging from humans to phytoplankton. We found that past work overestimated UVB irradiance but that relative estimates for increase in exposure to DNA-damaging radiation are still similar to our improved calculations. We also found that the intensity of biologically damaging radiation varies widely with organism and specific impact considered; these results have implications for biosphere-level damage following astrophysical ionizing radiation events. When considering changes in surface-level visible light irradiance, we found that, contrary to previous assumptions, a decrease in irradiance is only present for a short time in very limited geographical areas; instead we found a net increase for most of the modeled time-space region. This result has implications for proposed climate changes associated with ionizing radiation events.

Shining a light on galactic outflows: photoionized outflows

NASA Astrophysics Data System (ADS)

Chisholm, John; Tremonti, Christy A.; Leitherer, Claus; Chen, Yanmei; Wofford, Aida

2016-04-01

We study the ionization structure of galactic outflows in 37 nearby, star-forming galaxies with the Cosmic Origins Spectrograph on the Hubble Space Telescope. We use the O I, Si II, Si III, and Si IV ultraviolet absorption lines to characterize the different ionization states of outflowing gas. We measure the equivalent widths, line widths, and outflow velocities of the four transitions, and find shallow scaling relations between them and galactic stellar mass and star formation rate. Regardless of the ionization potential, lines of similar strength have similar velocities and line widths, indicating that the four transitions can be modelled as a comoving phase. The Si equivalent width ratios (e.g. Si IV/Si II) have low dispersion, and little variation with stellar mass; while ratios with O I and Si vary by a factor of 2 for a given stellar mass. Photoionization models reproduce these equivalent width ratios, while shock models under predict the relative amount of high ionization gas. The photoionization models constrain the ionization parameter (U) between -2.25 < log (U) < -1.5, and require that the outflow metallicities are greater than 0.5 Z⊙. We derive ionization fractions for the transitions, and show that the range of ionization parameters and stellar metallicities leads to a factor of 1.15-10 variation in the ionization fractions. Historically, mass outflow rates are calculated by converting a column density measurement from a single metal ion into a total hydrogen column density using an ionization fraction, thus mass outflow rates are sensitive to the assumed ionization structure of the outflow.

Tight-binding molecular-dynamics study of point defects in GaAs

NASA Astrophysics Data System (ADS)

Seong, Hyangsuk; Lewis, Laurent J.

1995-08-01

Tight-binding molecular-dynamics simulations at 0 K have been performed in order to study the effect of defects (vacancies and antisites) in different states of charge on the electronic and structural properties of GaAs. Relaxations are fully included in the model, and for each defect we calculate the local atomic structure, the volume change upon relaxing, the formation energy (including chemical potential contributions), and the ionization levels. We find Ga vacancies to relax by an amount which is independent of the state of charge, consistent with positron lifetime measurements. Our calculations also predict Ga vacancies to exhibit a negative-U effect, and to assume a triply negative charge state for most values of the electron chemical potential. The relaxation of As vacancies, on the contrary, depends sensitively on the state of charge. The model confirms the two experimentally observed ionization levels for this defect, just below the conduction-band minimum. Likewise, Ga antisites exhibit large relaxations. In fact, in the neutral state, relaxation is so large that it leads to a ``broken-bond'' configuration, in excellent accord with the first-principles calculations of Zhang and Chadi [Phys. Rev. Lett. 64, 1789 (1990)]. This system also exhibits a negative-U effect, for values of the electron chemical potential near midgap. For As antisites, we find only a weak relaxation, independent of the charge. The model predicts the neutral state of the defect to be the ground state for values of the electron chemical potential near and above midgap, which supports the view that the EL2 defect is a neutral As antisite. Upon comparing the formation energies of the various defects we finally find that, for all values of the atomic chemical potentials, antisites are most likely to occur than vacancies.

Vibrational spectroscopic and structural investigations on fullerene: A DFT approach

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

Christy, P. Anto; Premkumar, S.; Asath, R. Mohamed

2016-05-06

The molecular structure of fullerene (C{sub 60}) molecule was optimized by the DFT/B3LYP method with 6-31G and 6-31G(d,p) basis sets using Gaussian 09 program. The vibrational frequencies were calculated for the optimized molecular structure of the molecule. The calculated vibrational frequencies confirm that the molecular structure of the molecule was located at the minimum energy potential energy surface. The calculated vibrational frequencies were assigned on the basis of functional group analysis and also confirmed using the GaussView 05 software. The frontier molecular orbitals analysis was carried out. The FMOs related molecular properties were predicted. The higher ionization potential, higher electronmore » affinity, higher softness, lower band gap energy and lower hardness values were obtained, which confirm that the fullerene molecule has a higher molecular reactivity. The Mulliken atomic charge distribution of the molecule was also calculated. Hence, these results play an important role due to its potential applications as drug delivery devices.« less

Evaluation of antioxidant activity and electronic structure of aspirin and paracetamol

NASA Astrophysics Data System (ADS)

Motozaki, W.; Nagatani, Y.; Kimura, Y.; Endo, K.; Takemura, T.; Kurmaev, E. Z.; Moewes, A.

2011-01-01

We present a study of electronic structure, chemical bonding, and antioxidant activity of phenolic antioxidants (aspirin and paracetamol). X-ray photoelectron and emission spectra of the antioxidants have been simulated by deMon density functional theory (DFT) calculations of the molecules. The chemical bonding of aspirin is characterized by the formation of oxygen 'lone-pair' π-orbitals which can neutralize free radicals and thus be related to antioxidant properties of the drug. In the case of paracetamol the additional nitrogen 'lone pair' is formed which can explain toxicity of the drug. We propose an evaluation method of antioxidant activity based on the relationship between experimental half-wave oxidation potential ( Ep/2 ) and calculated ionization potentials ( IP) by the DFT calculations, and can conclude that paracetamol has the higher antioxidant activity than aspirin.

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

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

Jacovella, U.; Holland, D. M. P.; Boyé-Péronne, S.

2015-07-21

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydbergmore » states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger molecules.« less

Scaling of the low-energy structure in above-threshold ionization in the tunneling regime: theory and experiment.

PubMed

Guo, L; Han, S S; Liu, X; Cheng, Y; Xu, Z Z; Fan, J; Chen, J; Chen, S G; Becker, W; Blaga, C I; DiChiara, A D; Sistrunk, E; Agostini, P; DiMauro, L F

2013-01-04

A calculation of the second-order (rescattering) term in the S-matrix expansion of above-threshold ionization is presented for the case when the binding potential is the unscreened Coulomb potential. Technical problems related to the divergence of the Coulomb scattering amplitude are avoided in the theory by considering the depletion of the atomic ground state due to the applied laser field, which is well defined and does not require the introduction of a screening constant. We focus on the low-energy structure, which was observed in recent experiments with a midinfrared wavelength laser field. Both the spectra and, in particular, the observed scaling versus the Keldysh parameter and the ponderomotive energy are reproduced. The theory provides evidence that the origin of the structure lies in the long-range Coulomb interaction.

Following electron impact excitations of Rn, Ra, Th, U and Pu single atom L sub-shells ionization cross section calculations by using Lotz’s equation

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

Ayinol, M., E-mail: aydinolm@dicle.edu.tr; Aydeniz, D., E-mail: daydeniz@hotmail.com

L shell ionization cross section and L{sub i} subshells ionization cross sections of Rn, Ra, Th, U, Pu atoms calculated. For each of atoms, ten different electron impact energy values (E{sub o}) are used. Calculations carried out by using Lotz equation in Matlab. First, calculations done for non-relativistic case by using non-relativistic Lotz equation then repeated with relativistic Lotz equation. σ{sub L} total and σ{sub Li}(i = 1,2,3) subshells ionisation cross section values obtained for E{sub o} values in the energy range of E{sub Li}

Electron emission from transfer ionization reaction in 30 keV amu‑1 He 2+ on Ar collision

NASA Astrophysics Data System (ADS)

Amaya-Tapia, A.; Antillón, A.; Estrada, C. D.

2018-06-01

A model is presented that describes the transfer ionization process in H{e}2++Ar collision at a projectile energy of 30 keV amu‑1. It is based on a semiclassical independent-particle close-coupling method that yields a reasonable agreement between calculated and experimental values of the total single-ionization and single-capture cross sections. It is found that the transfer ionization reaction is predominantly carried out through simultaneous capture and ionization, rather than by sequential processes. The transfer-ionization differential cross section in energy that is obtained satisfactorily reproduces the global behavior of the experimental data. Additionally, the probabilities of capture and ionization as function of the impact parameter for H{e}2++A{r}+ and H{e}++A{r}+ collisions are calculated, as far as we know, for the first time. The results suggest that the model captures essential elements that describe the two-electron transfer ionization process and could be applied to systems and processes of two electrons.

Continuum Lowering and Fermi-Surface Rising in Strongly Coupled and Degenerate Plasmas

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

Hu, S. X.

Here, continuum lowering is a well-known and important physics concept that describes the ionization potential depression (IPD) in plasmas caused by thermal-/pressure-induced ionization of outer-shell electrons. The existing IPD models are often used to characterize plasma conditions and to gauge opacity calculations. Recent precision measurements have revealed deficits in our understanding of continuum lowering in dense hot plasmas. However, these investigations have so far been limited to IPD in strongly coupled but nondegenerate plasmas. Here, we report a first-principles study of the K-edge shifting in both strongly coupled and fully degenerate carbon plasmas, with quantum molecular dynamics (QMD) calculations basedmore » on the all-electron density-functional theory (DFT). The resulted K-edge shifting versus plasma density, as a probe to the continuum lowering and the Fermi-surface rising, is found to be significantly different from predictions of existing IPD models. In contrast, a simple model of “single atom in box” (SAIB), developed in this work, accurately predicts K-edge locations as what ab-initio calculations provide.« less

Continuum Lowering and Fermi-Surface Rising in Strongly Coupled and Degenerate Plasmas

DOE PAGES

Hu, S. X.

2017-08-10

Here, continuum lowering is a well-known and important physics concept that describes the ionization potential depression (IPD) in plasmas caused by thermal-/pressure-induced ionization of outer-shell electrons. The existing IPD models are often used to characterize plasma conditions and to gauge opacity calculations. Recent precision measurements have revealed deficits in our understanding of continuum lowering in dense hot plasmas. However, these investigations have so far been limited to IPD in strongly coupled but nondegenerate plasmas. Here, we report a first-principles study of the K-edge shifting in both strongly coupled and fully degenerate carbon plasmas, with quantum molecular dynamics (QMD) calculations basedmore » on the all-electron density-functional theory (DFT). The resulted K-edge shifting versus plasma density, as a probe to the continuum lowering and the Fermi-surface rising, is found to be significantly different from predictions of existing IPD models. In contrast, a simple model of “single atom in box” (SAIB), developed in this work, accurately predicts K-edge locations as what ab-initio calculations provide.« less

Quantum statistical mechanics of dense partially ionized hydrogen

NASA Technical Reports Server (NTRS)

Dewitt, H. E.; Rogers, F. J.

1972-01-01

The theory of dense hydrogen plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. The statistical mechanical calculation of the plasma equation of state is intended for stellar interiors. The general approach is extended to the calculation of the equation of state of the outer layers of large planets.

Direct Simulation of Reentry Flows with Ionization

NASA Technical Reports Server (NTRS)

Carlson, Ann B.; Hassan, H. A.

1989-01-01

The Direct Simulation Monte Carlo (DSMC) method is applied in this paper to the study of rarefied, hypersonic, reentry flows. The assumptions and simplifications involved with the treatment of ionization, free electrons and the electric field are investigated. A new method is presented for the calculation of the electric field and handling of charged particles with DSMC. In addition, a two-step model for electron impact ionization is implemented. The flow field representing a 10 km/sec shock at an altitude of 65 km is calculated. The effects of the new modeling techniques on the calculation results are presented and discussed.

Near-Threshold Ionization of Argon by Positron Impact

NASA Astrophysics Data System (ADS)

Babij, T. J.; Machacek, J. R.; Murtagh, D. J.; Buckman, S. J.; Sullivan, J. P.

2018-03-01

The direct single-ionization cross section for Ar by positron impact has been measured in the region above the first ionization threshold. These measurements are compared to semiclassical calculations which give rise to a power law variation of the cross section in the threshold region. The experimental results appear to be in disagreement with extensions to the Wannier theory applied to positron impact ionization, with a smaller exponent than that calculated by most previous works. In fact, in this work, we see no difference in threshold behavior between the positron and electron cases. Possible reasons for this discrepancy are discussed.

Cascade Model of Ionization Multiplication of Electrons in Glow Discharge Plasma

NASA Astrophysics Data System (ADS)

Romanenko, V. A.; Solodky, S. A.; Kudryavtsev, A. A.; Suleymanov, I. A.

1996-10-01

For determination of EDF in non-uniform fields a Monte-Carlo simulation(Tran Ngoc An et al., J.Phys.D: Appl. Phys. 10, 2317 (1977))^,(J.P. Boeuf et al., Phys.D: Appl.Phys. 15, 2169 (1982)) is applied. As alternative multi-beam cascade model(H.B. Valentini, Contrib.Plasma Phys. 27, 331 (1987)) is offered. Our model eliminates defects of that model and enables to determine EDF of low pressure plasma in non-uniform fields. A cascade model (with EDF dividing in monoenergetic electron groups) for arbitrary electric potential profile was used. Modeling was carried out for electron forward scattering only, constant electron mean free path; ionization was considered only. The equation system was solved for the region with kinetic energies more than ionization energy. The boundary conditions (on ionization energy curve) take into account electron transitions from higher-lying level in the less than ionization energy region and secondary electron production. The problem solution in analytical functions was obtained. The insertion of additional processes does not make significant difficulties. EDF and electrokinetical parameters in helium from numerical calculations are well agreed with above-mentioned authors. Work was carried out under RFFI (project N 96-02-18417) support.

Modeling of Microplasmas with Nano-Engineered Electrodes

NASA Astrophysics Data System (ADS)

Macheret, Sergey; Tholeti, Siva Shashank; Alexeenko, Alina

2015-09-01

Microplasmas can potentially be used as unique tunable dielectrics for reconfigurable radio-frequency systems, if electron densities of 1010-1012 cm-3 can be sustained in cavities smaller than 100 micron. However, for low loss tangent, gas pressures below 10 mTorr would be required, whereas the physics of electron impact ionization dictates the pd scaling so that microplasmas must operate at high gas pressures, hundreds of Torr, and also high voltages. We analyze a new principle of plasma generation that goes well beyond the pd scaling by eliminating electron impact ionization. In the new concept, electrons are generated at the cathode by field emission from nanotubes, and ions are independently produced in field ionization at atomically-sharp tips on the anode. The electrons and ions then move in the opposite directions, mix, and create a plasma. The low pressure results in collisionless motion with no electron-impact ionization. One-dimensional PIC/MCC calculations show that emitters such as carbon nanotubes placed sparsely on the cathode, combined with field ionization nanorods at the anode, can indeed ensure steady-state electron densities of up to 1012 cm-3 at gas pressure lower than 10 mTorr with only 50-100 Volts applied cross a 40-50 μm gap.

The absorption of energetic electrons by molecular hydrogen gas

NASA Technical Reports Server (NTRS)

Cravens, T. E.; Victor, G. A.; Dalgarno, A.

1975-01-01

The processes by which energetic electrons lose energy in a weakly ionized gas of molecular hydrogen are analyzed, and calculations are carried out taking into account the discrete nature of the excitation processes. The excitation, ionization, and heating efficiencies are computed for electrons with energies up to 100 eV absorbed in a gas with fractional ionizations up to 0.01, and the mean energy per pair of neutral hydrogen atoms is calculated.

Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations.

PubMed

Lee, Edmond P F; Wright, Timothy G

2005-10-08

The heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) have been studied by high-level ab initio calculations. The RCCSD(T) method has been employed, combined with large flexible valence basis sets. All-electron basis sets are used for potassium and sulfur, with effective core potentials being used for the other metals, describing the core electrons. Potential-energy curves are calculated for the lowest two neutral and cationic states: all neutral monosulfide species have a (2)Pi ground state, in contrast with the alkali-metal monoxide species, which undergo a change in the electronic ground state from (2)Pi to (2)Sigma(+) as the group is descended. In the cases of KS, RbS, and CsS, spin-orbit curves are also calculated. We also calculate potential-energy curves for the lowest (3)Sigma(-) and (3)Pi states of the cations. From the potential-energy curves, spectroscopic constants are derived, and for KS the spectroscopic results are compared to experimental spectroscopic values. Ionization energies, dissociation energies, and heats of formation are also calculated; for KS, we explore the effects of relativity and basis set extrapolation on these values.

Low-lying electronic states of Li 2+ and Li 2-

NASA Astrophysics Data System (ADS)

Konowalow, Daniel D.; Fish, James L.

1984-02-01

Potential curves for the eight lowest lying electronic states of Li2+ and the two lowest-lying states of Li2- are obtained by valence configuration calculations which-utilize an effective core potential. The calculated ionization potential of the ground state of Li2 is found to b. 5.16 eV and its electron affinity is 0.429 eV. Both values are in excellent agreement with recent experimental values and with value deduced from other high quality ab initio quantum mechanical treatments. When our potential curve for the Li2+(12Σg+ state, is corrected for the core-valence correlation error we obtain spectroscopic constants which agree nicely with the experimental values of Bernheim, Gold and Tipton (BGT). For example, we findDe = 10460 ± 140 cm-1 while BGT reportDe = 10469 ± 6 cm-1.

Electron-impact Ionization of P-like Ions Forming Si-like Ions

NASA Astrophysics Data System (ADS)

Kwon, D.-H.; Savin, D. W.

2014-03-01

We have calculated electron-impact ionization (EII) for P-like systems from P to Zn15 + forming Si-like ions. The work was performed using the flexible atomic code (FAC) which is based on a distorted-wave approximation. All 3l → nl' (n = 3-35) excitation-autoionization (EA) channels near the 3p direct ionization threshold and 2l → nl' (n = 3-10) EA channels at the higher energies are included. Close attention has been paid to the detailed branching ratios. Our calculated total EII cross sections are compared both with previous FAC calculations, which omitted many of these EA channels, and with the available experimental results. Moreover, for Fe11 +, we find that part of the remaining discrepancies between our calculations and recent measurements can be accounted for by the inclusion of the resonant excitation double autoionization process. Lastly, at the temperatures where each ion is predicted to peak in abundances in collisional ionization equilibrium, the Maxwellian rate coefficients derived from our calculations differ by 50%-7% from the previous FAC rate coefficients, with the difference decreasing with increasing charge.

Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons - Effect of ionization

NASA Technical Reports Server (NTRS)

De Frees, D. J.; Miller, M. D.; Talbi, D.; Pauzat, F.; Ellinger, Y.

1993-01-01

In order to test the hypothesis of ionized PAHs as possible carriers of the UIR bands, we realized a computational exploration on selected PAHs of small dimension in order to identify which changes ionization would induce on their IR spectra. In this study we performed ab initio calculations of the spectra of neutral and positively ionized naphthalene, anthracene, and pyrene. The results are significantly important. The frequencies in the cations are slightly shifted with respect to the neutral species, but no general conclusion can be reached from the three molecules considered. By contrast, the relative intensities of most vibrations are strongly affected by ionization, leading to a much better agreement between the calculated CH/CC vibration intensity ratios and those deduced from observations.

Two- and three-photon ionization of hydrogen and lithium

NASA Technical Reports Server (NTRS)

Chang, T. N.; Poe, R. T.

1977-01-01

We present the detailed result of a calculation on two- and three-photon ionization of hydrogen and lithium based on a recently proposed calculational method. Our calculation has demonstrated that this method is capable of retaining the numerical advantages enjoyed by most of the existing calculational methods and, at the same time, circumventing their limitations. In particular, we have concentrated our discussion on the relative contribution from the resonant and nonresonant intermediate states.

Structural evolution study of 1-2 nm gold clusters

NASA Astrophysics Data System (ADS)

Beltrán, M. R.; Suárez Raspopov, R.; González, G.

2011-12-01

We have explored lowest energy minima structures of gold atom clusters both, charged and neutral (Aun^{ν}νn with n = 20, 28, 34, 38, 55, 75, 101, 146, 147, 192, 212 atoms and ν = 0, ±1). The structures have been obtained from first principles generalized gradient approximation, density functional theory (DFT) calculations based on norm-conserving pseudopotentials and numerical atomic basis sets. We have found two new disordered or defective isomers lower in energy than their ordered counterparts for n = 101, 147. The purpose of this work is to systematically study the difference between the electronic properties of the two lowest ordered and disordered isomers for each size. Our results agree with previous first principle calculations and with some recent experimental results (Au20 and Au101). For each case we report total energies, binding energies, ionization potentials, electron affinities, density of states, highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, Housdorff chirality measure index and their simulated image in a high resolution transmission electron microscopy (HRTEM). The calculated properties of the two low lying (ordered and disordered) isomers show clear differences as to be singled out in a suitable experimental setting. An extensive discussion on the evolution with size of the cohesive energy, the ionization potentials, the electron affinities, the HOMO-LUMO gaps and their index of chirality to determine the crossover between them is given.

First principles study of structural, electronic and magnetic properties of SnGe n (0, ±1) ( n = 1–17) clusters

NASA Astrophysics Data System (ADS)

Djaadi, Soumaia; Eddine Aiadi, Kamal; Mahtout, Sofiane

2018-04-01

The structures, relative stability and magnetic properties of pure Ge n +1, neutral cationic and anionic SnGe n (n = 1–17) clusters have been investigated by using the first principles density functional theory implemented in SIESTA packages. We find that with the increasing of cluster size, the Ge n +1 and SnGe n (0, ±1) clusters tend to adopt compact structures. It has been also found that the Sn atom occupied a peripheral position for SnGe n clusters when n < 12 and occupied a core position for n > 12. The structural and electronic properties such as optimized geometries, fragmentation energy, binding energy per atom, HOMO–LUMO gaps and second-order differences in energy of the pure Ge n +1 and SnGe n clusters in their ground state are calculated and analyzed. All isomers of neutral SnGe n clusters are generally nonmagnetic except for n = 1 and 4, where the total spin magnetic moments is 2μ b. The total (DOS) and partial density of states of these clusters have been calculated to understand the origin of peculiar magnetic properties. The cluster size dependence of vertical ionization potentials, vertical electronic affinities, chemical hardness, adiabatic electron affinities and adiabatic ionization potentials have been calculated and discussed.

Transition energy and potential energy curves for ionized inner-shell states of CO, O2 and N 2 calculated by several inner-shell multiconfigurational approaches.

PubMed

Moura, Carlos E V de; Oliveira, Ricardo R; Rocha, Alexandre B

2013-05-01

Potential energy curves and inner-shell ionization energies of carbon monoxide, oxygen and nitrogen molecules were calculated using several forms of the inner-shell multiconfigurational self-consistent field (IS-MCSCF) method-a recently proposed protocol to obtain specifically converged inner-shell states at this level. The particular forms of the IS-MCSCF method designated IS-GVB-PP, IS-FVBL and IS-CASSCF stand for perfect pairing generalized valence bond, full valence bond-like MCSCF and complete active space self consistent field, respectively. A comparison of these different versions of the IS-MCSCF method was carried out for the first time. The results indicate that inner-shell states are described accurately even for the simplest version of the method (IS-GVB-PP). Dynamic correlation was recovered by multireference configuration interaction or multireference perturbation theory. For molecules not having equivalent atoms, all methods led to comparable and accurate transition energies. For molecules with equivalent atoms, the most accurate results were obtained by multireference perturbation theory. Scalar relativistic effects were accounted for using the Douglas-Kroll-Hess Hamiltonian.

The importance of the external potential on group electronegativity.

PubMed

Leyssens, Tom; Geerlings, Paul; Peeters, Daniel

2005-11-03

The electronegativity of groups placed in a molecular environment is obtained using CCSD calculations of the electron affinity and ionization energy. A point charge model is used as an approximation of the molecular environment. The electronegativity values obtained in the presence of a point charge model are compared to the isolated group property to estimate the importance of the external potential on the group's electronegativity. The validity of the "group in molecule" electronegativities is verified by comparing EEM (electronegativity equalization method) charge transfer values to the explicitly calculated natural population analysis (NPA) ones, as well as by comparing the variation in electronegativity between the isolated functional group and the functional group in the presence of a modeled environment with the variation based on a perturbation expansion of the chemical potential.

Theoretical study of (e, 2e) process of atomic and molecular targets*

NASA Astrophysics Data System (ADS)

Houamer, Salim; Chinoune, Mehdi; Cappello, Claude Dal

2017-01-01

Triple differential ionization cross sections (TDCSs) by electron impact are calculated for some atomic and molecular targets by using several models where Post Collisional Interaction (PCI) is taken in account. We also investigate the effect of the short range potential and describe the ejected electron either by a Coulomb wave or by a distorted wave. Significant differences are observed between these models. A better agreement with experimental data is achieved when the short range potential and distortion effects are included.

An X-Ray Analysis Database of Photoionization Cross Sections Including Variable Ionization

NASA Technical Reports Server (NTRS)

Wang, Ping; Cohen, David H.; MacFarlane, Joseph J.; Cassinelli, Joseph P.

1997-01-01

Results of research efforts in the following areas are discussed: review of the major theoretical and experimental data of subshell photoionization cross sections and ionization edges of atomic ions to assess the accuracy of the data, and to compile the most reliable of these data in our own database; detailed atomic physics calculations to complement the database for all ions of 17 cosmically abundant elements; reconciling the data from various sources and our own calculations; and fitting cross sections with functional approximations and incorporating these functions into a compact computer code.Also, efforts included adapting an ionization equilibrium code, tabulating results, and incorporating them into the overall program and testing the code (both ionization equilibrium and opacity codes) with existing observational data. The background and scientific applications of this work are discussed. Atomic physics cross section models and calculations are described. Calculation results are compared with available experimental data and other theoretical data. The functional approximations used for fitting cross sections are outlined and applications of the database are discussed.

Comparison of depth-dose distributions of proton therapeutic beams calculated by means of logical detectors and ionization chamber modeled in Monte Carlo codes

NASA Astrophysics Data System (ADS)

Pietrzak, Robert; Konefał, Adam; Sokół, Maria; Orlef, Andrzej

2016-08-01

The success of proton therapy depends strongly on the precision of treatment planning. Dose distribution in biological tissue may be obtained from Monte Carlo simulations using various scientific codes making it possible to perform very accurate calculations. However, there are many factors affecting the accuracy of modeling. One of them is a structure of objects called bins registering a dose. In this work the influence of bin structure on the dose distributions was examined. The MCNPX code calculations of Bragg curve for the 60 MeV proton beam were done in two ways: using simple logical detectors being the volumes determined in water, and using a precise model of ionization chamber used in clinical dosimetry. The results of the simulations were verified experimentally in the water phantom with Marcus ionization chamber. The average local dose difference between the measured relative doses in the water phantom and those calculated by means of the logical detectors was 1.4% at first 25 mm, whereas in the full depth range this difference was 1.6% for the maximum uncertainty in the calculations less than 2.4% and for the maximum measuring error of 1%. In case of the relative doses calculated with the use of the ionization chamber model this average difference was somewhat greater, being 2.3% at depths up to 25 mm and 2.4% in the full range of depths for the maximum uncertainty in the calculations of 3%. In the dose calculations the ionization chamber model does not offer any additional advantages over the logical detectors. The results provided by both models are similar and in good agreement with the measurements, however, the logical detector approach is a more time-effective method.

Ionizing radiation calculations and comparisons with LDEF data

NASA Technical Reports Server (NTRS)

Armstrong, T. W.; Colborn, B. L.; Watts, J. W., Jr.

1992-01-01

In conjunction with the analysis of LDEF ionizing radiation dosimetry data, a calculational program is in progress to aid in data interpretation and to assess the accuracy of current radiation models for future mission applications. To estimate the ionizing radiation environment at the LDEF dosimeter locations, scoping calculations for a simplified (one dimensional) LDEF mass model were made of the primary and secondary radiations produced as a function of shielding thickness due to trapped proton, galactic proton, and atmospheric (neutron and proton cosmic ray albedo) exposures. Preliminary comparisons of predictions with LDEF induced radioactivity and dose measurements were made to test a recently developed model of trapped proton anisotropy.

Monte Carlo Simulations of Electron Energy-Loss Spectra with the Addition of Fine Structure from Density Functional Theory Calculations.

PubMed

Attarian Shandiz, Mohammad; Guinel, Maxime J-F; Ahmadi, Majid; Gauvin, Raynald

2016-02-01

A new approach is presented to introduce the fine structure of core-loss excitations into the electron energy-loss spectra of ionization edges by Monte Carlo simulations based on an optical oscillator model. The optical oscillator strength is refined using the calculated electron energy-loss near-edge structure by density functional theory calculations. This approach can predict the effects of multiple scattering and thickness on the fine structure of ionization edges. In addition, effects of the fitting range for background removal and the integration range under the ionization edge on signal-to-noise ratio are investigated.

Full-Scale Model of Subionospheric VLF Signal Propagation Based on First-Principles Charged Particle Transport Calculations

NASA Astrophysics Data System (ADS)

Kouznetsov, A.; Cully, C. M.; Knudsen, D. J.

2016-12-01

Changes in D-Region ionization caused by energetic particle precipitation are monitored by the Array for Broadband Observations of VLF/ELF Emissions (ABOVE) - a network of receivers deployed across Western Canada. The observed amplitudes and phases of subionospheric-propagating VLF signals from distant artificial transmitters depend sensitively on the free electron population created by precipitation of energetic charged particles. Those include both primary (electrons, protons and heavier ions) and secondary (cascades of ionized particles and electromagnetic radiation) components. We have designed and implemented a full-scale model to predict the received VLF signals based on first-principle charged particle transport calculations coupled to the Long Wavelength Propagation Capability (LWPC) software. Calculations of ionization rates and free electron densities are based on MCNP-6 (a general-purpose Monte Carlo N- Particle) software taking advantage of its capability of coupled neutron/photon/electron transport and novel library of cross-sections for low-energetic electron and photon interactions with matter. Cosmic ray calculations of background ionization are based on source spectra obtained both from PAMELA direct Cosmic Rays spectra measurements and based on the recently-implemented MCNP 6 galactic cosmic-ray source, scaled using our (Calgary) neutron monitor measurement results. Conversion from calculated fluxes (MCNP F4 tallies) to ionization rates for low-energy electrons are based on the total ionization cross-sections for oxygen and nitrogen molecules from the National Institute of Standard and Technology. We use our model to explore the complexity of the physical processes affecting VLF propagation.

Autoionizing resonances in electron-impact ionization of O5+ ions

NASA Astrophysics Data System (ADS)

Müller, A.; Teng, H.; Hofmann, G.; Phaneuf, R. A.; Salzborn, E.

2000-12-01

We report on a detailed experimental and theoretical study of electron-impact ionization of O5+ ions. A high-resolution scan measurement of the K-shell excitation threshold region has been performed with statistical uncertainties as low as 0.03%. At this level of precision a wealth of features in the cross section arising from indirect ionization processes becomes visible, and even interference of direct ionization with resonant-excitation/auto-double-ionization (READI) is clearly observed. The experimental results are compared with R-matrix calculations that include both direct and indirect processes in a unified way. Radiative damping of autoionizing Li-like states is found to be about 10-15 %. The calculations almost perfectly reproduce most of the experimental resonance features found in the present measurement including READI. They also agree with the direct-ionization converged close-coupling results of I. Bray [J. Phys. B 28, L247 (1995)] and the absolute total ionization cross section measurement of K. Rinn et al. [Phys. Rev. A 36, 595 (1987)].

Statistical time-dependent model for the interstellar gas

NASA Technical Reports Server (NTRS)

Gerola, H.; Kafatos, M.; Mccray, R.

1974-01-01

We present models for temperature and ionization structure of low, uniform-density (approximately 0.3 per cu cm) interstellar gas in a galactic disk which is exposed to soft X rays from supernova outbursts occurring randomly in space and time. The structure was calculated by computing the time record of temperature and ionization at a given point by Monte Carlo simulation. The calculation yields probability distribution functions for ionized fraction, temperature, and their various observable moments. These time-dependent models predict a bimodal temperature distribution of the gas that agrees with various observations. Cold regions in the low-density gas may have the appearance of clouds in 21-cm absorption. The time-dependent model, in contrast to the steady-state model, predicts large fluctuations in ionization rate and the existence of cold (approximately 30 K), ionized (ionized fraction equal to about 0.1) regions.

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

Aydinol, M., E-mail: aydinolm@dicle.edu.tr; Aydeniz, D., E-mail: daydeniz@hotmail.com

L shell ionization cross section and {sub Li} subshells ionization cross sections of Os, Pt, Hg, Pb, Po atoms calculated. For each atom, ten different electron impacty energy values E{sub oi} used. Calculations carried out by using nonrelativistic Lotz equation in Matlab. Ionization cross section values obtained for Eoi values in the energy range of E{sub Li} ≤E{sub oi}≤4E{sub Li} for each atom. Starting allmost from E{sub oi} = E{sub Li} (i = 1,2,3) values of the each subshell ionization threshold energy, ionization cross section are increasing rapidly with E{sub oi}. For a fixed E{sub oi} = 3. E{sub Li}more » values, while Z increases from Z = 76 to Z = 84, ionization cross section are decrease. These results help to understand some results which obtained from other electron-sigle atom impact studies on σ{sub Li} subshells.« less

Hydrogen molecules and chains in a superstrong magnetic field

NASA Technical Reports Server (NTRS)

Lai, Dong; Salpeter, Edwin E.; Shapiro, Stuart L.

1992-01-01

The electronic structures of hydrogen polymolecules H(n) (n = 2,3,4,...) is studied in a superstrong magnetic field (B greater than about 10 exp 12 G) typically found on the surface of a neutron star. Simple analytical scaling relations for several limiting cases (e.g., large n, high B field) are derived. The binding energies of H(n) molecules are numerically calculated for various magnetic-field strengths. For a given magnetic-field strength, the binding energy per atom in the H(n) molecules is found to approach a constant value as n increases. For typical field strengths of interest, energy saturation is essentially achieved once n exceeds 3 to 4. Also considered is the structure of negative H ions in a high magnetic field. For B about 10 exp 12 G, the dissociation energy of an atom in a hydrogen chain and the ionization potential of H(-) are smaller than the ionization potential of neutral atomic hydrogen.

DFT study of Al doped armchair SWCNTs

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

Dhiman, Shobhna, E-mail: s-dhiman@hotmail.com; Rani, Anita; Kumar, Ranjan

2016-05-23

Electronic properties of endohedrally doped armchair single-walled carbon nanotubes (SWCNTs) with a chain of six Al atoms have been studied using ab-initio density functional theory. We investigate the binding energy/atom, ionization potential, electron Affinity and Homo-Lumo gap of doped armchair SWNTs from (4,4) to (6,6) with two ends open. BE/dopant atom and ionization potential is maximum for (6, 6) doped armchair carbon nanotube; suggest that it is more stable than (4, 4) and (5, 5) doped tubes. HOMO - LUMO gap of Al doped arm chair carbon nanotubes decreases linearly with the increase in diameter of the tube. This showsmore » that confinement induce a strong effect on electronic properties of doped tubes. These combined systems can be used for future nano electronics. The ab–initio calculations were performed with SIESTA code using generalized gradient approximation (GGA).« less

Using Wannier functions to improve solid band gap predictions in density functional theory

DOE PAGES

Ma, Jie; Wang, Lin-Wang

2016-04-26

Enforcing a straight-line condition of the total energy upon removal/addition of fractional electrons on eigen states has been successfully applied to atoms and molecules for calculating ionization potentials and electron affinities, but fails for solids due to the extended nature of the eigen orbitals. Here we have extended the straight-line condition to the removal/addition of fractional electrons on Wannier functions constructed within the occupied/unoccupied subspaces. It removes the self-interaction energies of those Wannier functions, and yields accurate band gaps for solids compared to experiments. It does not have any adjustable parameters and the computational cost is at the DFT level.more » This method can also work for molecules, providing eigen energies in good agreement with experimental ionization potentials and electron affinities. Our approach can be viewed as an alternative approach of the standard LDA+U procedure.« less

[The study on the characteristics and particle densities of lightning discharge plasma].

PubMed

Wang, Jie; Yuan, Ping; Zhang, Hua-ming; Shen, Xiao-zhi

2008-09-01

According to the wavelengths, relative intensities and transition parameters of lines in cloud-to-ground lightning spectra obtained by a slit-less spectrograph in Qinghai province and Xizang municipality, and by theoretical calculations of plasma, the average temperature and electron density for individual lightning discharge channel were calculated, and then, using Saha equations, electric charge conservation equations and particle conservation equations, the particle densities of every ionized-state, the mass density, pressure and the average ionization degree were obtained. Moreover, the average ionization degree and characteristics of particle distributions in each lightning discharge channel were analyzed. Local thermodynamic equilibrium and an optically thin emitting gas were assumed in the calculations. The result shows that the characteristics of lightning discharge plasma have strong relationships with lightning intensities. For a certain return stroke channel, both temperatures and electron densities of different positions show tiny trend of falling away with increasing height along the discharge channel. Lightning channels are almost completely ionized, and the first ionized particles occupy the main station while N II has the highest particle density. On the other hand, the relative concentrations of N II and O II are near a constant in lightning channels with different intensities. Generally speaking, the more intense the lightning discharge, the higher are the values of channel temperature, electron density and relative concentrations of highly ionized particles, but the lower the concentration of the neutral atoms. After considering the Coulomb interactions between positive and negative particles in the calculations, the results of ionization energies decrease, and the particle densities of atoms and first ionized ions become low while high-ionized ions become high. At a temperature of 28000 K, the pressure of the discharge channel due to electrons, atoms and ions is about 10 atmospheric pressure, and it changes for different lightning stroke with different intensity. The mass density of channel is lower and changes from 0.01 to 0.1 compared to the mass density of air at standard temperature and pressure (STP).

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.

Determination of Pesticides by Gas Chromatography Combined with Mass Spectrometry Using Femtosecond Lasers Emitting at 267, 400, and 800 nm as the Ionization Source.

PubMed

Yang, Xixiang; Imasaka, Tomoko; Imasaka, Totaro

2018-04-03

A standard sample mixture containing 51 pesticides was separated by gas chromatography (GC), and the constituents were identified by mass spectrometry (MS) using femtosecond lasers emitting at 267, 400, and 800 nm as the ionization source. A two-dimensional display of the GC/MS was successfully used for the determination of these compounds. A molecular ion was observed for 38 of the compounds at 267 nm and for 30 of the compounds at 800 nm, in contrast to 27 among 50 compounds when electron ionization was used. These results suggest that the ultraviolet laser is superior to the near-infrared laser for molecular weight determinations and for a more reliable analysis of these compounds. In order to study the conditions for optimal ionization, the experimental data were examined using the spectral properties (i.e., the excitation and ionization energies and absorption spectra for the neutral and ionized species) obtained by quantum chemical calculations. A few molecules remained unexplained by the currently reported rules, requiring additional rules for developing a full understanding of the femtosecond ionization process. The pesticides in the homogenized matrix obtained from kabosu ( citrus sphaerocarpa) were measured using lasers emitting at 267 and 800 nm. The pesticides were clearly separated and measured on the two-dimensional display, especially for the data measured at 267 nm, suggesting that this technique would have potential for use in the practical trace analysis of the pesticides in the environment.

Modeling X-ray Absorbers in AGNs with MHD-Driven Accretion-Disk Winds

NASA Astrophysics Data System (ADS)

Fukumura, Keigo; Kazanas, D.; Shrader, C. R.; Tombesi, F.; Contopoulos, J.; Behar, E.

2013-04-01

We have proposed a systematic view of the observed X-ray absorbers, namely warm absorbers (WAs) in soft X-ray and highly-ionized ultra-fast outflows (UFOs), in the context of magnetically-driven accretion-disk wind models. While potentially complicated by variability and thermal instability in these energetic outflows, in this simplistic model we have calculated 2D kinematic field as well as density and ionization structure of the wind with density profile of 1/r corresponding to a constant column distribution per decade of ionization parameter. In particular we show semi-analytically that the inner layer of the disk-wind manifests itself as the strongly-ionized fast outflows while the outer layer is identified as the moderately-ionized absorbers. The computed characteristics of these two apparently distinct absorbers are consistent with X-ray data (i.e. a factor of ~100 difference in column and ionization parameters as well as low wind velocity vs. near-relativistic flow). With the predicted contour curves for these wind parameters one can constrain allowed regions for the presence of WAs and UFOs.The model further implies that the UFO's gas pressure is comparable to that of the observed radio jet in 3C111 suggesting that the magnetized disk-wind with density profile of 1/r is a viable agent to help sustain such a self-collimated jet at small radii.

Study of gas-phase O-H bond dissociation enthalpies and ionization potentials of substituted phenols - Applicability of ab initio and DFT/B3LYP methods

NASA Astrophysics Data System (ADS)

Klein, Erik; Lukeš, Vladimír

2006-11-01

In this paper, the study of phenol and 37 compounds representing various ortho-, para-, and meta-substituted phenols is presented. Molecules and their radical structures were studied using ab initio methods with inclusion of correlation energy and DFT in order to calculate the O-H bond dissociation enthalpies (BDEs) and vertical ionization potentials (IPs). Calculated BDEs and IPs were compared with available experimental values to ascertain the suitability of used methods, especially for the description of the substituent induced changes in BDE and IP. MP2, MP3, and MP4 methods do not give reliable results, since they significantly underestimate substituent induced changes in BDE and do not reflect distinct effect of substituents related to para and meta position correctly. DFT/B3LYP method reflects the effect of substituents on BDE satisfactorily, though ΔBDEs are in narrower range than experimental values. BDE of phenol was calculated also using CCSD(T) method in various basis sets. Both, DFT and HF methods describe the effect of substituents on IP identically. However, DFT considerably underestimates individual values. HF method gives IPs in very good agreement with experimental data. Obtained results show that dependences of BDEs and IPs on Hammett constants of the substituents are linear. Linearity of DFT BDE vs. IP dependence is even better than the dependences on Hammett constants and obtained equations allow estimating of O-H BDEs of meta- and para-substituted phenols from calculated IPs.

Theoretical and Experimental Photoelectron Spectroscopy Characterization of the Ground State of Thymine Cation.

PubMed

Majdi, Youssef; Hochlaf, Majdi; Pan, Yi; Lau, Kai-Chung; Poisson, Lionel; Garcia, Gustavo A; Nahon, Laurent; Al-Mogren, Muneerah Mogren; Schwell, Martin

2015-06-11

We report on the vibronic structure of the ground state X̃(2)A″ of the thymine cation, which has been measured using a threshold photoelectron photoion coincidence technique and vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum, recorded over ∼0.7 eV above the ionization potential (i.e., covering the whole ground state of the cation) shows rich vibrational structure that has been assigned with the help of calculated anharmonic modes of the ground electronic cation state at the PBE0/aug-cc-pVDZ level of theory. The adiabatic ionization energy has been experimentally determined as AIE = 8.913 ± 0.005 eV, in very good agreement with previous high resolution results. The corresponding theoretical value of AIE = 8.917 eV has been calculated in this work with the explicitly correlated method/basis set (R)CCSD(T)-F12/cc-pVTZ-F12, which validates the theoretical approach and benchmarks its accuracy for future studies of medium-sized biological molecules.

Depolarizing collisions with hydrogen: Neutral and singly ionized alkaline earths

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

Manso Sainz, Rafael; Ramos, Andrés Asensio; Bueno, Javier Trujillo

2014-06-20

Depolarizing collisions are elastic or quasielastic collisions that equalize the populations and destroy the coherence between the magnetic sublevels of atomic levels. In astrophysical plasmas, the main depolarizing collider is neutral hydrogen. We consider depolarizing rates on the lowest levels of neutral and singly ionized alkali earths Mg I, Sr I, Ba I, Mg II, Ca II, and Ba II, due to collisions with H°. We compute ab initio potential curves of the atom-H° system and solve the quantum mechanical dynamics. From the scattering amplitudes, we calculate the depolarizing rates for Maxwellian distributions of colliders at temperatures T ≤ 10,000more » K. A comparative analysis of our results and previous calculations in the literature is completed. We discuss the effect of these rates on the formation of scattering polarization patterns of resonant lines of alkali earths in the solar atmosphere, and their effect on Hanle effect diagnostics of solar magnetic fields.« less

Ionization correction factors for H II regions in blue compact dwarf galaxies

NASA Astrophysics Data System (ADS)

Holovatyi, V. V.; Melekh, B. Ya.

2002-08-01

Energy distributions in the spectra of the ionizing nuclei of H II regions beyond λ <= 91.2 nm were calculated. A grid of photoionization models of 270 H II regions was constructed. The free parameters of the model grid are the hydrogen density nH in the nebular gas, filling factor, energy Lc-spectrum of ionizing nuclei, and metallicity. The chemical composition from the studies of Izotov et al. were used for model grid initialization. The integral linear spectra calculated for the photoionization models were used to determine the concentration ne, temperatures Te of electrons, and ionic concentrations n(A+i)/n(H+) by the nebular gas diagnostic method. The averaged relative ionic abundances n(A+i)/n(H+) thus calculated were used to determine new expressions for ionization correction factors which we recommend for the determination of abundances in the H II regions of blue compact dwarf galaxies.

Relativistic, correlation, and polarization effects in two-photon photoionization of Xe

NASA Astrophysics Data System (ADS)

Lagutin, B. M.; Petrov, I. D.; Sukhorukov, V. L.; Demekhin, Ph. V.; Knie, A.; Ehresmann, A.

2017-06-01

Two-photon ionization of xenon was investigated theoretically for exciting-photon energies from 6.7 to 11.5 eV, which results in the ionization of Xe between 5 p1 /2 (13.43 eV) and 5 s (23.40 eV) thresholds. We describe the extension of a previously developed computational technique for the inclusion of relativistic effects to calculate energies of intermediate resonance state and cross sections for two-photon ionization. Reasonable consistency of cross sections calculated in length and velocity form was obtained only after considering many-electron correlations. Agreement between calculated and measured resonance energies is found when core polarization was additionally included in the calculations. The presently computed two-photon photoionization cross sections of Xe are compared with Ar cross sections in our previous work. Photoelectron angular distribution parameters calculated here indicate that intermediated resonances strongly influence photoelectron angular distribution of Xe.

Exploring the dynamics of reaction N((2)D)+C2H4 with crossed molecular-beam experiments and quantum-chemical calculations.

PubMed

Lee, Shih-Huang; Chin, Chih-Hao; Chen, Wei-Kan; Huang, Wen-Jian; Hsieh, Chu-Chun

2011-05-14

We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively. Measurements of kinetic-energy distributions, angular distributions, low-resolution photoionization spectra, and branching ratios of the two products were carried out. Furthermore, we evaluated total branching ratios of various exit channels using RRKM calculations based on the potential-energy surface of reaction N((2)D)+C(2)H(4) established with the method CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p)]. The combination of experimental and computational results allows us to reveal the reaction dynamics. The N((2)D) atom adds to the C=C π-bond of ethene (C(2)H(4)) to form a cyclic complex c-CH(2)(N)CH(2) that directly ejects a hydrogen atom or rearranges to other intermediates followed by elimination of a hydrogen atom to produce C(2)H(3)N; c-CH(2)(N)CH+H is the dominant product channel. Subsequently, most C(2)H(3)N radicals, notably c-CH(2)(N)CH, further decompose to CH(2)CN+H. This work provides results and explanations different from the previous work of Balucani et al. [J. Phys. Chem. A, 2000, 104, 5655], indicating that selective photoionization with synchrotron radiation as an ionization source is a good choice in chemical dynamics research.

Electron-impact ionization of P-like ions forming Si-like ions

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

Kwon, D.-H.; Savin, D. W., E-mail: hkwon@kaeri.re.kr

2014-03-20

We have calculated electron-impact ionization (EII) for P-like systems from P to Zn{sup 15+} forming Si-like ions. The work was performed using the flexible atomic code (FAC) which is based on a distorted-wave approximation. All 3ℓ → nℓ' (n = 3-35) excitation-autoionization (EA) channels near the 3p direct ionization threshold and 2ℓ → nℓ' (n = 3-10) EA channels at the higher energies are included. Close attention has been paid to the detailed branching ratios. Our calculated total EII cross sections are compared both with previous FAC calculations, which omitted many of these EA channels, and with the available experimentalmore » results. Moreover, for Fe{sup 11+}, we find that part of the remaining discrepancies between our calculations and recent measurements can be accounted for by the inclusion of the resonant excitation double autoionization process. Lastly, at the temperatures where each ion is predicted to peak in abundances in collisional ionization equilibrium, the Maxwellian rate coefficients derived from our calculations differ by 50%-7% from the previous FAC rate coefficients, with the difference decreasing with increasing charge.« less

Protonium Formation in Collisions of Antiprotons with Hydrogen Molecules

NASA Astrophysics Data System (ADS)

Cohen, James S.

1997-04-01

The first full-dynamics calculation of barp capture by the H2 molecule has been performed using the quasiclassical Kirschbaum-Wilets method with modifications for accurate treatment of the molecular structure. It had been speculated in calculations of heavy-negative-particle (μ^-) capture by the H atom(J. S. Cohen, R. L. Martin, and W. R. Wadt, Phys. Rev. A 27), 1821 (1983). that the capture cross section for the H2 molecule might be smaller than that for the atom at very low energies (based on the absence of adiabatic ionization for the molecule) but larger at higher energies (based on the molecule having two electrons and a higher ionization potential). This speculation seemed to be borne out by a diabatic-states calculation,(G. Ya. Korenman and V. P. Popov, AIP Conference Proceedings 181, p. 145 (1989).) which showed the two cross sections crossing at a center-of-mass energy of ~8 eV. However, both the qualitative argument and that calculation neglected the molecular vibrational and rotational dynamics. The present calculations show that the molecular degrees of freedom of the target are important and that the molecular capture cross section is always larger and extends to a higher collision energy ( ~80 eV vs. ~25 eV) than the atomic cross section. The distribution of n and l quantum numbers of the captured barp will also be presented.

Vibrational spectroscopic, structural and nonlinear optical activity studies on 2-amino-3-chloro-5-trifluoromethyl pyridine: A DFT approach

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

Asath, R. Mohamed; Premkumar, S.; Mathavan, T.

2016-05-23

The conformational analysis was carried out for 2-amino-3-chloro-5-trifluoromethylpyridine using potential energy surface (PES) scan and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program package. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness of the moleculemore » were carried out. The nonlinear optical (NLO) activity was studied and the first order hyperpolarizability value was computed, which was 3.48 times greater than the urea. The natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ACTP molecule is a promising candidate for NLO materials.« less

Vibrational spectroscopic, structural and nonlinear optical activity studies on 2-amino-3-chloro-5-trifluoromethyl pyridine: A DFT approach

NASA Astrophysics Data System (ADS)

Asath, R. Mohamed; Premkumar, S.; Rekha, T. N.; Jawahar, A.; Mathavan, T.; Benial, A. Milton Franklin

2016-05-01

The conformational analysis was carried out for 2-amino-3-chloro-5-trifluoromethylpyridine using potential energy surface (PES) scan and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program package. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness of the molecule were carried out. The nonlinear optical (NLO) activity was studied and the first order hyperpolarizability value was computed, which was 3.48 times greater than the urea. The natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ACTP molecule is a promising candidate for NLO materials.

Conformational, vibrational spectroscopic and nonlinear optical activity studies on N,N-Di-Boc-2-amino pyridine : A DFT approach

NASA Astrophysics Data System (ADS)

Asath, R. Mohamed; Premkumar, R.; Mathavan, T.; Benial, A. Milton Franklin

2017-05-01

The conformational analysis was carried out for N,N-Di-Boc-2-amino pyridine using potential energy surface (PES) scan and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVTZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program package. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness of the molecule were carried out. The nonlinear optical (NLO) activity was examined and the first order hyperpolarizability value was computed, which was 2.27 times greater than the urea. The natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the DBAP molecule is a promising candidate for NLO materials.

Calculation of total electron excitation cross-sections and partial electron ionization cross-sections for the elements. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Green, T. J.

1973-01-01

Computer programs were used to calculate the total electron excitation cross-section for atoms and the partial ionization cross-section. The approximations to the scattering amplitude used are as follows: (1) Born, Bethe, and Modified Bethe for non-exchange excitation; (2) Ochkur for exchange excitation; and (3) Coulomb-Born of non-exchange ionization. The amplitudes are related to the differential cross-sections which are integrated to give the total excitation (or partial ionization) cross-section for the collision. The atomic wave functions used are Hartree-Fock-Slater functions for bound states and the coulomb wave function for the continuum. The programs are presented and the results are examined.

Oxygen Pickup Ions Measured by MAVEN Outside the Martian Bow Shock

NASA Astrophysics Data System (ADS)

Rahmati, A.; Cravens, T.; Larson, D. E.; Lillis, R. J.; Dunn, P.; Halekas, J. S.; Connerney, J. E. P.; Eparvier, F. G.; Thiemann, E.; Mitchell, D. L.; Jakosky, B. M.

2015-12-01

The MAVEN (Mars Atmosphere and Volatile EvolutioN) spacecraft entered orbit around Mars on September 21, 2014 and has since been detecting energetic oxygen pickup ions by its SEP (Solar Energetic Particles) and SWIA (Solar Wind Ion Analyzer) instruments. The oxygen pickup ions detected outside the Martian bowshock and in the upstream solar wind are associated with the extended hot oxygen exosphere of Mars, which is created mainly by the dissociative recombination of molecular oxygen ions with electrons in the ionosphere. We use analytic solutions to the equations of motion of pickup ions moving in the undisturbed upstream solar wind magnetic and motional electric fields and calculate the flux of oxygen pickup ions at the location of MAVEN. Our model calculates the ionization rate of oxygen atoms in the exosphere based on the hot oxygen densities predicted by Rahmati et al. (2014), and the sources of ionization include photo-ionization, charge exchange, and electron impact ionization. The photo-ionization frequency is calculated using the FISM (Flare Irradiance Spectral Model) solar flux model, based on MAVEN EUVM (Extreme Ultra-Violet Monitor) measurements. The frequency of charge exchange between a solar wind proton and an oxygen atom is calculated using MAVEN SWIA solar wind proton flux measurements, and the electron impact ionization frequency is calculated based on MAVEN SWEA (Solar Wind Electron Analyzer) solar wind electron flux measurements. The solar wind magnetic field used in the model is from the measurements taken by MAVEN MAG (magnetometer) in the upstream solar wind. The good agreement between our predicted pickup oxygen fluxes and the MAVEN SEP and SWIA measured ones confirms detection of oxygen pickup ions and these model-data comparisons can be used to constrain models of hot oxygen densities and photochemical escape flux.

Novel approach for calculating the charge carrier mobility and Hall factor for semiconductor materials

NASA Astrophysics Data System (ADS)

Colibaba, G. V.

2018-06-01

The additive Matthiessen's rule is the simplest and most widely used rule for the rapid experimental characterization and modeling of the charge carrier mobility. However, the error when using this rule can be higher than 40% and the contribution of the assumed additional scattering channels due to the difference between the experimental data and results calculated based on this rule can be misestimated by several times. In this study, a universal semi-additive equation is proposed for the total mobility and Hall factor, which is applicable to any quantity of scattering mechanisms, where it considers the energy dependence of the relaxation time and the error is 10-20 times lower compared with Matthiessen's rule. Calculations with accuracy of 99% are demonstrated for materials with polar-optical phonon, acoustic phonon via the piezoelectric potential, ionized, and neutral impurity scattering. The proposed method is extended to the deformation potential, dislocation, localized defect, alloy potential, and dipole scattering, for nondegenerate and partially degenerate materials.

Structural, vibrational spectroscopic and nonlinear optical activity studies on 2-hydroxy- 3, 5-dinitropyridine: A DFT approach

NASA Astrophysics Data System (ADS)

Asath, R. Mohamed; Premkumar, S.; Jawahar, A.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin

2015-06-01

The conformational analysis was carried out for 2-Hydroxy- 3, 5-dinitropyridine molecule using potential energy surface scan and the most stable optimized conformer was predicted. The vibrational frequencies and Mulliken atomic charge distribution were calculated for the optimized geometry of the molecule using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intramolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness values of the title molecule were carried out. The nonlinear optical activity of the molecule was studied by means of first order hyperpolarizability, which was computed as 7.64 times greater than urea. The natural bond orbital analysis was performed to confirm the nonlinear optical activity of the molecule.

Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry

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

Isselhardt, B. H.; Prussin, S. G.; Savina, M. R.

2016-01-01

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the U-235/U-238 ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equationmore » model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the U-235/U-238 ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. Development of this model has highlighted several important considerations for properly interpreting experimental results.« less

Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry

DOE PAGES

Isselhardt, B. H.; Prussin, S. G.; Savina, M. R.; ...

2015-12-07

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the 235U/238U ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equationmore » model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the 235U/ 238U ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. As a result, development of this model has highlighted several important considerations for properly interpreting experimental results.« less

Electron impact ionization cross section studies of C2Fx (x = 1 - 6) and C3Fx (x = 1 - 8) fluorocarbon species

NASA Astrophysics Data System (ADS)

Gupta, Dhanoj; Choi, Heechol; Song, Mi-Young; Karwasz, Grzegorz P.; Yoon, Jung-Sik

2017-05-01

The total ionization cross section for C2Fx (x = 1 - 6) and C3Fx (x = 1 - 8) fluorocarbon species are studied with the Binary-Encounter Bethe (BEB) model using various orbital parameters calculated from restricted/unrestricted Hartree-Fock (RHF/UHF) and Density Functional Theory (DFT). All the targets were optimized for their minimal structures and energies with several ab-initio methods with the aug-cc-pVTZ basis set. Among them, the present results with RHF/UHF orbital energies showed good agreement with the experimental results for stable targets C2F6, C2F4, C3F6 and C3F8. The results with the DFT (ωB97X/ωB97X-D) showed a reasonable agreement with the recent calculation of Bull et al. [J.N. Bull, M. Bart, C. Vallance, P.W. Harland, Phys. Rev. A 88, 062710 (2013)] for C2F6, C3F6 and C3F8 targets. The ionization cross section for C2F, C2F2, C2F3, C3F, C3F2, C3F3, C3F4, C3F5 and C3F7 were computed for the first time in the present study. We have also computed the vertical ionization potentials and polarizability for all the targets and compared them with other experimental and theoretical values. A good agreement is found between the present and the previous results. The calculated polarizability in turn is used to study the correlation with maximum ionization cross section and in general a good correlation is found among them, confirming the consistency and reliability of the present data. The cross section data reported in this article are very important for plasma modeling especially related to fluorocarbon plasmas. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Pseudopotentials for quantum Monte Carlo studies of transition metal oxides

DOE PAGES

Krogel, Jaron T.; Santana Palacio, Juan A.; Reboredo, Fernando A.

2016-02-22

Quantum Monte Carlo (QMC) calculations of transition metal oxides are partially limited by the availability of high-quality pseudopotentials that are both accurate in QMC and compatible with major plane-wave electronic structure codes. We have generated a set of neon-core pseudopotentials with small cutoff radii for the early transition metal elements Sc to Zn within the local density approximation of density functional theory. The pseudopotentials have been directly tested for accuracy within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (M) atoms and the binding curve of each M-O dimer. We find the ionization potentialsmore » to be accurate to 0.16(1) eV, on average, relative to experiment. The equilibrium bond lengths of the dimers are within 0.5(1)% of experimental values, on average, and the binding energies are also typically accurate to 0.18(3) eV. The level of accuracy we find for atoms and dimers is comparable to what has recently been observed for bulk metals and oxides using the same pseudopotentials. Our QMC pseudopotential results compare well with the findings of previous QMC studies and benchmark quantum chemical calculations.« less

Impact of Coulomb potential on peak structures arising in momentum and low-energy photoelectron spectra produced in strong-field ionization of laser-irradiated atoms

NASA Astrophysics Data System (ADS)

Pyak, P. E.; Usachenko, V. I.

2018-03-01

The phenomenon of pronounced peak structure(s) of longitudinal momentum distributions as well as a spike-like structure of low-energy spectra of photoelectrons emitted from laser-irradiated Ar and Ne atoms in a single ionization process is theoretically studied in the tunneling and multiphoton regimes of ionization. The problem is addressed assuming only the direct above-threshold ionization (ATI) as a physical mechanism underlying the phenomenon under consideration (viz. solely contributing to observed photoelectron momentum distributions (PMD)) and using the Coulomb-Volkov (CV) ansatz within the frame of conventional strong-field approximation (SFA) applied in the length-gauge formulation. The developed CV-SFA approach also incorporates the density functional theory essentially exploited for numerical composition of initial (laser-free) atomic state(s) constructed from atomic orbitals of Gaussian type. Our presented CV-SFA based (and laser focal-volume averaged) calculation results proved to be well reproducing both the pronounced double-peak and/or ATI-like multi-peak structure(s) experimentally observed in longitudinal PMD under conditions of tunneling and/or multiphoton regime, respectively. In addition, our CV-SFA results presented for tunneling regime also suggest and remarkably reproduce a pronounced structure observed in relevant experiments as a ‘spike-like’ enhanced maximum arising in low-energy region (around the value of about 1 eV) of photoelectron spectra. The latter consistency allows to identify and interpret these results as the so-called low-energy structure (LES) since the phenomenon proved to appear as the most prominent if the influence of Coulomb potential on photoelectron continuum states is maximally taken into account under calculations (viz. if the parameter Z in CV’s functions is put equal to 1). Moreover, the calculated LES proved to correspond (viz., established as closely related) to the mentioned double-peak structure arising in the low-momentum region ({p}| | ≤slant | 0.2| a.u.) of longitudinal PMDs calculated under condition of the tunneling regime. Thus, the phenomena under consideration can be well understood and adequately interpreted beyond the terms and/or concepts of various different alternative strong-field approaches and models (such as e.g., extensively invoked and exploited nowadays though, more sophisticated SFA-based ‘rescattering’ mechanism) compared to which, the currently applied CV-SFA model (through the same underlying physical mechanism of solely direct ATI suggested) is additionally able to provide and reveal an intimate and transparent interrelation between the phenomena of LES and double-peak structure arising in PMDs observed in the tunneling regime.

Ratios of double to single ionization of He and Ne by strong 400-nm laser pulses using the quantitative rescattering theory

NASA Astrophysics Data System (ADS)

Chen, Zhangjin; Li, Xiaojin; Zatsarinny, Oleg; Bartschat, Klaus; Lin, C. D.

2018-01-01

We present numerical simulations of the ratio between double and single ionization of He and Ne by intense laser pulses at wavelengths of 390 and 400 nm, respectively. The yields of doubly charged ions due to nonsequential double ionization (NSDI) are obtained by employing the quantitative rescattering (QRS) model. In this model, the NSDI ionization probability is expressed as a product of the returning electron wave packet (RWP) and the total scattering cross sections for laser-free electron impact excitation and electron impact ionization of the parent ion. According to the QRS theory, the same RWP is also responsible for the emission of high-energy above-threshold ionization photoelectrons. To obtain absolute double-ionization yields, the RWP is generated by solving the time-dependent Schrödinger equation (TDSE) within a one-electron model. The same TDSE results can also be taken to obtain single-ionization yields. By using the TDSE results to calibrate single ionization and the RWP obtained from the strong-field approximation, we further simplify the calculation such that the nonuniform laser intensity distribution in the focused laser beam can be accounted for. In addition, laser-free electron impact excitation and ionization cross sections are calculated using the state-of-the-art many-electron R -matrix theory. The simulation results for double-to-single-ionization ratios are found to compare well with experimental data and support the validity of the nonsequential double-ionization mechanism for the covered intensity region.

Electron- and photon-impact ionization of furfural

NASA Astrophysics Data System (ADS)

Jones, D. B.; Ali, E.; Nixon, K. L.; Limão-Vieira, P.; Hubin-Franskin, M.-J.; Delwiche, J.; Ning, C. G.; Colgan, J.; Murray, A. J.; Madison, D. H.; Brunger, M. J.

2015-11-01

The He(i) photoelectron spectrum of furfural has been investigated, with its vibrational structure assigned for the first time. The ground and excited ionized states are assigned through ab initio calculations performed at the outer-valence Green's function level. Triple differential cross sections (TDCSs) for electron-impact ionization of the unresolved combination of the 4a″ + 21a' highest and next-highest occupied molecular orbitals have also been obtained. Experimental TDCSs are recorded in a combination of asymmetric coplanar and doubly symmetric coplanar kinematics. The experimental TDCSs are compared to theoretical calculations, obtained within a molecular 3-body distorted wave framework that employed either an orientation average or proper TDCS average. The proper average calculations suggest that they may resolve some of the discrepancies regarding the angular distributions of the TDCS, when compared to calculations employing the orbital average.

grid-model: Semi-numerical reionization code

NASA Astrophysics Data System (ADS)

Hutter, Anne

2018-05-01

grid-model computes the time and spatially dependent ionization of neutral hydrogen (HI), neutral (HeI) and singly ionized helium (HeII) in the intergalactic medium (IGM). It accounts for recombinations and provides different descriptions for the photoionization rate that are used to calculate the residual HI fraction in ionized regions. The ionizing emissivity is directly derived from the RT simulation spectra.

Approximate treatment of semicore states in GW calculations with application to Au clusters.

PubMed

Xian, Jiawei; Baroni, Stefano; Umari, P

2014-03-28

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G0W0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au20 and Au32, that would be otherwise very difficult to deal with.

Approximate treatment of semicore states in GW calculations with application to Au clusters

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

Xian, Jiawei; Baroni, Stefano; CNR-IOM Democritos, Theory-Elettra group, Trieste

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G{sub 0}W{sub 0} level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore statesmore » are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au{sub 20} and Au{sub 32}, that would be otherwise very difficult to deal with.« less

New size-expanded RNA nucleobase analogs: a detailed theoretical study.

PubMed

Zhang, Laibin; Zhang, Zhenwei; Ren, Tingqi; Tian, Jianxiang; Wang, Mei

2015-04-05

Fluorescent nucleobase analogs have attracted much attention in recent years due to their potential applications in nucleic acids research. In this work, four new size-expanded RNA base analogs were computationally designed and their structural, electronic, and optical properties are investigated by means of DFT calculations. The results indicate that these analogs can form stable Watson-Crick base pairs with natural counterparts and they have smaller ionization potentials and HOMO-LUMO gaps than natural ones. Particularly, the electronic absorption spectra and fluorescent emission spectra are calculated. The calculated excitation maxima are greatly red-shifted compared with their parental and natural bases, allowing them to be selectively excited. In gas phase, the fluorescence from them would be expected to occur around 526, 489, 510, and 462 nm, respectively. The influences of water solution and base pairing on the relevant absorption spectra of these base analogs are also examined. Copyright © 2015 Elsevier B.V. All rights reserved.

Numerical simulation of ion charge breeding in electron beam ion source

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

Zhao, L., E-mail: zhao@far-tech.com; Kim, Jin-Soo

2014-02-15

The Electron Beam Ion Source particle-in-cell code (EBIS-PIC) tracks ions in an EBIS electron beam while updating electric potential self-consistently and atomic processes by the Monte Carlo method. Recent improvements to the code are reported in this paper. The ionization module has been improved by using experimental ionization energies and shell effects. The acceptance of injected ions and the emittance of extracted ion beam are calculated by extending EBIS-PIC to the beam line transport region. An EBIS-PIC simulation is performed for a Cs charge-breeding experiment at BNL. The charge state distribution agrees well with experiments, and additional simulation results ofmore » radial profiles and velocity space distributions of the trapped ions are presented.« less

Theoretical dissociation energies for the alkali and alkaline-earth monofluorides and monochlorides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.

Studies on the synthesis, spectroscopic analysis, molecular docking and DFT calculations on 1-hydroxy-2-(4-hydroxyphenyl)-4,5-dimethyl-imidazol 3-oxide

NASA Astrophysics Data System (ADS)

Benzon, K. B.; Sheena, Mary Y.; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Pradhan, Kiran; Nanda, Ashis Kumar; Van Alsenoy, C.

2017-02-01

In this work we have investigated in details the spectroscopic and reactive properties of newly synthesized imidazole derivative, namely the 1-hydroxy-2-(4-hydroxyphenyl)-4,5-dimethyl-imidazole 3-oxide (HHPDI). FT-IR and NMR spectra were measured and compared with theoretically obtained data provided by calculations of potential energy distribution and chemical shifts, respectively. Insight into the global reactivity properties has been obtained by analysis of frontier molecular orbitals, while local reactivity properties have been investigated by analysis of charge distribution, ionization energies and Fukui functions. NBO analysis was also employed to understand the stability of molecule, while hyperpolarizability has been calculated in order to assess the nonlinear optical properties of title molecule. Sensitivity towards autoxidation and hydrolysis mechanisms has been investigated by calculations of bond dissociation energies and radial distribution functions, respectively. Molecular docking study was also performed, in order to determine the pharmaceutical potential of the investigated molecule.

Molecular Data for a Biochemical Model of DNA Radiation Damage: Electron Impact Ionization and Dissociative Ionization of DNA Bases and Sugar-Phosphate Backbone

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Fletcher, Graham D.

2004-01-01

As part of the database for building up a biochemical model of DNA radiation damage, electron impact ionization cross sections of sugar-phosphate backbone and DNA bases have been calculated using the improved binary-encounter dipole (iBED) model. It is found that the total ionization cross sections of C3'- and C5'-deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 10%. Of the four DNA bases, the ionization cross section of guanine is the largest, then in decreasing order, adenine, thymine, and cytosine. The order is in accordance with the known propensity of oxidation of the bases by ionizing radiation. Dissociative ionization (DI), a process that both ionizes and dissociates a molecule, is investigated for cytosine. The DI cross section for the formation of H and (cytosine-Hl)(+), with the cytosine ion losing H at the 1 position, is also reported. The threshold of this process is calculated to be 17.1 eV. Detailed analysis of ionization products such as in DI is important to trace the sequential steps in the biochemical process of DNA damage.

Monte Carlo calculations of k{sub Q}, the beam quality conversion factor

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

Muir, B. R.; Rogers, D. W. O.

2010-11-15

Purpose: To use EGSnrc Monte Carlo simulations to directly calculate beam quality conversion factors, k{sub Q}, for 32 cylindrical ionization chambers over a range of beam qualities and to quantify the effect of systematic uncertainties on Monte Carlo calculations of k{sub Q}. These factors are required to use the TG-51 or TRS-398 clinical dosimetry protocols for calibrating external radiotherapy beams. Methods: Ionization chambers are modeled either from blueprints or manufacturers' user's manuals. The dose-to-air in the chamber is calculated using the EGSnrc user-code egs{sub c}hamber using 11 different tabulated clinical photon spectra for the incident beams. The dose to amore » small volume of water is also calculated in the absence of the chamber at the midpoint of the chamber on its central axis. Using a simple equation, k{sub Q} is calculated from these quantities under the assumption that W/e is constant with energy and compared to TG-51 protocol and measured values. Results: Polynomial fits to the Monte Carlo calculated k{sub Q} factors as a function of beam quality expressed as %dd(10){sub x} and TPR{sub 10}{sup 20} are given for each ionization chamber. Differences are explained between Monte Carlo calculated values and values from the TG-51 protocol or calculated using the computer program used for TG-51 calculations. Systematic uncertainties in calculated k{sub Q} values are analyzed and amount to a maximum of one standard deviation uncertainty of 0.99% if one assumes that photon cross-section uncertainties are uncorrelated and 0.63% if they are assumed correlated. The largest components of the uncertainty are the constancy of W/e and the uncertainty in the cross-section for photons in water. Conclusions: It is now possible to calculate k{sub Q} directly using Monte Carlo simulations. Monte Carlo calculations for most ionization chambers give results which are comparable to TG-51 values. Discrepancies can be explained using individual Monte Carlo calculations of various correction factors which are more accurate than previously used values. For small ionization chambers with central electrodes composed of high-Z materials, the effect of the central electrode is much larger than that for the aluminum electrodes in Farmer chambers.« less

Electron-Atom Ionization Calculations using Propagating Exterior Complex Scaling

NASA Astrophysics Data System (ADS)

Bartlett, Philip

2007-10-01

The exterior complex scaling method (Science 286 (1999) 2474), pioneered by Rescigno, McCurdy and coworkers, provided highly accurate ab initio solutions for electron-hydrogen collisions by directly solving the time-independent Schr"odinger equation in coordinate space. An extension of this method, propagating exterior complex scaling (PECS), was developed by Bartlett and Stelbovics (J. Phys. B 37 (2004) L69, J. Phys. B 39 (2006) R379) and has been demonstrated to provide computationally efficient and accurate calculations of ionization and scattering cross sections over a large range of energies below, above and near the ionization threshold. An overview of the PECS method for three-body collisions and the computational advantages of its propagation and iterative coupling techniques will be presented along with results of: (1) near-threshold ionization of electron-hydrogen collisions and the Wannier threshold laws, (2) scattering cross section resonances below the ionization threshold, and (3) total and differential cross sections for electron collisions with excited targets and hydrogenic ions from low through to high energies. Recently, the PECS method has been extended to solve four-body collisions using time-independent methods in coordinate space and has initially been applied to the s-wave model for electron-helium collisions. A description of the extensions made to the PECS method to facilitate these significantly more computationally demanding calculations will be given, and results will be presented for elastic, single-excitation, double-excitation, single-ionization and double-ionization collisions.

[Ionization energies and infrared spectra studies of histidine using density functional theory].

PubMed

Hu, Qiong; Wang, Guo-Ying; Liu, Gang; Ou, Jia-Ming; Wang, Rui-Li

2010-05-01

Histidines provide axial ligands to the primary electron donors in photosynthetic reaction centers (RCs) and play an important role in the protein environments of these donors. In this paper the authors present a systematic study of ionization energies and vibrational properties of histidine using hybrid density functional theory (DFT). All calculations were undertaken by using B3LYP method in combination with four basis sets: 6-31G(d), 6-31G(df, p), 6-31+G(d) and 6-311+G(2d, 2p) with the aim to investigate how the basis sets influence the calculation results. To investigate solvent effects and gain a detailed understanding of marker bands of histidine, the ionization energies of histidine and the vibrational frequencies of histidine which are unlabeled and 13C, 15N, and 2H labeled in the gas phase, CCl4, protein environment, THF and water solution, which span a wide range of dielectric constant, were also calculated. Our results showed that: (1) The main geometry parameters of histidine were impacted by basis sets and mediums, and C2-N3 and N3-C4 bond of imidazole ring of histidine side chain display the maximum bond lengths in the gas phase; (2) single point energies and frequencies calculated were decreased while ionization energies increased with the increasing level of basis sets and diffuse function applied in the same solvent; (3) with the same computational method, the higher the dielectric constant of the solvent used, the lower the ionization energy and vibrational frequency and the higher the intensity obtained. In addition, calculated ionization energy in the gas phase and marker bands of histidine as well as frequency shift upon 13C and 15N labeling at the computationally more expensive 6-311+G(2d, 2p) level are in good agreement with experimental observations available in literatures. All calculations indicated that the results calculated by using higher level basis set with diffuse function were more accurate and closer to the experimental value. In conclusion, the results provide useful information for the further studies of the functional and vibrational properties of chlorophyll-a ligated to histidine residue in photosynthetic reaction center.

Influence of defects on the absorption edge of InN thin films: The band gap value

NASA Astrophysics Data System (ADS)

Thakur, J. S.; Danylyuk, Y. V.; Haddad, D.; Naik, V. M.; Naik, R.; Auner, G. W.

2007-07-01

We investigate the optical-absorption spectra of InN thin films whose electron density varies from ˜1017tõ1021cm-3 . The low-density films are grown by molecular-beam-epitaxy deposition while highly degenerate films are grown by plasma-source molecular-beam epitaxy. The optical-absorption edge is found to increase from 0.61to1.90eV as the carrier density of the films is increased from low to high density. Since films are polycrystalline and contain various types of defects, we discuss the band gap values by studying the influence of electron degeneracy, electron-electron, electron-ionized impurities, and electron-LO-phonon interaction self-energies on the spectral absorption coefficients of these films. The quasiparticle self-energies of the valence and conduction bands are calculated using dielectric screening within the random-phase approximation. Using one-particle Green’s function analysis, we self-consistently determine the chemical potential for films by coupling equations for the chemical potential and the single-particle scattering rate calculated within the effective-mass approximation for the electron scatterings from ionized impurities and LO phonons. By subtracting the influence of self-energies and chemical potential from the optical-absorption edge energy, we estimate the intrinsic band gap values for the films. We also determine the variations in the calculated band gap values due to the variations in the electron effective mass and static dielectric constant. For the lowest-density film, the estimated band gap energy is ˜0.59eV , while for the highest-density film, it varies from ˜0.60tõ0.68eV depending on the values of electron effective mass and dielectric constant.

Photoionization research on atomic radiation. 3: The ionization cross section of atomic nitrogen

NASA Technical Reports Server (NTRS)

Comes, F. J.; Elzer, A.

1982-01-01

The photoionization cross section of atomic nitrogen was measured between the ionization limit and 432 A. The experimental values are well fitted by those from a calculation of HENRY due to the dipole velocity approximation. A Rydberg series converging to the 5S-state of the ion is clearly identified from the ionization measurements and is shown to ionize.

Particle precipitation: How the spectrum fit impacts atmospheric chemistry

NASA Astrophysics Data System (ADS)

Wissing, J. M.; Nieder, H.; Yakovchouk, O. S.; Sinnhuber, M.

2016-11-01

Particle precipitation causes atmospheric ionization. Modeled ionization rates are widely used in atmospheric chemistry/climate simulations of the upper atmosphere. As ionization rates are based on particle measurements some assumptions concerning the energy spectrum are required. While detectors measure particles binned into certain energy ranges only, the calculation of a ionization profile needs a fit for the whole energy spectrum. Therefore the following assumptions are needed: (a) fit function (e.g. power-law or Maxwellian), (b) energy range, (c) amount of segments in the spectral fit, (d) fixed or variable positions of intersections between these segments. The aim of this paper is to quantify the impact of different assumptions on ionization rates as well as their consequences for atmospheric chemistry modeling. As the assumptions about the particle spectrum are independent from the ionization model itself the results of this paper are not restricted to a single ionization model, even though the Atmospheric Ionization Module OSnabrück (AIMOS, Wissing and Kallenrode, 2009) is used here. We include protons only as this allows us to trace changes in the chemistry model directly back to the different assumptions without the need to interpret superposed ionization profiles. However, since every particle species requires a particle spectrum fit with the mentioned assumptions the results are generally applicable to all precipitating particles. The reader may argue that the selection of assumptions of the particle fit is of minor interest, but we would like to emphasize on this topic as it is a major, if not the main, source of discrepancies between different ionization models (and reality). Depending on the assumptions single ionization profiles may vary by a factor of 5, long-term calculations may show systematic over- or underestimation in specific altitudes and even for ideal setups the definition of the energy-range involves an intrinsic 25% uncertainty for the ionization rates. The effects on atmospheric chemistry (HOx, NOx and Ozone) have been calculated by 3dCTM, showing that the spectrum fit is responsible for a 8% variation in Ozone between setups, and even up to 50% for extreme setups.

Single-Photon Ionization Soft-X-Ray Laser Mass Spectrometry of Potential Hydrogen Storage Materials

NASA Astrophysics Data System (ADS)

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

A desk-top size capillary discharge 46.9 nm lasear is applied in the gas phase study of nanoclusters. The high photon energy allows for single-photon ionization mass spectrometry with reduced cluster fragmentation. In the present studies, neutral Al m C n and Al m C n H x cluster are investigation for the first time. Single photon ionization through 46.9 nm, 118 nm, 193 nm lasers is used to detect neutral cluster distributions through time of flight mass spectrometry. Al m C n clusters are generated through laser ablation of a mixture of Al and C powders pressed into a disk. An oscillation of the vertical ionization energies (VIEs) of Al m C n clusters is observed in the experiments. The VIEs of Al m C n clusters changes as a function of the numbers of Al and C atoms in the clusters. Al m C n H x clusters are generated through an Al ablation plasma-hydrocarbon reaction, an Al-C ablation plasma reacting with H2 gas, or through cold Al m C n clusters reacting with H2 gas in a fast flow reactor. DFT and ab inito calculations are carried out to explore the structures, IEs, and electronic structures of Al m C n H x clusters. C=C bonds are favored for the lowest energy structures for Al m C n clusters. Be m C n H x are generated through a beryllium ablation plasma-hydrocarbon reaction and detected by single photon ionization of 193 nm laser. Both Al m C n H x and Be m C n H x are considered as potential hydrogen storage materials.

Theoretical electron-impact-ionization cross section for Fe11+ forming Fe12+

NASA Astrophysics Data System (ADS)

Kwon, Duck-Hee; Savin, Daniel Wolf

2012-08-01

We have calculated cross sections for electron impact ionization (EII) of P-like Fe11+ forming Si-like Fe12+. We have used the flexible atomic code (FAC) and a distorted-wave (DW) approximation. Particular attention has been paid to the ionization through the 3l→nl' and 2l→nl' excitation autoionization (EA) channels. We compare our results to previously published FAC DW results and recent experimental results. We find that the previous discrepancy between theory and experiment at the EII threshold can be accounted for by the 3l→nl' EA channels which were not included in the earlier calculations. At higher energies the discrepancy previously seen between theory and experiment for the magnitude of the 2l→nl'(n≥4) EA remains, though the difference has been reduced by our newer results. The resulting Maxwellian rate coefficient derived from our calculations lies within 11% of the experimentally derived rate coefficient in the temperature range where Fe11+ forms in collisional ionization equilibrium.

Kinetics of plasma formation in sodium vapor excited by nanosecond resonant laser pulses

NASA Astrophysics Data System (ADS)

Mahmoud, M. A.; Gamal, Y. E. E.

2012-07-01

We have studied theoretically formation of molecular ion Na2 + and the atomic ion Na+ which are created in laser excited sodium vapor at the first resonance transition, 3S1/2-3P1/2. A set of rate equations, which describe the temporal variation of the electron energy distribution function (EEDF), the electron density, the population density of the excited states as well as the atomic Na+ and molecular ion Na2 +, are solved numerically. The calculations are carried out at different laser energy and different sodium atomic vapor densities. The numerical calculations of the EEDF show that a deviation from the Maxwellian distribution due to the superelastic collisions effect. In addition to the competition between associative ionization (3P-3P), associative ionization (3P-3D) and Molnar-Hornbeck ionization processes for producing Na2 +, the calculations have also shown that the atomic ions Na+ are formed through the Penning ionization and photoionization processes. These results are found to be consistent with the experimental observations.

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

Grondein, P.; Lafleur, T.; Chabert, P.

Most state-of-the-art electric space propulsion systems such as gridded and Hall effect thrusters use xenon as the propellant gas. However, xenon is very rare, expensive to produce, and used in a number of competing industrial applications. Alternatives to xenon are currently being investigated, and iodine has emerged as a potential candidate. Its lower cost and larger availability, its solid state at standard temperature and pressure, its low vapour pressure and its low ionization potential make it an attractive option. In this work, we compare the performances of a gridded ion thruster operating separately with iodine and xenon, under otherwise identicalmore » conditions using a global model. The thruster discharge properties such as neutral, ion, and electron densities and electron temperature are calculated, as well as the thruster performance parameters such as thrust, specific impulse, and system efficiencies. For similar operating conditions, representative of realistic thrusters, the model predicts similar thrust levels and performances for both iodine and xenon. The thruster efficiency is however slightly higher for iodine compared with xenon, due to its lower ionization potential. This demonstrates that iodine could be a viable alternative propellant for gridded plasma thrusters.« less

Effects of weakly coupled and dense quantum plasmas environments on charge exchange and ionization processes in Na+ + Rb(5s) atom collisions

NASA Astrophysics Data System (ADS)

Pandey, Mukesh Kumar; Lin, Yen-Chang; Ho, Yew Kam

2017-02-01

The effects of weakly coupled or classical and dense quantum plasmas environment on charge exchange and ionization processes in Na+ + Rb(5s) atom collision at keV energy range have been investigated using classical trajectory Monte Carlo (CTMC) method. The interaction of three charged particles are described by the Debye-Hückel screen potential for weakly coupled plasma, whereas exponential cosine-screened Coulomb potential have been used for dense quantum plasma environment and the effects of both conditions on the cross sections are compared. It is found that screening effects on cross sections in high Debye length condition is quite small in both plasma environments. However, enhanced screening effects on cross sections are observed in dense quantum plasmas for low Debye length condition, which becomes more effective while decreasing the Debye length. Also, we have found that our calculated results for plasma-free case are comparable with the available theoretical results. These results are analyzed in light of available theoretical data with the choice of model potentials.

Estimating the intrinsic limit of the Feller-Peterson-Dixon composite approach when applied to adiabatic ionization potentials in atoms and small molecules

NASA Astrophysics Data System (ADS)

Feller, David

2017-07-01

Benchmark adiabatic ionization potentials were obtained with the Feller-Peterson-Dixon (FPD) theoretical method for a collection of 48 atoms and small molecules. In previous studies, the FPD method demonstrated an ability to predict atomization energies (heats of formation) and electron affinities well within a 95% confidence level of ±1 kcal/mol. Large 1-particle expansions involving correlation consistent basis sets (up to aug-cc-pV8Z in many cases and aug-cc-pV9Z for some atoms) were chosen for the valence CCSD(T) starting point calculations. Despite their cost, these large basis sets were chosen in order to help minimize the residual basis set truncation error and reduce dependence on approximate basis set limit extrapolation formulas. The complementary n-particle expansion included higher order CCSDT, CCSDTQ, or CCSDTQ5 (coupled cluster theory with iterative triple, quadruple, and quintuple excitations) corrections. For all of the chemical systems examined here, it was also possible to either perform explicit full configuration interaction (CI) calculations or to otherwise estimate the full CI limit. Additionally, corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, non-adiabatic effects, and other minor factors were considered. The root mean square deviation with respect to experiment for the ionization potentials was 0.21 kcal/mol (0.009 eV). The corresponding level of agreement for molecular enthalpies of formation was 0.37 kcal/mol and for electron affinities 0.20 kcal/mol. Similar good agreement with experiment was found in the case of molecular structures and harmonic frequencies. Overall, the combination of energetic, structural, and vibrational data (655 comparisons) reflects the consistent ability of the FPD method to achieve close agreement with experiment for small molecules using the level of theory applied in this study.

Evaluation of modern DFT functionals and G3n-RAD composite methods in the modelization of organic singlet diradicals.

PubMed

López-Carballeira, Diego; Ruipérez, Fernando

2016-04-01

The evaluation of four high-level composite methods based on the modification of Gaussian-3 (G3) theory for radicals and 18 exchange-correlation density functionals, including modern long-range and dispersion-corrected functionals, in the modelization of singlet diradicals has been performed in this work. Structural parameters and properties such as singlet-triplet gaps, electron affinities, ionization potentials, dipole moments, enthalpies of formation, and bond dissociation energies have been calculated in a set of six well-characterized singlet diradicals, and benchmarked against experimental data and wavefunction-based CASSCF/CASPT2 calculations. The complexity of the open-shell singlet ground state is revealed in the difficulties to properly represent the diradical character reported by some DFT functionals, specially those that do not comprise a certain amount of Hartree-Fock exchange in their formulation. We find that STGs, EAs, dipole moments, and thermochemical properties are, in general, satisfactorily calculated, while for IPs larger deviations with respect to the experiments are found in all cases. The best overall performance is accounted for by hybrid functionals, including some of the long-range corrected functionals, but also pure functionals, comprising the kinetic energy density in their formulation, are found to be competent. Composite methods perform satisfactorily, especially G3(MP2)-RAD and G3X(MP2)-RAD, which calculate singlet-triplet gaps and electron affinities more accurately. On the other hand, G3-RAD and G3X-RAD provide better ionization potentials. This study emphasizes that the use of recently developed functionals, within the broken symmetry approximation, is an appropriate tool for the simulation of organic singlet diradicals, with similar accuracy compared to more expensive composite methods. Nevertheless, suitable selection of the methodology is still crucial for the accomplishment of accurate results.

Plasma density enhancements created by the ionization of the Earth's upper atmosphere by artificial electron beams

NASA Technical Reports Server (NTRS)

Neubert, Torsten; Banks, Peter M.

1990-01-01

Analytical calculations and experimental observations relating to the interaction with the Earth's upper atmosphere of electron beams emitted from low altitude spacecraft are presented. The problem is described by two coupled nonlinear differential equations in the up-going (along a magnetic field line) and down-going differential energy flux. The equations are solved numerically, using the MSIS atmospheric model and the IRI ionospheric model. The results form the model compare well with recent observations from the CHARGE 2 sounding rocket experiment. Two aspects of the beam-neutral atmosphere interaction are discussed. First, the limits on the electron beam current that can be emitted from a spacecraft without substantial spacecraft charging are investigated. This is important because the charging of the spacecraft to positive potentials limits the current and the escape energy of the beam electrons and thereby limits the ionization of the neutral atmosphere. As an example, we find from CHARGE 2 observations and from the model calculations that below about 180 km, secondary electrons generated through the ionization of the neutral atmosphere by 1 to 10 keV electron beams from sounding rockets, completely balance the beam current, thereby allowing the emission of very high beam currents. Second, the amount of plasma production in the beam-streak is discussed. Results are shown for selected values of the beam energy, spacecraft velocity, and spacecraft altitude.

Monte Carlo simulations of ionization potential depression in dense plasmas

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

Stransky, M., E-mail: stransky@fzu.cz

A particle-particle grand canonical Monte Carlo model with Coulomb pair potential interaction was used to simulate modification of ionization potentials by electrostatic microfields. The Barnes-Hut tree algorithm [J. Barnes and P. Hut, Nature 324, 446 (1986)] was used to speed up calculations of electric potential. Atomic levels were approximated to be independent of the microfields as was assumed in the original paper by Ecker and Kröll [Phys. Fluids 6, 62 (1963)]; however, the available levels were limited by the corresponding mean inter-particle distance. The code was tested on hydrogen and dense aluminum plasmas. The amount of depression was up tomore » 50% higher in the Debye-Hückel regime for hydrogen plasmas, in the high density limit, reasonable agreement was found with the Ecker-Kröll model for hydrogen plasmas and with the Stewart-Pyatt model [J. Stewart and K. Pyatt, Jr., Astrophys. J. 144, 1203 (1966)] for aluminum plasmas. Our 3D code is an improvement over the spherically symmetric simplifications of the Ecker-Kröll and Stewart-Pyatt models and is also not limited to high atomic numbers as is the underlying Thomas-Fermi model used in the Stewart-Pyatt model.« less

Double proton transfer behavior and one-electron oxidation effect in double H-bonded glycinamide-formic acid complex.

PubMed

Li, Ping; Bu, Yuxiang

2004-11-22

The behavior of double proton transfer occurring in a representative glycinamide-formic acid complex has been investigated at the B3LYP/6-311 + + G( * *) level of theory. Thermodynamic and, especially, kinetic parameters, such as tautomeric energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the double proton transfer process, such as geometrical changes, interaction energies, and intrinsic reaction coordinate calculations have also been studied. Computational results show that the participation of a formic acid molecule favors the proceeding of the proton transfer for glycinamide compared with that without mediate-assisted case. The double proton transfer process proceeds with a concerted mechanism rather than a stepwise one since no ion-pair complexes have been located during the proton transfer process. The calculated barrier heights are 11.48 and 0.85 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 2.95 and 2.61 kcal/mol to 8.53 and -1.76 kcal/mol if further inclusion of zero-point vibrational energy corrections, where the negative barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to that occurring between glycinamide and formamide. Furthermore, solvent effects on the thermodynamic and kinetic processes have also been predicted qualitatively employing the isodensity surface polarized continuum model within the framework of the self-consistent reaction field theory. Additionally, the oxidation process for the double H-bonded glycinamide-formic acid complex has also been investigated. Contrary to that neutral form possessing a pair of two parallel intermolecular H bonds, only a single H bond with a comparable strength has been found in its ionized form. The vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 9.40 and 8.69 eV, respectively, where ionization is mainly localized on the glycinamide fragment. Like that ionized glycinamide-formamide complex, the proton transfer in the ionized complex is characterized by a single-well potential, implying that the proton initially attached to amide N4 in the glycinamide fragment cannot be transferred to carbonyl O13 in the formic acid fragment at the geometry of the optimized complex. Copyright 2004 American Institute of Physics.

Relationship between the Macroscopic and Quantum Characteristics of Dynamic Viscosity for Hydrocarbons upon the Compensation Effect

NASA Astrophysics Data System (ADS)

Dolomatov, M. Yu.; Kovaleva, E. A.; Khamidullina, D. A.

2018-05-01

An approach that allows the calculation of dynamic viscosity for liquid hydrocarbons from quantum (ionization energies) and molecular (Wiener topological indices) parameters is proposed. A physical relationship is revealed between ionization and the energies of viscous flow activation. This relationship is due to the contribution from the dispersion component of Van der Waals forces to intermolecular interaction. A two-parameter dependence of the energy of viscous flow activation, energy of ionization, and Wiener topological indices is obtained. The dynamic viscosities of liquid hydrocarbons can be calculated from the kinetic compensation effect of dynamic viscosity, which indicates a relationship between the energy of activation and the Arrhenius pre-exponental factor of the Frenkel-Eyring hole model. Calculation results are confirmed through statistical processing of the experimental data.

A theoretical study of the adiabatic and vertical ionization potentials of water.

PubMed

Feller, David; Davidson, Ernest R

2018-06-21

Theoretical predictions of the three lowest adiabatic and vertical ionization potentials of water were obtained from the Feller-Peterson-Dixon approach. This approach combines multiple levels of coupled cluster theory with basis sets as large as aug-cc-pV8Z in some cases and various corrections up to and including full configuration interaction theory. While agreement with experiment for the adiabatic ionization potential of the lowest energy 2 B 1 state was excellent, differences for other states were much larger, sometimes exceeding 10 kcal/mol (0.43 eV). Errors of this magnitude are inconsistent with previous benchmark work on 52 adiabatic ionization potentials, where a root mean square of 0.20 kcal/mol (0.009 eV) was found. Difficulties in direct comparisons between theory and experiment for vertical ionization potentials are discussed. With regard to the differences found for the 2 A 1 / 2 Π u and 2 B 2 adiabatic ionization potentials, a reinterpretation of the experimental spectrum appears justified.

Nuclear-Recoil Differential Cross Sections for the Two Photon Double Ionization of Helium

NASA Astrophysics Data System (ADS)

Abdel Naby, Shahin; Ciappina, M. F.; Lee, T. G.; Pindzola, M. S.; Colgan, J.

2013-05-01

In support of the reaction microscope measurements at the free-electron laser facility at Hamburg (FLASH), we use the time-dependent close-coupling method (TDCC) to calculate fully differential nuclear-recoil cross sections for the two-photon double ionization of He at photon energy of 44 eV. The total cross section for the double ionization is in good agreement with previous calculations. The nuclear-recoil distribution is in good agreement with the experimental measurements. In contrast to the single-photon double ionization, maximum nuclear recoil triple differential cross section is obtained at small nuclear momenta. This work was supported in part by grants from NSF and US DoE. Computational work was carried out at NERSC in Oakland, California and the National Institute for Computational Sciences in Knoxville, Tennessee.

Scaling Cross Sections for Ion-atom Impact Ionization

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

Igor D. Kaganovich; Edward Startsev; Ronald C. Davidson

2003-06-06

The values of ion-atom ionization cross sections are frequently needed for many applications that utilize the propagation of fast ions through matter. When experimental data and theoretical calculations are not available, approximate formulas are frequently used. This paper briefly summarizes the most important theoretical results and approaches to cross section calculations in order to place the discussion in historical perspective and offer a concise introduction to the topic. Based on experimental data and theoretical predictions, a new fit for ionization cross sections is proposed. The range of validity and accuracy of several frequently used approximations (classical trajectory, the Born approximation,more » and so forth) are discussed using, as examples, the ionization cross sections of hydrogen and helium atoms by various fully stripped ions.« less

Charge transfer collisions of Si^3+ with H at low energies

NASA Astrophysics Data System (ADS)

Joseph, D. C.; Gu, J. P.; Saha, B. C.

2009-11-01

Charge transfer of positively charged ions with atomic hydrogen is important not only in magnetically confined plasmas between impurity ions and H atoms from the chamber walls influences the overall ionization balance and effects the plasma cooling but also in astrophysics, where it plays a key role in determining the properties of the observed gas. It also provides a recombination mechanism for multiply charged ions in X-ray ionized astronomical environments. We report an investigation using the molecular-orbital close-coupling (MOCC) method, both quantum mechanically and semi-classically, in the adiabatic representation. Ab initio adiabatic potentials and coupling matrix elements--radial and angular--are calculated using the MRD-CI method. Comparison of our results with other theoretical as well as experimental findings will be discussed.

Physical processes associated with current collection by plasma contactors

NASA Technical Reports Server (NTRS)

Katz, Ira; Davis, Victoria A.

1990-01-01

Recent flight data confirms laboratory observations that the release of neutral gas increases plasma sheath currents. Plasma contactors are devices which release a partially ionized gas in order to enhance the current flow between a spacecraft and the space plasma. Ionization of the expellant gas and the formation of a double layer between the anode plasma and the space plasma are the dominant physical processes. A theory is presented of the interaction between the contactor plasma and the background plasma. The conditions for formation of a double layer between the two plasmas are derived. Double layer formation is shown to be a consequence of the nonlinear response of the plasmas to changes in potential. Numerical calculations based upon this model are compared with laboratory measurements of current collection by hollow cathode-based plasma contactors.

The variance of dispersion measure of high-redshift transient objects as a probe of ionized bubble size during reionization

NASA Astrophysics Data System (ADS)

Yoshiura, Shintaro; Takahashi, Keitaro

2018-01-01

The dispersion measure (DM) of high-redshift (z ≳ 6) transient objects such as fast radio bursts can be a powerful tool to probe the intergalactic medium during the Epoch of Reionization. In this paper, we study the variance of the DMs of objects with the same redshift as a potential probe of the size distribution of ionized bubbles. We calculate the DM variance with a simple model with randomly distributed spherical bubbles. It is found that the DM variance reflects the characteristics of the probability distribution of the bubble size. We find that the variance can be measured precisely enough to obtain the information on the typical size with a few hundred sources at a single redshift.

Solar Irradiance Changes And Photobiological Effects At Earth's Surface Following Astrophysical Ionizing Radiation Events

NASA Astrophysics Data System (ADS)

Thomas, Brian; Neale, Patrick

2016-01-01

Astrophysical ionizing radiation events have been recognized as a potential threat to life on Earth for decades. Although there is some direct biological damage on the surface from redistributed radiation several studies have indicated that the greatest long term threat is from ozone depletion and subsequent heightened solar ultraviolet (UV) radiation. It is known that organisms exposed to this irradiation experience harmful effects such as sunburn and even direct damage to DNA, proteins, or other cellular structures. Simulations of the atmospheric effects of a variety of events (such as supernovae, gamma-ray bursts, and solar proton events) have been previously published, along with estimates of biological damage at Earth's surface. In the present work, we employed a radiative transfer model to expand and improve calculations of surface-level irradiance and biological impacts following an ionizing radiation event. We considered changes in surface-level UVB, UVA, and photosynthetically active radiation (visible light). Using biological weighting functions we have considered a wide range of effects, including: erythema and skin cancer in humans; inhibition of photosynthesis in the diatom Phaeodactylum sp. and dinoflagellate Prorocentrum micans inhibition of carbon fixation in Antarctic phytoplankton; inhibition of growth of oat (Avena sativa L. cv. Otana) seedlings; and cataracts. We found that past work overestimated UVB irradiance, but that relative estimates for increase in exposure to DNA damaging radiation are still similar to our improved calculations. We also found that the intensity of biologically damaging radiation varies widely with organism and specific impact considered; these results have implications for biosphere-level damage following astrophysical ionizing radiation events. When considering changes in surface-level visible light irradiance, we found that, contrary to previous assumptions, a decrease in irradiance is only present for a short time in very limited geographical areas; instead we found a net increase for most of the modeled time-space region. This result has implications for proposed climate changes associated with ionizing radiation events.

Relativistic Ionization with Intense Linearly Polarized Light

NASA Astrophysics Data System (ADS)

Crawford, Douglas Plummer

The Strong Field Approximation (SFA) method is used to derive relativistic ionization rate expressions for ground state hydrogen-like atoms in the presence of an intense electromagnetic field. The emitted particle, which is initially bound to a hydrogen nucleus, is either an electron described by the Dirac equation, with spin effects fully included, or a spinless "electron" described by the Klein-Gordon equation. The derivations and subsequent calculations for both particles are made assuming a linearly polarized electromagnetic field which is monochromatic and which exhibits neither diffraction nor temporal dependence. From each of the relativistic ionization rate expressions, the corresponding expression in the nonrelativistic limit is derived. The resultant expressions are found to be equivalent to those derived using the SFA with the nonrelativistic formalism. This comparison provides the first check of the validity for the core results of this dissertation. Intensity-dependent ionization rates are then calculated for two ultraviolet frequencies using a numerical implementation of the derived expressions. Calculations of ionization rates and related phenomena demonstrate that there are negligible differences between relativistic and nonrelativistic predictions for low intensities. In addition, the differences in behavior between linearly and circularly polarized ionizing fields and between particles with and without spin are explored. The spin comparisons provide additional confidence in the derivations by showing negligible differences between ionization rates for Dirac and Klein -Gordon particles in strong linearly-polarized fields. Also of interest are the differential transition rates which exhibit dynamic profiles as the intensity is increased. This behavior is interpreted as an indication of more atomic influence for linearly polarized electromagnetic (em) fields than for circularly polarized em fields.

The size-luminosity relationship of quasar narrow-line regions

NASA Astrophysics Data System (ADS)

Dempsey, Ross; Zakamska, Nadia L.

2018-07-01

The presence of an active galactic nucleus (AGN) can strongly affect its host. Due to the copious radiative power of the nucleus, the effects of radiative feedback can be detected over the entire host galaxy and sometimes well into the intergalactic space. In this paper we model the observed size-luminosity relationship of the narrow-line regions (NLRs) of AGN. We model the NLR as a collection of clouds in pressure equilibrium with the ionizing radiation, with each cloud producing line emission calculated by Cloudy. The sizes of the NLRs of powerful quasars are reproduced without any free parameters, as long as they contain massive (105-107 M⊙) ionization-bounded clouds. At lower AGN luminosities the observed sizes are larger than the model sizes, likely due to additional unmodeled sources of ionization (e.g. star formation). We find that the observed saturation of sizes at ˜10 kpc which is observed at high AGN luminosities (Lion ≃ 1046 erg s-1) is naturally explained by optically thick clouds absorbing the ionizing radiation and preventing illumination beyond a critical distance. Using our models in combination with observations of the [O III]/IR ratio and the [O III] size-IR luminosity relationship, we calculate the covering factor of the obscuring torus (and therefore the type 2 fraction within the quasar population) to be f = 0.5, though this is likely an upper bound. Finally, because the gas behind the ionization front is invisible in ionized gas transitions, emission-based NLR mass calculations underestimate the mass of the NLR and therefore of the energetics of ionized-gas winds.

The Size-Luminosity Relationship of Quasar Narrow-Line Regions

NASA Astrophysics Data System (ADS)

Dempsey, Ross; Zakamska, Nadia L.

2018-04-01

The presence of an active galactic nucleus (AGN) can strongly affect its host. Due to the copious radiative power of the nucleus, the effects of radiative feedback can be detected over the entire host galaxy and sometimes well into the intergalactic space. In this paper we model the observed size-luminosity relationship of the narrow-line regions (NLRs) of AGN. We model the NLR as a collection of clouds in pressure equilibrium with the ionizing radiation, with each cloud producing line emission calculated by Cloudy. The sizes of the NLRs of powerful quasars are reproduced without any free parameters, as long as they contain massive (105M⊙ to 107M⊙) ionization-bounded clouds. At lower AGN luminosities the observed sizes are larger than the model sizes, likely due to additional unmodeled sources of ionization (e.g., star formation). We find that the observed saturation of sizes at ˜10kpc which is observed at high AGN luminosities (Lion ≃ 1046erg/s) is naturally explained by optically thick clouds absorbing the ionizing radiation and preventing illumination beyond a critical distance. Using our models in combination with observations of the [O III]/IR ratio and the [O III] size - IR luminosity relationship, we calculate the covering factor of the obscuring torus (and therefore the type 2 fraction within the quasar population) to be f = 0.5, though this is likely an upper bound. Finally, because the gas behind the ionization front is invisible in ionized gas transitions, emission-based NLR mass calculations underestimate the mass of the NLR and therefore of the energetics of ionized-gas winds.

Population inversion calculations using near resonant charge exchange as a pumping mechanism

NASA Technical Reports Server (NTRS)

Chubb, D. L.; Rose, J. R.

1972-01-01

Near resonance charge exchange between ions of a large ionization potential gas such as helium or neon and vapors of metals such as zinc, cadmium, selenium, or tellurium has produced laser action in the metal ion gas. The possibility of obtaining population inversions in near resonant charge exchange systems (Xe-Ca, Xe-Mg, Xe-Sr, Xe-Ba, Ar-Mg, N-Ca) was investigated. The analysis is an initial value problem that utilizes rate equations for the densities of relevant levels of the laser gas (Ca, Ba, Mg, or Sr) and an electron energy equation. Electron excitation rates are calculated using the Bohr-Thomson approximation for the cross section. Approximations to experimental values of the electron ionization cross section and the ion-atom charge exchange cross section are used. Preliminary results have been obtained for the Ca-Xe system and show that it is possible to obtain gains greater than 10 to the 14th power/m with inversion times up to 8x10 to the minus 7th power second. A possible charge exchange laser system using a MPD arc plasma accelerator is also described.

Experimental verification of gain drop due to general ion recombination for a carbon-ion pencil beam

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

Tansho, Ryohei, E-mail: r-tansho@nirs.go.jp; Furukawa, Takuji; Hara, Yousuke

Purpose: Accurate dose measurement in radiotherapy is critically dependent on correction for gain drop, which is the difference of the measured current from the ideal saturation current due to general ion recombination. Although a correction method based on the Boag theory has been employed, the theory assumes that ionized charge density in an ionization chamber (IC) is spatially uniform throughout the irradiation volume. For particle pencil beam scanning, however, the charge density is not uniform, because the fluence distribution of a pencil beam is not uniform. The aim of this study was to verify the effect of the nonuniformity ofmore » ionized charge density on the gain drop due to general ion recombination. Methods: The authors measured the saturation curve, namely, the applied voltage versus measured current, using a large plane-parallel IC and 24-channel parallel-plate IC with concentric electrodes. To verify the effect of the nonuniform ionized charge density on the measured saturation curve, the authors calculated the saturation curve using a method which takes into account the nonuniform ionized charge density and compared it with the measured saturation curves. Results: Measurement values of the different saturation curves in the different channels of the concentric electrodes differed and were consistent with the calculated values. The saturation curves measured by the large plane-parallel IC were also consistent with the calculation results, including the estimation error of beam size and of setup misalignment. Although the impact of the nonuniform ionized charge density on the gain drop was clinically negligible with the conventional beam intensity, it was expected that the impact would increase with higher ionized charge density. Conclusions: For pencil beam scanning, the assumption of the conventional Boag theory is not valid. Furthermore, the nonuniform ionized charge density affects the prediction accuracy of gain drop when the ionized charge density is increased by a higher dose rate and/or lower beam size.« less

Transition-matrix theory for two-photon ionization of rare-gas atoms and isoelectronic ions with application to argon

NASA Astrophysics Data System (ADS)

Starace, Anthony F.; Jiang, Tsin-Fu

1987-08-01

A transition-matrix theory for two-photon ionization processes in rare-gas atoms or isoelectronic ions is presented. Uncoupled ordinary differential equations are obtained for the radial functions needed to calculate the two-photon transition amplitude. The implications of these equations are discussed in detail. In particular, the role of correlations involving virtually excited electron pairs, which are known to be essential to the description of single-photon processes, is examined for multiphoton ionization processes. Additionally, electron scattering interactions between two electron-hole pairs are introduced into our transition amplitude in the boson approximation since these have been found important in two-photon ionization of xenon by L'Huillier and Wendin [J. Phys. B 20, L37 (1987)]. Application of our theory is made to two-photon ionization of the 3p subshell of argon below the one-photon ionization threshold. Our results are compared to previous calculations of McGuire [Phys. Rev. A 24, 835 (1981)], of Moccia, Rahman, and Rizzo [J. Phys. B 16, 2737 (1983)], and of Pindzola and Kelly [Phys. Rev. A 11, 1543 (1975)]. Results are presented for both circularly and linearly polarized photons. Among our findings are, firstly, that the electron scattering interactions, which have not been included in previous calculations for argon, produce a substantial reduction in the two-photon single-ionization cross section below the one-photon ionization threshold, which is in agreement with findings of L'Huillier and Wendin for xenon. Secondly, we find that de-excitation of virtually excited electron pairs by absorption of a photon is important for describing the interaction of the atom with the photon field, as in the case of single-photon ionization processes, but that further excitation of virtually excited electron pairs by the photon field has completely negligible effects, indicating a major simplification of the theory for higher-order absorption processes.

Mechanistic Analysis of the C-H Amination Reaction of Menthol by CuBr2 and Selectfluor.

PubMed

Sathyamoorthi, Shyam; Lai, Yin-Hung; Bain, Ryan M; Zare, Richard N

2018-05-18

The mechanism of the Ritter-type C-H amination reaction of menthol with acetonitrile using CuBr 2 , Selectfluor, and Zn(OTf) 2 , first disclosed by Baran and coworkers in 2012, was studied using a combination of online electrospray ionization mass spectrometry, continuous UV/vis spectrometric monitoring, and density functional theory calculations. In addition to corroborating Baran's original mechanistic proposal, these studies uncovered a second pathway to product formation, which likely only occurs in microdroplets. DFT calculations show that neither pathway has a barrier that is greater than 6.8 kcal/mol, suggesting that both mechanisms are potentially operative under ambient conditions.

FAMBE-pH: A Fast and Accurate Method to Compute the Total Solvation Free Energies of Proteins

PubMed Central

Vorobjev, Yury N.; Vila, Jorge A.

2009-01-01

A fast and accurate method to compute the total solvation free energies of proteins as a function of pH is presented. The method makes use of a combination of approaches, some of which have already appeared in the literature; (i) the Poisson equation is solved with an optimized fast adaptive multigrid boundary element (FAMBE) method; (ii) the electrostatic free energies of the ionizable sites are calculated for their neutral and charged states by using a detailed model of atomic charges; (iii) a set of optimal atomic radii is used to define a precise dielectric surface interface; (iv) a multilevel adaptive tessellation of this dielectric surface interface is achieved by using multisized boundary elements; and (v) 1:1 salt effects are included. The equilibrium proton binding/release is calculated with the Tanford–Schellman integral if the proteins contain more than ∼20–25 ionizable groups; for a smaller number of ionizable groups, the ionization partition function is calculated directly. The FAMBE method is tested as a function of pH (FAMBE-pH) with three proteins, namely, bovine pancreatic trypsin inhibitor (BPTI), hen egg white lysozyme (HEWL), and bovine pancreatic ribonuclease A (RNaseA). The results are (a) the FAMBE-pH method reproduces the observed pKa's of the ionizable groups of these proteins within an average absolute value of 0.4 pK units and a maximum error of 1.2 pK units and (b) comparison of the calculated total pH-dependent solvation free energy for BPTI, between the exact calculation of the ionization partition function and the Tanford–Schellman integral method, shows agreement within 1.2 kcal/mol. These results indicate that calculation of total solvation free energies with the FAMBE-pH method can provide an accurate prediction of protein conformational stability at a given fixed pH and, if coupled with molecular mechanics or molecular dynamics methods, can also be used for more realistic studies of protein folding, unfolding, and dynamics, as a function of pH. PMID:18683966

On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies

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

McKechnie, Scott; Booth, George H.; Cohen, Aron J.

The best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density-functional theory (DFT) and wave function methods: Hartree-Fock theory (HF), second-order Møller-Plesset perturbation theory (MP2) and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionizationmore » energies obtained from total energy diff calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correction give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared.« less

Momentum and Heat Flux Measurements in the Exhaust of VASIMR Using Helium Propellant

NASA Technical Reports Server (NTRS)

Chavers, D. Gregory

2002-01-01

Electromagnetic thrusters typically use electric and magnetic fields to accelerate and exhaust plasma through interactions with the charged particles in the plasma. The energy required to create the plasma, i.e. ionization energy, is potential energy between the electron and ion. This potential energy is typically lost since it is not recovered as the plasma is exhausted and is known as frozen flow loss. If the frozen flow energy is a small fraction of the total plasma energy, this frozen flow loss may be negligible. However, if the frozen flow energy is a major fraction of the total plasma energy, this loss can severely reduce the energy efficiency of the thruster. Recovery and utilization of this frozen flow energy can improve the energy efficiency of a thruster during low specific impulse operating regimes when the ionization energy is a large fraction of the total plasma energy. This paper quantifies the recovery of the frozen flow energy, i.e. recombination energy, via the process of surface recombination for helium. To accomplish this task the momentum flux and heat flux of the plasma flow were measured and compared to calculated values from electrostatic probe data. This information was used to deduce the contribution of recombination energy to the total heat flux on a flat plate as well as to characterize the plasma conditions. Helium propellant was investigated initially due to its high ionization potential and hence available recombination energy.

G W calculations using the spectral decomposition of the dielectric matrix: Verification, validation, and comparison of methods

DOE PAGES

Pham, T. Anh; Nguyen, Huy -Viet; Rocca, Dario; ...

2013-04-26

Inmore » a recent paper we presented an approach to evaluate quasiparticle energies based on the spectral decomposition of the static dielectric matrix. This method does not require the calculation of unoccupied electronic states or the direct diagonalization of large dielectric matrices, and it avoids the use of plasmon-pole models. The numerical accuracy of the approach is controlled by a single parameter, i.e., the number of eigenvectors used in the spectral decomposition of the dielectric matrix. Here we present a comprehensive validation of the method, encompassing calculations of ionization potentials and electron affinities of various molecules and of band gaps for several crystalline and disordered semiconductors. Lastly, we demonstrate the efficiency of our approach by carrying out G W calculations for systems with several hundred valence electrons.« less

Prospects and limitations for p-type doping in boron nitride polymorphs

NASA Astrophysics Data System (ADS)

Weston, Leigh; van de Walle, Chris G.

Using first-principles calculations, we examine the potential for p-type doping of BN polymorphs via substitutional impurities. Based on density functional theory with a hybrid functional, our calculations reveal that group-IV elements (C, Si) substituting at the N site result in acceptor levels that are more than 1 eV above the valence-band maximum in all of the BN polymorphs, and hence far too deep to allow for p-type doping. On the other hand, group-II elements (Be, Mg) substituting at the B site lead to shallower acceptor levels. However, for the ground-state hexagonal phase (h-BN), we show that p-type doping at the B site is inhibited by the formation of hole polarons. Our calculations reveal that hole localization is intrinsic to sp2 bonded h-BN, and this places fundamental limits on hole conduction in this material. In contrast, the sp3 bonded wurtzite (w-BN) and cubic (c-BN) polymorphs are capable of forming shallow acceptor levels. For Be dopants, the acceptor ionization energies are 0.31 eV and 0.24 eV for w-BN and c-BN, respectively; these values are only slightly larger than the ionization energy of the Mg acceptor in GaN. This work was supported by NSF.

Properties of air-aluminum thermal plasmas

NASA Astrophysics Data System (ADS)

Cressault, Y.; Gleizes, A.; Riquel, G.

2012-07-01

We present the calculation and the main results of the properties of air-aluminum thermal plasmas, useful for complete modelling of arc systems involving aluminum contacts. The properties are calculated assuming thermal equilibrium and correspond to the equilibrium composition, thermodynamic functions, transport coefficients including diffusion coefficients and net emission coefficient representing the divergence of the radiative flux in the hottest plasma regions. The calculation is developed in the temperature range between 2000 and 30 000 K, for a pressure range from 0.1 to 1 bar and for several metal mass proportions. As in the case of other metals, the presence of aluminum vapours has a strong influence on three properties at intermediate temperatures: the electron number density, the electrical conductivity and the net emission coefficient. Some comparisons with other metal vapour (Cu, Fe and Ag) properties are made and show the original behaviour for Al-containing mixtures: mass density at high temperatures is low due to the low Al atomic mass; high electrical conductivity at T < 10 000 K due to low ionization potential (around 2 V less for Al than for the other metals); very strong self-absorption of ionized aluminum lines, leading to a net emission coefficient lower than that of pure air when T > 10 000 K, in contrast to copper or iron radiation.

Partially ionized hydrogen plasma in strong magnetic fields.

PubMed

Potekhin, A Y; Chabrier, G; Shibanov, Y A

1999-08-01

We study the thermodynamic properties of a partially ionized hydrogen plasma in strong magnetic fields, B approximately 10(12)-10(13) G, typical of neutron stars. The properties of the plasma depend significantly on the quantum-mechanical sizes and binding energies of the atoms, which are strongly modified by thermal motion across the field. We use new fitting formulas for the atomic binding energies and sizes, based on accurate numerical calculations and valid for any state of motion of the atom. In particular, we take into account decentered atomic states, neglected in previous studies of thermodynamics of magnetized plasmas. We also employ analytic fits for the thermodynamic functions of nonideal fully ionized electron-ion Coulomb plasmas. This enables us to construct an analytic model of the free energy. An ionization equilibrium equation is derived, taking into account the strong magnetic field effects and the nonideality effects. This equation is solved by an iteration technique. Ionization degrees, occupancies, and the equation of state are calculated.

Electron-impact total ionization cross sections of DNA sugar-phosphate backbone and an additivity principle

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Dateo, Christopher E.

2005-01-01

The improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64, 042719-1 (2001)l is used to study the total ionization cross sections of the DNA sugar-phosphate backbone by electron impact. Calculations using neutral fragments found that the total ionization cross sections of C3' - and C5', -deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3' - and C5" -deoxyribose-phospate cross sections, differing by less than 10%. The result implies that certain properties of the-DNA, like the total singly ionization cross section, are localized properties and a building-up or additivity principle may apply. This allows us to obtain accurate properties of larger molecular systems built up from the results of smaller subsystem fragments. Calculations are underway using a negatively charged sugar-phosphate backbone with a metal counter-ion.

Application of galvanomagnetic measurements in temperature range 70-300 K to MBE GaAs layers characterization

NASA Astrophysics Data System (ADS)

Wolkenberg, Andrzej; Przeslawski, Tomasz

1996-04-01

Galvanomagnetic measurements were performed on the square shaped samples after Van der Pauw and on the Hall bar at low electric fields app. 1.5 V/cm and magnetic induction app. 6 kG in order to make a comparison between the theoretical and experimental results of the temperature dependence of mobility and resistivity from 70 K to 300 K. A calculation method was obtained of the drift mobility and the Hall mobility in which the scatterings are applied: on ionized impurities, on polar optical phonons, on acoustic phonons (deformation potential), on acoustic phonons (piezoelectric potential) and on dislocations. The elaborated method transformed to a computer program allows us to fit experimental values of the resistivity and the Hall mobility to those calculated. The fitting procedure makes it possible to characterize the quality of the n-type GaAs MBE layer, i.e. the net electron concentration, whole ionized impurities concentration and dislocation density after Read space charge cylinders model. The calculations together with the measurements allow us to obtain compensation ratio value in the layer, too. The influence of the epitaxial layer thickness on layers measurements accuracy in the case of Van der Pauw square probe was investigated. It was stated that in the layers under 3 micrometer the bulk properties are strongly influenced by both surfaces. The results of measurements of the same layer using the Van der Pauw and the Hall bar structure were compared. It was stated that the Hall bar structure only could be used to obtain proper measurements results.

Silyl group internal rotation in S1 phenylsilane and phenylsilane cation: Experiments and ab initio calculations

NASA Astrophysics Data System (ADS)

Lu, Kueih-Tzu; Weisshaar, James C.

1993-09-01

Resonant two-photon ionization (R2PI) and pulsed field ionization (PFI) were used to measure S1-S0 and cation-S1 spectra of internally cold phenylsilane. We measure the adiabatic ionization potentials IP(phenylsilane)=73 680±5 cm-1, IP(phenylsilane ṡAr)=73 517±5 cm-1 and IP(phenylsilane ṡAr2)=73 359±5 cm-1. We assign many low lying torsion-vibration levels of the S1 (à 1A1) state and of X˜ 2B1 of phenylsilane+. In both states, the pure torsional transitions are well fit by a simple sixfold hindered rotor Hamiltonian. The results for the rotor inertial constant B and internal rotation potential barrier V6 are, in S1, B=2.7±0.2 cm-1 and V6=-44±4 cm-1; in the cation, B=2.7±0.2 cm-1 and V6=+19±3 cm-1. The sign of V6 and the conformation of minimum energy are inferred from spectral intensities of bands terminating on the 3a`1 and 3a`2 torsional levels. In S1 the staggered conformation is most stable, while in the cation ground state the eclipsed conformation is most stable. For all sixfold potentials whose absolute phase is known experimentally, the most stable conformer is staggered in the neutral states (S0 and S1 p-fluorotoluene, S1 toluene, S1 p-fluorotoluene) and eclipsed in the cationic states (ground state toluene+ and phenylsilane+). In phenylsilane+ we estimate several potential energy coupling matrix elements between torsional and vibrational states. For small V6, the term PαPa in the rigid-frame model Hamiltonian strongly mixes the 6a'1 and 6a'2 torsional states, which mediates further torsion-vibrational coupling. In addition, the cation X˜ 2B1 vibrational structure is badly perturbed, apparently by strong vibronic coupling with the low-lying à 2A2 state. Accordingly, ab initio calculations find a substantial in-plane distortion of the equilibrium geometry of the X˜ 2B1 state, while the à 2A2 state is planar and symmetric. The calculations also correctly predict the lowest energy conformer for S0 states and for cation ground states. Finally, we adapt the natural resonance theory (NRT) of Glendening and Weinhold to suggest why sixfold barriers for methyl and silyl rotors are uniformly small, while some threefold barriers are quite large. The phase of the sixfold potential is apparently determined by a subtle competition between two types of rotor-ring potential terms: attractive donor-acceptor interactions and repulsive van der Waals interactions (steric effects).

The Inverse-Square Law and the Exponential Attenuation Law Used to the Shielding Calculation in Radiotherapy on a High School Level

NASA Astrophysics Data System (ADS)

de Paiva, Eduardo

2016-04-01

Every year millions of people contract cancer in the world, and according to prediction of the World Health Organization by the year 2030 there will be about 27 million new cases. Because of these figures and the resulting social and economic implications of this disease, radiotherapy, which is one form of treatment that uses ionizing radiation, has a great importance. In the classroom the teacher can introduce the subject of the use of ionizing radiation in medicine and the basic physical principles to calculate the thickness of the walls of the rooms that house ionizing radiation sources.

Electron- and positron-impact atomic scattering calculations using propagating exterior complex scaling

NASA Astrophysics Data System (ADS)

Bartlett, P. L.; Stelbovics, A. T.; Rescigno, T. N.; McCurdy, C. W.

2007-11-01

Calculations are reported for four-body electron-helium collisions and positron-hydrogen collisions, in the S-wave model, using the time-independent propagating exterior complex scaling (PECS) method. The PECS S-wave calculations for three-body processes in electron-helium collisions compare favourably with previous convergent close-coupling (CCC) and time-dependent exterior complex scaling (ECS) calculations, and exhibit smooth cross section profiles. The PECS four-body double-excitation cross sections are significantly different from CCC calculations and highlight the need for an accurate representation of the resonant helium final-state wave functions when undertaking these calculations. Results are also presented for positron-hydrogen collisions in an S-wave model using an electron-positron potential of V12 = - (8 + (r1 - r2)2)-1/2. This model is representative of the full problem, and the results demonstrate that ECS-based methods can accurately calculate scattering, ionization and positronium formation cross sections in this three-body rearrangement collision.

Calculations of the Electron Energy Distribution Function in a Uranium Plasma by Analytic and Monte Carlo Techniques. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Bathke, C. G.

1976-01-01

Electron energy distribution functions were calculated in a U235 plasma at 1 atmosphere for various plasma temperatures and neutron fluxes. The distributions are assumed to be a summation of a high energy tail and a Maxwellian distribution. The sources of energetic electrons considered are the fission-fragment induced ionization of uranium and the electron induced ionization of uranium. The calculation of the high energy tail is reduced to an electron slowing down calculation, from the most energetic source to the energy where the electron is assumed to be incorporated into the Maxwellian distribution. The pertinent collisional processes are electron-electron scattering and electron induced ionization and excitation of uranium. Two distinct methods were employed in the calculation of the distributions. One method is based upon the assumption of continuous slowing and yields a distribution inversely proportional to the stopping power. An iteration scheme is utilized to include the secondary electron avalanche. In the other method, a governing equation is derived without assuming continuous electron slowing. This equation is solved by a Monte Carlo technique.

Effects of target heating on experiments using Kα and Kβ diagnostics.

PubMed

Palmeri, P; Boutoux, G; Batani, D; Quinet, P

2015-09-01

We describe the impact of heating and ionization on emission from the target of Kα and Kβ radiation induced by the propagation of hot electrons generated by laser-matter interaction. We consider copper as a test case and, starting from basic principles, we calculate the changes in emission wavelength, ionization cross section, and fluorescence yield as Cu is progressively ionized. We have finally considered the more realistic case when hot electrons have a distribution of energies with average energies of 50 and 500 keV (representative respectively of "shock ignition" and of "fast ignition" experiments) and in which the ions are distributed according to ionization equilibrium. In addition, by confronting our theoretical calculations with existing data, we demonstrate that this study offers a generic theoretical background for temperature diagnostics in laser-plasma interactions.

Accurate Cross Sections for Microanalysis.

PubMed

Rez, Peter

2002-01-01

To calculate the intensity of x-ray emission in electron beam microanalysis requires a knowledge of the energy distribution of the electrons in the solid, the energy variation of the ionization cross section of the relevant subshell, the fraction of ionizations events producing x rays of interest and the absorption coefficient of the x rays on the path to the detector. The theoretical predictions and experimental data available for ionization cross sections are limited mainly to K shells of a few elements. Results of systematic plane wave Born approximation calculations with exchange for K, L, and M shell ionization cross sections over the range of electron energies used in microanalysis are presented. Comparisons are made with experimental measurement for selected K shells and it is shown that the plane wave theory is not appropriate for overvoltages less than 2.5 V.

Ionization of nS, nP, and nD lithium, potassium, and cesium Rydberg atoms by blackbody radiation

NASA Astrophysics Data System (ADS)

Beterov, I. I.; Ryabtsev, I. I.; Tretyakov, D. B.; Bezuglov, N. N.; Ékers, A.

2008-07-01

The results of theoretical calculations of the blackbody ionization rates of lithium, potassium, and cesium atoms residing in Rydberg states are presented. The calculations are performed for nS, nP, and nD states in a wide range of principal quantum numbers, n = 8-65, for blackbody radiation temperatures T = 77, 300, and 600 K. The calculations are performed using the known quasi-classical formulas for the photoionization cross sections and for the radial matrix elements of transitions in the discrete spectrum. The effect of the blackbody-radiation-induced population redistribution between Rydberg states on the blackbody ionization rates measured under laboratory conditions is quantitatively analyzed. Simple analytical formulas that approximate the numerical results and that can be used to estimate the blackbody ionization rates of Rydberg atoms are presented. For the S series of lithium, the rate of population of high-lying Rydberg levels by blackbody radiation is found to anomalously behave as a function of n. This anomaly is similar to the occurrence of the Cooper minimum in the discrete spectrum.

Space charge dosimeters for extremely low power measurements of radiation in shipping containers

DOEpatents

Britton, Jr., Charles L.; Buckner, Mark A [Oak Ridge, TN; Hanson, Gregory R [Clinton, TN; Bryan, William L [Knoxville, TN

2011-05-03

Methods and apparatus are described for space charge dosimeters for extremely low power measurements of radiation in shipping containers. A method includes insitu polling a suite of passive integrating ionizing radiation sensors including reading-out dosimetric data from a first passive integrating ionizing radiation sensor and a second passive integrating ionizing radiation sensor, where the first passive integrating ionizing radiation sensor and the second passive integrating ionizing radiation sensor remain situated where the dosimetric data was integrated while reading-out. Another method includes arranging a plurality of ionizing radiation sensors in a spatially dispersed array; determining a relative position of each of the plurality of ionizing radiation sensors to define a volume of interest; collecting ionizing radiation data from at least a subset of the plurality of ionizing radiation sensors; and triggering an alarm condition when a dose level of an ionizing radiation source is calculated to exceed a threshold.

Space charge dosimeters for extremely low power measurements of radiation in shipping containers

DOEpatents

Britton, Jr; Charles, L [Alcoa, TN; Buckner, Mark A [Oak Ridge, TN; Hanson, Gregory R [Clinton, TN; Bryan, William L [Knoxville, TN

2011-04-26

Methods and apparatus are described for space charge dosimeters for extremely low power measurements of radiation in shipping containers. A method includes in situ polling a suite of passive integrating ionizing radiation sensors including reading-out dosimetric data from a first passive integrating ionizing radiation sensor and a second passive integrating ionizing radiation sensor, where the first passive integrating ionizing radiation sensor and the second passive integrating ionizing radiation sensor remain situated where the dosimetric data was integrated while reading-out. Another method includes arranging a plurality of ionizing radiation sensors in a spatially dispersed array; determining a relative position of each of the plurality of ionizing radiation sensors to define a volume of interest; collecting ionizing radiation data from at least a subset of the plurality of ionizing radiation sensors; and triggering an alarm condition when a dose level of an ionizing radiation source is calculated to exceed a threshold.

BADGER v1.0: A Fortran equation of state library

NASA Astrophysics Data System (ADS)

Heltemes, T. A.; Moses, G. A.

2012-12-01

The BADGER equation of state library was developed to enable inertial confinement fusion plasma codes to more accurately model plasmas in the high-density, low-temperature regime. The code had the capability to calculate 1- and 2-T plasmas using the Thomas-Fermi model and an individual electron accounting model. Ion equation of state data can be calculated using an ideal gas model or via a quotidian equation of state with scaled binding energies. Electron equation of state data can be calculated via the ideal gas model or with an adaptation of the screened hydrogenic model with ℓ-splitting. The ionization and equation of state calculations can be done in local thermodynamic equilibrium or in a non-LTE mode using a variant of the Busquet equivalent temperature method. The code was written as a stand-alone Fortran library for ease of implementation by external codes. EOS results for aluminum are presented that show good agreement with the SESAME library and ionization calculations show good agreement with the FLYCHK code. Program summaryProgram title: BADGERLIB v1.0 Catalogue identifier: AEND_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEND_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 41 480 No. of bytes in distributed program, including test data, etc.: 2 904 451 Distribution format: tar.gz Programming language: Fortran 90. Computer: 32- or 64-bit PC, or Mac. Operating system: Windows, Linux, MacOS X. RAM: 249.496 kB plus 195.630 kB per isotope record in memory Classification: 19.1, 19.7. Nature of problem: Equation of State (EOS) calculations are necessary for the accurate simulation of high energy density plasmas. Historically, most EOS codes used in these simulations have relied on an ideal gas model. This model is inadequate for low-temperature, high-density plasma conditions; the gaseous and liquid phases; and the solid phase. The BADGER code was developed to give more realistic EOS data in these regimes. Solution method: BADGER has multiple, user-selectable models to treat the ions, average-atom ionization state and electrons. Ion models are ideal gas and quotidian equation of state (QEOS), ionization models are Thomas-Fermi and individual accounting method (IEM) formulation of the screened hydrogenic model (SHM) with l-splitting, electron ionization models are ideal gas and a Helmholtz free energy minimization method derived from the SHM. The default equation of state and ionization models are appropriate for plasmas in local thermodynamic equilibrium (LTE). The code can calculate non-LTE equation of state (EOS) and ionization data using a simplified form of the Busquet equivalent-temperature method. Restrictions: Physical data are only provided for elements Z=1 to Z=86. Multiple solid phases are not currently supported. Liquid, gas and plasma phases are combined into a generalized "fluid" phase. Unusual features: BADGER divorces the calculation of average-atom ionization from the electron equation of state model, allowing the user to select ionization and electron EOS models that are most appropriate to the simulation. The included ion ideal gas model uses ground-state nuclear spin data to differentiate between isotopes of a given element. Running time: Example provided only takes a few seconds to run.

A theoretical study of the photoinduced desorption of I — from a CF3I dimer

NASA Astrophysics Data System (ADS)

Tossell, J. A.

1997-04-01

Ab initio SCF-MO calculations using effective core-potential basis sets are employed to evaluate ionization potentials and electron affinities for CF3I and the geometries and energies of the singlet and triplet states of the CF3I dimer. The calculated geometry of the single state of the dimer is in qualitative agreement with the experimental geometry for condensed phase CF3I. The calculated energy for vertical excitation from the singlet to the triplet state is 4.1 eV at the Hartree-Fock level and 4.5 eV after incorporation of correlation at the Moller-Plesset 2nd-order level, consistent with excitation by 193 nm (6.4 eV) light. The equilibrium geometry of the triplet consists essentially of a CF3I+, CF3I- ion pair, in which the Csbnd I bond distance in the anionic component has increased to 5.5Å, compared with 2.1Åin the neutral molecule. The calculated binding energy of the triplet ion pair is about 4 eV.

Perturbative calculation of two-photon double electron ionization of helium

NASA Astrophysics Data System (ADS)

Ivanov, I. A.; Kheifets, A. S.

2008-05-01

We report the total integrated cross-section (TICS) of two-photon double ionization of helium in the photon energy range from 40 to 54 eV. We compute the TICS in the lowest order perturbation theory (LOPT) using the length and Kramers-Henneberger gauges of the electromagnetic interaction. Our findings indicate that the LOPT gives results for the TICS in agreement with our earlier non-perturbative calculations.

A group electronegativity equalization scheme including external potential effects.

PubMed

Leyssens, Tom; Geerlings, Paul; Peeters, Daniel

2006-07-20

By calculating the electron affinity and ionization energy of different functional groups, CCSD electronegativity values are obtained, which implicitly account for the effect of the molecular environment. This latter is approximated using a chemically justified point charge model. On the basis of Sanderson's electronegativity equalization principle, this approach is shown to lead to reliable "group in molecule" electronegativities. Using a slight adjustment of the modeled environment and first-order principles, an electronegativity equalization scheme is obtained, which implicitly accounts for the major part of the external potential effect. This scheme can be applied in a predictive manner to estimate the charge transfer between two functional groups, without having to rely on cumbersome calibrations. A very satisfactory correlation is obtained between these charge transfers and those obtained from an ab initio calculation of the entire molecule.

Computational Model of D-Region Ion Production Caused by Energetic Electron Precipitations Based on General Monte Carlo Transport Calculations

NASA Astrophysics Data System (ADS)

Kouznetsov, A.; Cully, C. M.

2017-12-01

During enhanced magnetic activities, large ejections of energetic electrons from radiation belts are deposited in the upper polar atmosphere where they play important roles in its physical and chemical processes, including VLF signals subionospheric propagation. Electron deposition can affect D-Region ionization, which are estimated based on ionization rates derived from energy depositions. We present a model of D-region ion production caused by an arbitrary (in energy and pitch angle) distribution of fast (10 keV - 1 MeV) electrons. The model relies on a set of pre-calculated results obtained using a general Monte Carlo approach with the latest version of the MCNP6 (Monte Carlo N-Particle) code for the explicit electron tracking in magnetic fields. By expressing those results using the ionization yield functions, the pre-calculated results are extended to cover arbitrary magnetic field inclinations and atmospheric density profiles, allowing ionization rate altitude profile computations in the range of 20 and 200 km at any geographic point of interest and date/time by adopting results from an external atmospheric density model (e.g. NRLMSISE-00). The pre-calculated MCNP6 results are stored in a CDF (Common Data Format) file, and IDL routines library is written to provide an end-user interface to the model.

Ultrafast internal conversion dynamics of highly excited pyrrole studied with VUV/UV pump probe spectroscopy.

PubMed

Horton, Spencer L; Liu, Yusong; Chakraborty, Pratip; Matsika, Spiridoula; Weinacht, Thomas

2017-02-14

We study the relaxation dynamics of pyrrole after excitation with an 8 eV pump pulse to a state just 0.2 eV below the ionization potential using vacuum ultraviolet/ultraviolet pump probe spectroscopy. Our measurements in conjunction with electronic structure calculations indicate that pyrrole undergoes rapid internal conversion to the ground state in less than 300 fs. We find that internal conversion to the ground state dominates over dissociation.

Web-Based Computational Chemistry Education with CHARMMing III: Reduction Potentials of Electron Transfer Proteins

PubMed Central

Perrin, B. Scott; Miller, Benjamin T.; Schalk, Vinushka; Woodcock, H. Lee; Brooks, Bernard R.; Ichiye, Toshiko

2014-01-01

A module for fast determination of reduction potentials, E°, of redox-active proteins has been implemented in the CHARMM INterface and Graphics (CHARMMing) web portal (www.charmming.org). The free energy of reduction, which is proportional to E°, is composed of an intrinsic contribution due to the redox site and an environmental contribution due to the protein and solvent. Here, the intrinsic contribution is selected from a library of pre-calculated density functional theory values for each type of redox site and redox couple, while the environmental contribution is calculated from a crystal structure of the protein using Poisson-Boltzmann continuum electrostatics. An accompanying lesson demonstrates a calculation of E°. In this lesson, an ionizable residue in a [4Fe-4S]-protein that causes a pH-dependent E° is identified, and the E° of a mutant that would test the identification is predicted. This demonstration is valuable to both computational chemistry students and researchers interested in predicting sequence determinants of E° for mutagenesis. PMID:25058418

Analytical instruments, ionization sources, and ionization methods

DOEpatents

Atkinson, David A.; Mottishaw, Paul

2006-04-11

Methods and apparatus for simultaneous vaporization and ionization of a sample in a spectrometer prior to introducing the sample into the drift tube of the analyzer are disclosed. The apparatus includes a vaporization/ionization source having an electrically conductive conduit configured to receive sample particulate which is conveyed to a discharge end of the conduit. Positioned proximate to the discharge end of the conduit is an electrically conductive reference device. The conduit and the reference device act as electrodes and have an electrical potential maintained between them sufficient to cause a corona effect, which will cause at least partial simultaneous ionization and vaporization of the sample particulate. The electrical potential can be maintained to establish a continuous corona, or can be held slightly below the breakdown potential such that arrival of particulate at the point of proximity of the electrodes disrupts the potential, causing arcing and the corona effect. The electrical potential can also be varied to cause periodic arcing between the electrodes such that particulate passing through the arc is simultaneously vaporized and ionized. The invention further includes a spectrometer containing the source. The invention is particularly useful for ion mobility spectrometers and atmospheric pressure ionization mass spectrometers.

Ambient mass spectrometry: Direct analysis of dimethoate, tebuconazole, and trifloxystrobin on olive and vine leaves by desorption electrospray ionization interface.

PubMed

Mainero Rocca, Lucia; Cecca, Juri; L'Episcopo, Nunziata; Fabrizi, Giovanni

2017-11-01

A new field of application for a relatively new mass-spectrometric interface such as desorption electrospray ionization was evaluated. For this purpose, its behavior was tested versus quantitative analysis of dimethoate, trifloxystrobin, and tebuconazole directly on olive and vine leaves surface. The goal was workers exposure assessment during field re-entry operations since evidence suggests an association between chronic occupational exposure to some agrochemicals and severe adverse effects. Desorption electrospray ionization gave good response working in positive ionization mode, while numerous test were necessary for the choice of a unique blend of spray solvents suitable for all 3 substances. The best compromise, in terms of signal to noise ratios, was obtained with the CH 3 OH/H 2 O (80:20) mixture. The obvious difficulties related to the impossibility to use the internal standard were overcome through an accurate validation. Limits of detection and quantitation, dynamic ranges, matrix effects, and intraday precisions were calculated, and a small monitoring campaign was arranged to test method applicability and to evaluate potential dermal exposure. This protocol was developed in work safety field, but after a brief investigation, it was find to be suitable also for food residue evaluation. Copyright © 2017 John Wiley & Sons, Ltd.

Effect of the corrected ionization potential and spatial distribution on the angular and energy distribution in tunnel ionization

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

Petrović, V. M.; Miladinović, T. B., E-mail: tanja.miladinovic@gmail.com

2016-05-15

Within the framework of the Ammosov–Delone–Krainov theory, we consider the angular and energy distribution of outgoing electrons due to ionization by a circularly polarized electromagnetic field. A correction of the ground ionization potential by the ponderomotive and Stark shift is incorporated in both distributions. Spatial dependence is analyzed.

Dynamic target ionization using an ultrashort pulse of a laser field

NASA Astrophysics Data System (ADS)

Makarov, D. N.; Matveev, V. I.; Makarova, K. A.

2014-09-01

Ionization processes under the interaction of an ultrashort pulse of an electromagnetic field with atoms in nonstationary states are considered. As an example, the ionization probability of the hydrogen-like atom upon the decay of quasi-stationary state is calculated. The method developed can be applied to complex systems, including targets in collisional states and various chemical reactions.

Reprint of: Ionization probabilities of Ne, Ar, Kr, and Xe by proton impact for different initial states and impact energies

NASA Astrophysics Data System (ADS)

Montanari, C. C.; Miraglia, J. E.

2018-01-01

In this contribution we present ab initio results for ionization total cross sections, probabilities at zero impact parameter, and impact parameter moments of order +1 and -1 of Ne, Ar, Kr, and Xe by proton impact in an extended energy range from 100 keV up to 10 MeV. The calculations were performed by using the continuum distorted wave eikonal initial state approximation (CDW-EIS) for energies up to 1 MeV, and using the first Born approximation for larger energies. The convergence of the CDW-EIS to the first Born above 1 MeV is clear in the present results. Our inner-shell ionization cross sections are compared with the available experimental data and with the ECPSSR results. We also include in this contribution the values of the ionization probabilities at the origin, and the impact parameter dependence. These values have been employed in multiple ionization calculations showing very good description of the experimental data. Tables of the ionization probabilities are presented, disaggregated for the different initial bound states, considering all the shells for Ne and Ar, the M-N shells of Kr and the N-O shells of Xe.

Electron mobility in modulation-doped heterostructures

NASA Technical Reports Server (NTRS)

Walukiewicz, W.; Ruda, H. E.; Lagowski, J.; Gatos, H. C.

1984-01-01

A model for electron mobility in a two-dimensional electron gas confined in a triangular well was developed. All major scattering processes (deformation potential and piezoelectric acoustic, polar optical, ionized impurity, and alloy disorder) were included, as well as intrasubband and intersubband scattering. The model is applied to two types of modulation-doped heterostructures, namely GaAs-GaAlAs and In(0.53)Ga(0.47)As-Al(0.52)In(0.48)As. In the former case, phonons and remote ionized impurities ultimately limit the mobility, whereas in the latter, alloy disorder is a predominant scattering process at low temperatures. The calculated mobilities are in very good agreement with recently reported experimental characteristics for both GaAs-Ga(1-x)Al(x)As and In(0.53)Ga(0.47)As-Al(0.52)In(0.48)As modulation-doped heterostructures.

Electron ionization of metastable nitrogen and oxygen atoms in relation to the auroral emissions

NASA Astrophysics Data System (ADS)

Pandya, Siddharth; Joshipura, K. N.

Atomic and molecular excited metastable states (EMS) are exotic systems due to their special properties like long radiative life-time, large size (average radius) and large polarizability along with relatively smaller first ionization energy compared to their respective ground states (GS). The present work includes our theoretical calculations on electron impact ionization of metastable atomic states N( (2) P), N( (2) D) of nitrogen and O( (1) S), O( (1) D) of oxygen. The targets of our present interest, are found to be present in our Earth's ionosphere and they play an important role in auroral emissions observed in Earth’s auroral regions [1] as also in the emissions observed from cometary coma [2, 3] and airglow emissions. In particular, atomic oxygen in EMS can radiate, the visible O( (1) D -> (3) P) doublet 6300 - 6364 Å red doublet, the O( (1) S -> (1) D) 5577 Å green line, and the ultraviolet O( (1) S -> (3) P) 2972 Å line. For metastable atomic nitrogen one observes the similar emissions, in different wavelengths, from (2) D and (2) P states. At the Earth's auroral altitudes, from where these emissions take place in the ionosphere, energetic electrons are also present. In particular, if the metastable N as well as O atoms are ionized by the impact of electrons then these species are no longer available for emissions. This is a possible loss mechanism, and hence it is necessary to analyze the importance of electron ionization of the EMS of atomic O and N, by calculating the relevant cross sections. In the present paper we investigate electron ionization of the said metastable species by calculating relevant total cross sections. Our quantum mechanical calculations are based on projected approximate ionization contribution in the total inelastic cross sections [4]. Detailed results and discussion along with the significance of these calculations will be presented during the COSPAR-2014. References [1] A.Bhardwaj, and G. R. Gladstone, Rev. Geophys., 38(3), 295-353 (2000) [2] A.Bhardwaj, and S. A. Haider, Adv. Space Res., 29(5), 745-750 (2002) [3] A. Bhardwaj and S. Raghuram, ApJ, 748:13 (2012) [4] S. H. Pandya et al.,Int. J. Mass Spectrom. 323-324, 28-33 (2012)

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.

Attenuation characteristics of electromagnetic waves in a weak collisional and fully ionized dusty plasma

NASA Astrophysics Data System (ADS)

Dan, Li; Guo, Li-Xin; Li, Jiang-Ting; Chen, Wei; Yan, Xu; Huang, Qing-Qing

2017-09-01

The expression of complex dielectric permittivity for non-magnetized fully ionized dusty plasma is obtained based on the kinetic equation in the Fokker-Planck-Landau collision model and the charging equation of the statistical theory. The influences of density, average size of dust grains, and balanced charging of the charge number of dust particles on the attenuation properties of electromagnetic waves in fully ionized dusty plasma are investigated by calculating the attenuation constant. In addition, the attenuation characteristics of weakly ionized and fully ionized dusty plasmas are compared. Results enriched the physical mechanisms of microwave attenuation for fully ionized dusty plasma and provide a theoretical basis for future studies.

HF-enhanced 4278-Å airglow: evidence of accelerated ionosphere electrons?

NASA Astrophysics Data System (ADS)

Fallen, C. T.; Watkins, B. J.

2013-12-01

We report calculations from a one-dimensional physics-based self-consistent ionosphere model (SCIM) demonstrating that HF-heating of F-region electrons can produce 4278-Å airglow enhancements comparable in magnitude to those reported during ionosphere HF modification experiments at the High-frequency Active Auroral Research Program (HAARP) observatory in Alaska. These artificial 'blue-line' emissions, also observed at the EISCAT ionosphere heating facility in Norway, have been attributed to arise solely from additional production of N2+ ions through impact ionization of N2 molecules by HF-accelerated electrons. Each N2+ ion produced by impact ionization or photoionization has a probability of being created in the N2+(1N) excited state, resulting in a blue-line emission from the allowed transition to its ground state. The ionization potential of N2 exceeds 18 eV, so enhanced impact ionization of N2 implies that significant electron acceleration processes occur in the HF-modified ionosphere. Further, because of the fast N2+ emission time, measurements of 4278-Å intensity during ionosphere HF modification experiments at HAARP have also been used to estimate artificial ionization rates. To the best of our knowledge, all observations of HF-enhanced blue-line emissions have been made during twilight conditions when resonant scattering of sunlight by N2+ ions is a significant source of 4278-Å airglow. Our model calculations show that F-region electron heating by powerful O-mode HF waves transmitted from HAARP is sufficient to increase N2+ ion densities above the shadow height through temperature-enhanced ambipolar diffusion and temperature-suppressed ion recombination. Resonant scattering from the modified sunlit region can cause a 10-20 R increase in 4278-Å airglow intensity, comparable in magnitude to artificial emissions measured during ionosphere HF-modification experiments. This thermally-induced artificial 4278-Å aurora occurs independently of any artificial aurora maintained by HF-accelerated (non-thermal) electrons. The numerical results presented here do not necessarily rule out the presence of HF-accelerated electrons with energies exceeding 18 eV. However, vertical or field-aligned airglow intensity measurements made during twilight conditions do not provide definitive evidence of energetic HF-accelerated electrons. Consequently, artificial blue-line airglow measurements should not be used to estimate N2+ ionization rates without also accounting for temperature-dependent chemistry and diffusion. Future experiments that make simultaneous measurements of N2+ ion airglow emissions from both the first negative bands and the Meinel bands can potentially resolve the relative contributions of accelerated electron and resonant scattering mechanisms. Airglow emission rates from these bands are expected to be in strict proportion when the emissions result from electron impact ionization of N2 molecules. Side-view altitude-resolved 4278-Å airglow measurements may also indicate the presence of energetic HF-accelerated electrons if the blue-line emissions are determined to occur below the shadow height.

Simple and universal model for electron-impact ionization of complex biomolecules

NASA Astrophysics Data System (ADS)

Tan, Hong Qi; Mi, Zhaohong; Bettiol, Andrew A.

2018-03-01

We present a simple and universal approach to calculate the total ionization cross section (TICS) for electron impact ionization in DNA bases and other biomaterials in the condensed phase. Evaluating the electron impact TICS plays a vital role in ion-beam radiobiology simulation at the cellular level, as secondary electrons are the main cause of DNA damage in particle cancer therapy. Our method is based on extending the dielectric formalism. The calculated results agree well with experimental data and show a good comparison with other theoretical calculations. This method only requires information of the chemical composition and density and an estimate of the mean binding energy to produce reasonably accurate TICS of complex biomolecules. Because of its simplicity and great predictive effectiveness, this method could be helpful in situations where the experimental TICS data are absent or scarce, such as in particle cancer therapy.

Theoretical studies of photoexcitation and ionization in H2O

NASA Technical Reports Server (NTRS)

Diercksen, G. H. F.; Kraemer, W. P.; Rescigno, T. N.; Bender, C. F.; Mckoy, B. V.; Langhoff, S. R.; Langhoff, P. W.

1982-01-01

Theoretical studies using Franck-Condon and static-exchange approximations are reported for the complete dipole excitation and ionization spectrum in H2O, where (1) large Cartesian Gaussian basis sets are used to represent the required discrete and continuum electronic eigenfunctions at the ground state equilibrium geometry, and (2) previously devised moment-theory techniques are employed in constructing the continuum oscillator-strength densities from the calculated spectra. Comparisons are made of the calculated excitation and ionization profiles with recent experimental photoabsorption studies and corresponding spectral assignments, electron impact-excitation cross sections, and dipole and synchrotron-radiation studies of partial-channel photoionization cross sections. The calculated partial-channel cross sections are found to be atomic-like, and dominated by 2p-kd components. It is suggested that the latter transition couples with the underlying 1b(1)-kb(1) channel, accounting for a prominent feature in recent synchrotron-radiation measurements.

Calculation of fully differential cross sections for the near threshold double ionization of helium atoms

NASA Astrophysics Data System (ADS)

Singh, Prithvi; Purohit, Ghanshyam; Dorn, Alexander; Ren, Xueguang; Patidar, Vinod

2016-01-01

Fully differential cross sectional (FDCS) results are reported for the electron-impact double ionization of helium atoms at 5 and 27 eV excess energy. The present attempt to calculate the FDCS in the second Born approximation and treating the postcollision interaction is helpful to analyze the measurements of Ren et al (2008 Phys. Rev. Lett. 101 093201) and Durr et al (2007 Phys. Rev. Lett. 98 193201). The second-order processes and postcollision interaction have been found to be significant in describing the trends of the FDCS. More theoretical effort is required to describe the collision dynamics of electron-impact double ionization of helium atoms at near threshold.

Summary of Research/Publications

NASA Technical Reports Server (NTRS)

1997-01-01

Summary of research/publications include:(1) Comment on broadening of water microwave lines by collisions with helium atoms; (2) Calculations of ion-molecule deuterium fractionation reactions involving HD; (3) Ab initio predictions on the rotational spectra of carbon-chain carbene molecules; (4) Theoretical IR spectra of ionized naphthalene; (5) Improved collisional excitation rates for interstellar water; (6) Calculations on the competition between association and reaction for C3H+ + H2; (7) Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization; (8) Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2; (9) New calculations on the ion-molecule processes C2H2+ + H2 C2H3+ + H and C2H2+ + H2 C2H4+; (10) Anisotropic rigid rotor potential energy function for H2O-H2; (11) A correlated ab initio study of linear carbon-chain radicals CnH (n=2-7); (12) Ab initio characterization of MgCCH, MgCCH+, and MgC2 and pathways to their formation in the interstellar medium; (13) Why HOC+ is detectable in interstellar clouds: The rate of the reaction between HOC+ and H2; (14) A correlated ab initio study of the X 2A 1 and A 2E states of MgCH3; (15) On the stability of interstellar carbon clusters: The rate of the reaction between C3 and O; and (16) The rate of the reaction between CN and C2H2 at interstellar temperatures.

Effect of a magnetic field on the track structure of low-energy electrons: a Monte Carlo study

NASA Astrophysics Data System (ADS)

Bug, M. U.; Gargioni, E.; Guatelli, S.; Incerti, S.; Rabus, H.; Schulte, R.; Rosenfeld, A. B.

2010-10-01

The increasing use of MRI-guided radiation therapy evokes the necessity to investigate the potential impact of a magnetic field on the biological effectiveness of therapeutic radiation beams. While it is known that a magnetic field, applied during irradiation, can improve the macroscopic absorbed dose distribution of electrons in the tumor region, effects on the microscopic distribution of energy depositions and ionizations have not yet been investigated. An effect on the number of ionizations in a DNA segment, which is related to initial DNA damage in form of complex strand breaks, could be beneficial in radiation therapy. In this work we studied the effects of a magnetic field on the pattern of ionizations at nanometric level by means of Monte Carlo simulations using the Geant4-DNA toolkit. The track structure of low-energy electrons in the presence of a uniform static magnetic field of strength up to 14 T was calculated for a simplified DNA segment model in form of a water cylinder. In the case that no magnetic field is applied, nanodosimetric results obtained with Geant4-DNA were compared with those from the PTB track structure code. The obtained results suggest that any potential enhancement of complexity of DNA strand breaks induced by irradiation in a magnetic field is not related to modifications of the low-energy secondary electrons track structure.

First-principle interaction potentials for metastable He(3S) and Ne(3P) with closed-shell molecules: Application to Penning-ionizing systems

NASA Astrophysics Data System (ADS)

Hapka, Michał; Chałasiński, Grzegorz; Kłos, Jacek; Żuchowski, Piotr S.

2013-07-01

We present new interaction potential curves, calculated from first-principles, for the He(3S, 1s12s1)⋯H2 and He(3S)⋯Ar systems, relevant in recent Penning ionization experiments of Henson et al. [Science 338, 234 (2012), 10.1126/science.1229141]. Two different approaches were applied: supermolecular using coupled cluster (CC) theory and perturbational within symmetry-adapted perturbation theory (SAPT). Both methods gave consistent results, and the potentials were used to study the elastic scattering and determine the positions of shape resonances for low kinetic energy (up to 1 meV). We found a good agreement with the experiment. In addition, we investigated two other dimers composed of metastable Ne (3P, 2p53s1) and ground state He and Ar atoms. For the Ne(3P)⋯He system, a good agreement between CC and SAPT approaches was obtained. The Ne(3P)⋯Ar dimer was described only with SAPT, as CC gave divergent results. Ne* systems exhibit extremely small electronic orbital angular momentum anisotropy of the potentials. We attribute this effect to screening of an open 2p shell by a singly occupied 3s shell.

Ionization Processes in the Atmosphere of Titan (Research Note). III. Ionization by High-Z Nuclei Cosmic Rays

NASA Technical Reports Server (NTRS)

Gronoff, G.; Mertens, C.; Lilensten, J.; Desorgher, L.; Fluckiger, E.; Velinov, P.

2011-01-01

Context. The Cassini-Huygens mission has revealed the importance of particle precipitation in the atmosphere of Titan thanks to in-situ measurements. These ionizing particles (electrons, protons, and cosmic rays) have a strong impact on the chemistry, hence must be modeled. Aims. We revisit our computation of ionization in the atmosphere of Titan by cosmic rays. The high-energy high-mass ions are taken into account to improve the precision of the calculation of the ion production profile. Methods. The Badhwahr and O Neill model for cosmic ray spectrum was adapted for the Titan model. We used the TransTitan model coupled with the Planetocosmics model to compute the ion production by cosmic rays. We compared the results with the NAIRAS/HZETRN ionization model used for the first time for a body that differs from the Earth. Results. The cosmic ray ionization is computed for five groups of cosmic rays, depending on their charge and mass: protons, alpha, Z = 8 (oxygen), Z = 14 (silicon), and Z = 26 (iron) nucleus. Protons and alpha particles ionize mainly at 65 km altitude, while the higher mass nucleons ionize at higher altitudes. Nevertheless, the ionization at higher altitude is insufficient to obscure the impact of Saturn s magnetosphere protons at a 500 km altitude. The ionization rate at the peak (altitude: 65 km, for all the different conditions) lies between 30 and 40/cu cm/s. Conclusions. These new computations show for the first time the importance of high Z cosmic rays on the ionization of the Titan atmosphere. The updated full ionization profile shape does not differ significantly from that found in our previous calculations (Paper I: Gronoff et al. 2009, 506, 955) but undergoes a strong increase in intensity below an altitude of 400 km, especially between 200 and 400 km altitude where alpha and heavier particles (in the cosmic ray spectrum) are responsible for 40% of the ionization. The comparison of several models of ionization and cosmic ray spectra (in intensity and composition) reassures us about the stability of the altitude of the ionization peak (65 km altitude) with respect to the solar activity.

Efficient GW calculations using eigenvalue-eigenvector decomposition of the dielectric matrix

NASA Astrophysics Data System (ADS)

Nguyen, Huy-Viet; Pham, T. Anh; Rocca, Dario; Galli, Giulia

2011-03-01

During the past 25 years, the GW method has been successfully used to compute electronic quasi-particle excitation spectra of a variety of materials. It is however a computationally intensive technique, as it involves summations over occupied and empty electronic states, to evaluate both the Green function (G) and the dielectric matrix (DM) entering the expression of the screened Coulomb interaction (W). Recent developments have shown that eigenpotentials of DMs can be efficiently calculated without any explicit evaluation of empty states. In this work, we will present a computationally efficient approach to the calculations of GW spectra by combining a representation of DMs in terms of its eigenpotentials and a recently developed iterative algorithm. As a demonstration of the efficiency of the method, we will present calculations of the vertical ionization potentials of several systems. Work was funnded by SciDAC-e DE-FC02-06ER25777.

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

NASA Astrophysics Data System (ADS)

Poklonski, N. A.; Vyrko, S. A.; Poklonskaya, O. N.; Kovalev, A. I.; Zabrodskii, A. G.

2016-06-01

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator-metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atoms with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature Tj is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature Tj, the concentration of "free" holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3Tj/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to Tj hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (-1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the range from 3 × 1017 to 3 × 1020 cm-3, i.e., up to the Mott transition. The model uses no fitting parameters.

Rydberg States of Alkali Metal Atoms on Superfluid Helium Droplets - Theoretical Considerations

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

2017-06-01

The bound states of electrons on the surface of superfluid helium have been a research topic for several decades. One of the first systems treated was an electron bound to an ionized helium cluster. Here, a similar system is considered, which consists of a helium droplet with an ionized dopant inside and an orbiting electron on the outside. In our theoretical investigation we select alkali metal atoms (AK) as central ions, stimulated by recent experimental studies of Rydberg states for Na, Rb, and Cs attached to superfluid helium nanodroplets. Experimental spectra , obtained by electronic excitation and subsequent ionization, showed blueshifts for low lying electronic states and redshifts for Rydberg states. In our theoretical treatment the diatomic AK^+-He potential energy curves are first computed with ab initio methods. These potentials are then used to calculate the solvation energy of the ion in a helium droplet as a function of the number of atoms. Additional potential terms, derived from the obtained helium density distribution, are added to the undisturbed atomic pseudopotential in order to simulate a 'modified' potential felt by the outermost electron. This allows us to compute a new set of eigenstates and eigenenergies, which we compare to the experimentally observed energy shifts for highly excited alkali metal atoms on helium nanodroplets. A. Golov and S. Sekatskii, Physica B, 1994, 194, 555-556 E. Loginov, C. Callegari, F. Ancilotto, and M. Drabbels, J. Phys. Chem. A, 2011, 115, 6779-6788 F. Lackner, G. Krois, M. Koch, and W. E. Ernst, J. Phys. Chem. Lett., 2012, 3, 1404-1408 F. Lackner, G. Krois, M. Theisen, M. Koch, and W. E. Ernst, Phys. Chem. Chem. Phys., 2011, 13, 18781-18788

A fresh look at the photoelectron spectrum of bromobenzene: A third-order non-Dyson electron propagator study.

PubMed

Schneider, M; Soshnikov, D Yu; Holland, D M P; Powis, I; Antonsson, E; Patanen, M; Nicolas, C; Miron, C; Wormit, M; Dreuw, A; Trofimov, A B

2015-10-14

The valence-shell ionization spectrum of bromobenzene, as a representative halogen substituted aromatic, was studied using the non-Dyson third-order algebraic-diagrammatic construction [nD-ADC(3)] approximation for the electron propagator. This method, also referred to as IP-ADC(3), was implemented as a part of the Q-Chem program and enables large-scale calculations of the ionization spectra, where the computational effort scales as n(5) with respect to the number of molecular orbitals n. The IP-ADC(3) scheme is ideally suited for investigating low-lying ionization transitions, so fresh insight could be gained into the cationic state manifold of bromobenzene. In particular, the present IP-ADC(3) calculations with the cc-pVTZ basis reveal a whole class of low-lying low-intensity two-hole-one-particle (2h-1p) doublet and quartet states, which are relevant to various photoionization processes. The good qualitative agreement between the theoretical spectral profile for the valence-shell ionization transitions generated with the smaller cc-pVDZ basis set and the experimental photoelectron spectrum measured at a photon energy of 80 eV on the PLÉIADES beamline at the Soleil synchrotron radiation source allowed all the main features to be assigned. Some theoretical aspects of the ionization energy calculations concerning the use of various approximation schemes and basis sets are discussed.

A fresh look at the photoelectron spectrum of bromobenzene: A third-order non-Dyson electron propagator study

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

Schneider, M.; Wormit, M.; Dreuw, A.

2015-10-14

The valence-shell ionization spectrum of bromobenzene, as a representative halogen substituted aromatic, was studied using the non-Dyson third-order algebraic-diagrammatic construction [nD-ADC(3)] approximation for the electron propagator. This method, also referred to as IP-ADC(3), was implemented as a part of the Q-Chem program and enables large-scale calculations of the ionization spectra, where the computational effort scales as n{sup 5} with respect to the number of molecular orbitals n. The IP-ADC(3) scheme is ideally suited for investigating low-lying ionization transitions, so fresh insight could be gained into the cationic state manifold of bromobenzene. In particular, the present IP-ADC(3) calculations with the cc-pVTZmore » basis reveal a whole class of low-lying low-intensity two-hole-one-particle (2h-1p) doublet and quartet states, which are relevant to various photoionization processes. The good qualitative agreement between the theoretical spectral profile for the valence-shell ionization transitions generated with the smaller cc-pVDZ basis set and the experimental photoelectron spectrum measured at a photon energy of 80 eV on the PLÉIADES beamline at the Soleil synchrotron radiation source allowed all the main features to be assigned. Some theoretical aspects of the ionization energy calculations concerning the use of various approximation schemes and basis sets are discussed.« less

Electron impact ionization in the vicinity of comets

NASA Astrophysics Data System (ADS)

Cravens, T. E.; Kozyra, J. U.; Nagy, A. F.; Gombosi, T. I.; Kurtz, M.

1987-07-01

The solar wind interacts very strongly with the extensive cometary coma, and the various interaction processes are initiated by the ionization of cometary neutrals. The main ionization mechanism far outside the cometary bow shock is photoionization by solar extreme ultraviolet radiation.Electron distributions measured in the vicinity of comets Halley and Giacobini-Zinner by instruments on the VEGA and ICE spacecraft, respectively, are used to calculate electron impact ionization frequencies. Ionization by electrons is of comparable importance to photoionization in the magnetosheaths of Comets Halley and Giacobini-Zinner. The ionization frequency in the inner part of the cometary plasma region of comet Halley is several times greater than the photoionization value. Tables of ionization frequencies as functions of electron temperature are presented for H2O, CO2, CO, O, N2, and H.

Kβ/ Kα intensity ratios for X-ray production in 3d metals by gamma-rays and protons

NASA Astrophysics Data System (ADS)

Bhuinya, C. R.; Padhi, H. C.

1994-04-01

Systematic measurements of Kβ/ Kα intensity ratios for X-ray production in 3d metals have been carried out using γ-ray and fast proton ionization methods. The measured ratios from proton ionization experiments indicate production of multivacancies in the L shell giving rise to higher Kβ/ Kα ratios compared to the present γRF results and 2 MeV proton ionization results of Perujo et al. [Perujo A., Maxwell J. A., Teesdale W. J. and Cambell J. L. (1987) J. Phys. B: Atom. Molec. Phys.20, 4973]. This is consistent with the SCA model calculation which gives increased simultaneous K- and L-shell ionization at 4 MeV. The present results from γRF experiments are in close agreement with the 2 MeV proton ionization results of Perujo et al. (1987) and also with the theoretical calculation of jankowski and Polasik [Jankowski K. and Polasik M. (1989) J. Phys. B: Atom. Molec. Optic. Phys. 22, 2369] but the theoretical results of Scofield [Scofield J. H. (1974a) Atom. Data Nucl. Data Tables14, 12] are somewhat higher.

How Very Massive Metal-Free Stars Start Cosmological Reionization

NASA Technical Reports Server (NTRS)

Wise, John H.; Abel, Tom

2008-01-01

The initial conditions and relevant physics for the formation of the earliest galaxies are well specified in the concordance cosmology. Using ab initio cosmological Eulerian adaptive mesh refinement radiation hydrodynamical calculations, we discuss how very massive stars start the process of cosmological reionization. The models include nonequilibrium primordial gas chemistry and cooling processes and accurate radiation transport in the case B approximation using adaptively ray-traced photon packages, retaining the time derivative in the transport equation. Supernova feedback is modeled by thermal explosions triggered at parsec scales. All calculations resolve the local Jeans length by at least 16 grid cells at all times and as such cover a spatial dynamic range of approx.10(exp 6). These first sources of reionization are highly intermittent and anisotropic and first photoionize the small-scale voids surrounding the halos they form in, rather than the dense filaments they are embedded in. As the merging objects form larger, dwarf-sized galaxies, the escape fraction of UV radiation decreases and the H II regions only break out on some sides of the galaxies, making them even more anisotropic. In three cases, SN blast waves induce star formation in overdense regions that were formed earlier from ionization front instabilities. These stars form tens of parsecs away from the center of their parent DM halo. Approximately five ionizing photons are needed per sustained ionization when star formation in 10(exp 6) stellar Mass halos is dominant in the calculation. As the halos become larger than approx.10(exp 7) Stellar Mass, the ionizing photon escape fraction decreases, which in turn increases the number of photons per ionization to 15-50, in calculations with stellar feedback only. Radiative feedback decreases clumping factors by 25% when compared to simulations without star formation and increases the average temperature of ionized gas to values between 3000 and 10,000 K.

Electronic structure and pair potential energy analysis of 4-n-methoxy-4′-cyanobiphenyl: A nematic liquid crystal

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

Sharma, Dipendra, E-mail: d-11sharma@rediffmail.com; Tiwari, S. N., E-mail: sntiwari123@rediffmail.com; Dwivedi, M. K., E-mail: dwivedi-ji@gmail.com

2016-05-06

Electronic structure properties of 4-n-methoxy-4′-cyanobiphenyl, a pure nematic liquid crystal have been examined using an ab‒initio, HF/6‒31G(d,p) technique with GAMESS program. Conformational and charge distribution analysis have been carried out. MEP, HOMO and LUMO surfaces have been scanned. Ionization potential, electron affinity, electronegativity, global hardness and softness of the liquid crystal molecule have been calculated. Further, stacking, side by side and end to end interactions between a molecular pair have been evaluated. Results have been used to elucidate the physico-chemical and liquid crystalline properties of the system.

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

Whittles, Thomas J.; Veal, Tim D.; Savory, Christopher N.

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa (1-x)Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from themore » antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.« less

Estimated congener specific gas-phase atmospheric behavior and fractionation of perfluoroalkyl compounds: rates of reaction with atmospheric oxidants, air-water partitioning, and wet/dry deposition lifetimes.

PubMed

Rayne, Sierra; Forest, Kaya; Friesen, Ken J

2009-08-01

A quantitative structure-activity model has been validated for estimating congener specific gas-phase hydroxyl radical reaction rates for perfluoroalkyl sulfonic acids (PFSAs), carboxylic acids (PFCAs), aldehydes (PFAls) and dihydrates, fluorotelomer olefins (FTOls), alcohols (FTOHs), aldehydes (FTAls), and acids (FTAcs), and sulfonamides (SAs), sulfonamidoethanols (SEs), and sulfonamido carboxylic acids (SAAs), and their alkylated derivatives based on calculated semi-empirical PM6 method ionization potentials. Corresponding gas-phase reaction rates with nitrate radicals and ozone have also been estimated using the computationally derived ionization potentials. Henry's law constants for these classes of perfluorinated compounds also appear to be reasonably approximated by the SPARC software program, thereby allowing estimation of wet and dry atmospheric deposition rates. Both congener specific gas-phase atmospheric and air-water interface fractionation of these compounds is expected, complicating current source apportionment perspectives and necessitating integration of such differential partitioning influences into future multimedia models. The findings will allow development and refinement of more accurate and detailed local through global scale atmospheric models for the atmospheric fate of perfluoroalkyl compounds.

Theoretical investigation of structures and energetics of sodium adatom and its dimer on graphene: DFT study

NASA Astrophysics Data System (ADS)

Kaur, Gagandeep; Gupta, Shuchi; Rani, Pooja; Dharamvir, Keya

2015-11-01

Extensive ab initio calculations have been performed to study the energetics of a sodium (Na) atom and its dimer adsorbed on graphene using the SIESTA package Soler et al. (2002) [1] which works within a DFT(density functional theory)-GGA (generalized gradient approximation) pseudopotential framework. The adsorption energy, geometry, charge transfer, ionization potential and density of states (DOS), partial density states (PDOS) of adatom/dimer-graphene system have been calculated. After considering various sites for adsorption of Na on graphene, the center of a hexagonal ring of carbon atoms is found to be the preferred site of adsorption while the Na2 dimer prefers to rest parallel to the graphene sheet. We find insignificant energy differences among adsorption configurations involving different possible sites in parallel orientation, which implies high mobility of the dimer on the graphene sheet. We also notice only a slight distortion of the graphene sheet perpendicular to its plane upon adatom adsorption. However, some lateral displacements seen are more perceptible. Summary The adsorption energy, geometry, charge transfer, ionization potential and density of states (DOS) and PDOS of adatom/dimer-graphene system have been calculated using SIESTA package Soler et al. (2002) [1] which works within a DFT(density functional theory)-GGA (generalized gradient approximation) pseudopotential framework. Preferred site for adsorption of a sodium atom on graphene is the hollow site. For the Na dimer adsorption, we found that horizontal orientation is favored over the vertical one. From DOS plots, it is clear that graphene's states are nearly unaffected by the adsorption of Na adatom and Interaction between sodium and graphene is predominantly ionic

Exploring the surface reactivity of 3d metal endofullerenes: a density-functional theory study.

PubMed

Estrada-Salas, Rubén E; Valladares, Ariel A

2009-09-24

Changes in the preferential sites of electrophilic, nucleophilic, and radical attacks on the pristine C60 surface with endohedral doping using 3d transition metal atoms were studied via two useful reactivity indices, namely the Fukui functions and the molecular electrostatic potential. Both of these were calculated at the density functional BPW91 level of theory with the DNP basis set. Our results clearly show changes in the preferential reactivity sites on the fullerene surface when it is doped with Mn, Fe, Co, or Ni atoms, whereas there are no significant changes in the preferential reactivity sites on the C60 surface upon endohedral doping with Cu and Zn atoms. Electron affinities (EA), ionization potentials (IP), and HOMO-LUMO gaps (Eg) were also calculated to complete the study of the endofullerene's surface reactivity. These findings provide insight into endofullerene functionalization, an important issue in their application.

DISCOVERY OF RUBIDIUM, CADMIUM, AND GERMANIUM EMISSION LINES IN THE NEAR-INFRARED SPECTRA OF PLANETARY NEBULAE

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

Sterling, N. C.; Dinerstein, Harriet L.; Kaplan, Kyle F.

We identify [Rb iv] 1.5973 and [Cd iv] 1.7204 μm emission lines in high-resolution (R = 40,000) near-infrared spectra of the planetary nebulae (PNe) NGC 7027 and IC 5117, obtained with the Immersion GRating INfrared Spectrometer (IGRINS) on the 2.7 m telescope at McDonald Observatory. We also identify [Ge vi] 2.1930 μm in NGC 7027. Alternate identifications for these features are ruled out based on the absence of other multiplet members and/or transitions with the same upper levels. Ge, Rb, and Cd can be enriched in PNe by s-process nucleosynthesis during the asymptotic giant branch stage of evolution. To determine ionic abundances, we calculate [Rb iv] collision strengthsmore » and use approximations for those of [Cd iv] and [Ge vi]. Our identification of [Rb iv] 1.5973 μm is supported by the agreement between Rb{sup 3+}/H{sup +} abundances found from this line and the 5759.55 Å feature in NGC 7027. Elemental Rb, Cd, and Ge abundances are derived with ionization corrections based on similarities in ionization potential ranges between the detected ions and O and Ne ionization states. Our analysis indicates abundances 2–4 times solar for Rb and Cd in both nebulae. Ge is subsolar in NGC 7027, but its abundance is uncertain due to the large and uncertain ionization correction. The general consistency of the measured relative s-process enrichments with predictions from models appropriate for these PNe (2.0–2.5 M{sub ⊙}, [Fe/H] = −0.37) demonstrates the potential of using PN compositions to test s-process nucleosynthesis models.« less

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

The flow of a dust particle by highly collisional drifting plasma

NASA Astrophysics Data System (ADS)

Grach, Veronika; Semenov, Vladimir; Trakhtengerts, Victor

We present the study of the flow of a dust particle by a weakly ionized highly collisional drifting plasma. The charging of a conductive sphere and wake formation downstream and upstream of it is analyzed in the case of a strong external field l0 = E0 /(4πen0 ) λD a (E0 is the magnitude of the external field, n0 is plasma density, λD is Debye length and a is a radius of the sphere). Under such conditions, the effects of the space charge field and ionization-recombination processes play crucial role. The sphere charge and the spatial distributions of plasma ions and electrons are calculated nu-merically; analytical expressions are obtained for some limiting cases. We obtain that the size of the wake is determined by the external field and the recombination rate. At low recombination rates (α/(4πµ+,- ) 1, where α is the recombination coefficient, µ+,- are mobilities of positive and negative plasma particles) the longitudinal scale of wake is about 20l0 , at high recombina-tion rates the longitudinal scale is about l0 . The transverse scale of the wake is determined by the ratio of the mobilities and can reach several dust particle radii. It was also shown that the absolute value of the dust particle charge decreases with increasing recombination rate. The total electric charge (the sphere charge plus the plasma space charge) is shown to be zero in accordance with predictions of the theory of static currents in a conducting medium. On the basis of the obtained spatial distributions of charged plasma particles, the electrostatic potential around the sphere is calculated numerically. The interaction potential between two systems "particle+wake" is analyzed for arbitrary locations of such systems. We obtain that the potential can be attractive at moderate and large distances, if the particles are not aligned in the direction perpendicular to the external electric field. The results can be important in understanding intergrain interactions in weakly ionized highly collisional anisotropic dusty plasmas.

Adenine radicals generated in alternating AT duplexes by direct absorption of low-energy UV radiation.

PubMed

Banyasz, Akos; Ketola, Tiia; Martínez-Fernández, Lara; Improta, Roberto; Markovitsi, Dimitra

2018-04-17

There is increasing evidence that the direct absorption of photons with energies that are lower than the ionization potential of nucleobases may result in oxidative damage to DNA. The present work, which combines nanosecond transient absorption spectroscopy and quantum mechanical calculations, studies this process in alternating adenine-thymine duplexes (AT)n. We show that the one-photon ionization quantum yield of (AT)10 at 266 nm (4.66 eV) is (1.5 ± 0.3) × 10-3. According to our PCM/TD-DFT calculations carried out on model duplexes composed of two base pairs, (AT)1 and (TA)1, simultaneous base pairing and stacking does not induce important changes in the absorption spectra of the adenine radical cation and deprotonated radical. The adenine radicals, thus identified in the time-resolved spectra, disappear with a lifetime of 2.5 ms, giving rise to a reaction product that absorbs at 350 nm. In parallel, the fingerprint of reaction intermediates other than radicals, formed directly from singlet excited states and assigned to AT/TA dimers, is detected at shorter wavelengths. PCM/TD-DFT calculations are carried out to map the pathways leading to such species and to characterize their absorption spectra; we find that, in addition to the path leading to the well-known TA* photoproduct, an AT photo-dimerization path may be operative in duplexes.

Ionospheres of the terrestrial planets

NASA Astrophysics Data System (ADS)

Schunk, R. W.; Nagy, A. F.

1980-11-01

The theory and observations relating to the ionospheres of the terrestrial planets Venus, the earth, and Mars are reviewed. Emphasis is placed on comparing the basic differences and similarities between the planetary ionospheres. The review covers the plasma and electric-magnetic field environments that surround the planets, the theory leading to the creation and transport of ionization in the ionospheres, the relevant observations, and the most recent model calculations. The theory section includes a discussion of ambipolar diffusion in a partially ionized plasma, diffusion in a fully ionized plasma, supersonic plasma flow, photochemistry, and heating and cooling processes. The sections on observations and model calculations cover the neutral atmosphere composition, the ion composition, the electron density, and the electron, ion, and neutral temperatures.

Electron impact ionization dynamics of para-benzoquinone

NASA Astrophysics Data System (ADS)

Jones, D. B.; Ali, E.; Ning, C. G.; Colgan, J.; Ingólfsson, O.; Madison, D. H.; Brunger, M. J.

2016-10-01

Triple differential cross sections (TDCSs) for the electron impact ionization of the unresolved combination of the 4 highest occupied molecular orbitals (4b3g, 5b2u, 1b1g, and 2b3u) of para-benzoquinone are reported. These were obtained in an asymmetric coplanar geometry with the scattered electron being observed at the angles -7.5°, -10.0°, -12.5° and -15.0°. The experimental cross sections are compared to theoretical calculations performed at the molecular 3-body distorted wave level, with a marginal level of agreement between them being found. The character of the ionized orbitals, through calculated momentum profiles, provides some qualitative interpretation for the measured angular distributions of the TDCS.

Single and double multiphoton ionization of Li and Be atoms by strong laser fields

NASA Astrophysics Data System (ADS)

Telnov, Dmitry; Heslar, John; Chu, Shih-I.

2011-05-01

The time-dependent density functional theory with self-interaction correction and proper asymptotic long-range potential is extended for nonperturbative treatment of multiphoton single and double ionization of Li and Be atoms by strong 800 nm laser fields. We make use of the time-dependent Krieger-Li-Iafrate (TDKLI) exchange-correlation potential with the integer discontinuity which improves the description of the double ionization process. However, we have found that the discontinuity of the TDKLI potential is not sufficient to reproduce the characteristic feature of double ionization. This may happen because the discontinuity of the TDKLI potential is related to the spin particle numbers only and not to the total particle number. Introducing a discontinuity with respect to the total particle number to the exchange-correlation potential, we were able to obtain the knee structure in the intensity dependence of the double ionization probability of Be. This work was partially supported by DOE and NSF and by NSC-Taiwan.

Total Dose Effects of Ionizing and Non-Ionizing Radiation on Piezoresistive Pressure Transducer Chips

DTIC Science & Technology

2003-03-01

facility and Mr. Joseph Talnagi of the Ohio State Research Reactor facility for their personal guidance and insight into reactor dosimetry and neutron...62 Test C1: Dosimetry ..................................................................................................... 63 Special...66 Annex A-3. Preliminary Dosimetry Calculations

Synthesis of photochromic nanoparticles and determination of the mechanism of photochromism

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

Inoue, Shuhei, E-mail: shu18@hiroshima-u.ac.jp; Matsumura, Yukihiko; Kawamoto, Takahiro

2016-05-15

Photochromic nanoparticles of zinc-silicon oxide were synthesized using plasma enhanced chemical vapor deposition. These particles turned black upon irradiating with ultraviolet light. We investigated this phenomenon using density functional theory calculations. Silicon inclusions create trap levels and oxygen defects that reduce the ionization potential of ZnO. This forms a quantum potential between ZnO and zinc-silicon oxide, and the excited electron is stable. Because oxygen defects also increase the bond overlap population between the zinc atoms in a ZnO crystal, they introduce further defects and help in the formation of quantum potentials. Growth of a perfect crystal of ZnO prevents themore » formation of oxygen defects, which is not desirable for photochromism.« less

Secondary ionization in a flat universe

NASA Technical Reports Server (NTRS)

Atrio-Barandela, F.; Doroshkevich, A. G.

1994-01-01

We analyze the effect of a secondary ionization on the evolution of temperature fluctuations in cosmic background radiation. The main results presented in this paper are appropriate analytic expressions of the transfer function relating temperature fluctuations to matter density perturbations at recombination for all possible recombination histories. Furthermore, we particularize our calculation to the standard cold dark matter model, where we study the erasure of primordial temperature fluctuations and calculate the magnitude and angular scale of the damping induced by a late recombination.

Design of Shallow Acceptors in GaN through Zinc-Magnium Codoping: First-Principles Calculation

NASA Astrophysics Data System (ADS)

Liu, Zhiqiang; Melton, Andrew G.; Yi, Xiaoyan; Wang, Jianwei; Kucukgok, Bahadir; Kang, Jun; Lu, Na; Wang, Junxi; Li, Jinmin; Ferguson, Ian

2013-04-01

In this work, we propose a novel approach to reduce the ionization energy of acceptors in GaN through Zn-Mg codoping. The characteristics of the defect states and the valence-band maximum (VBM) were investigated via first-principles calculation. Our results indicated that the original VBM of the host GaN could be altered by Zn-Mg codoping, thus improving the p-type dopability. We show that the calculated ionization energy ɛ(0/-) of the Zn-Mg acceptor is only 117 meV, which is about 90 meV shallower than that of the isolated Mg acceptor.

Ionization chamber-based reference dosimetry of intensity modulated radiation beams.

PubMed

Bouchard, Hugo; Seuntjens, Jan

2004-09-01

The present paper addresses reference dose measurements using thimble ionization chambers for quality assurance in IMRT fields. In these radiation fields, detector fluence perturbation effects invalidate the application of open-field dosimetry protocol data for the derivation of absorbed dose to water from ionization chamber measurements. We define a correction factor C(Q)IMRT to correct the absorbed dose to water calibration coefficient N(D, w)Q for fluence perturbation effects in individual segments of an IMRT delivery and developed a calculation method to evaluate the factor. The method consists of precalculating, using accurate Monte Carlo techniques, ionization chamber, type-dependent cavity air dose, and in-phantom dose to water at the reference point for zero-width pencil beams as a function of position of the pencil beams impinging on the phantom surface. These precalculated kernels are convolved with the IMRT fluence distribution to arrive at the dose-to-water-dose-to-cavity air ratio [D(a)w (IMRT)] for IMRT fields and with a 10x10 cm2 open-field fluence to arrive at the same ratio D(a)w (Q) for the 10x10 cm2 reference field. The correction factor C(Q)IMRT is then calculated as the ratio of D(a)w (IMRT) and D(a)w (Q). The calculation method was experimentally validated and the magnitude of chamber correction factors in reference dose measurements in single static and dynamic IMRT fields was studied. The results show that, for thimble-type ionization chambers the correction factor in a single, realistic dynamic IMRT field can be of the order of 10% or more. We therefore propose that for accurate reference dosimetry of complete n-beam IMRT deliveries, ionization chamber fluence perturbation correction factors must explicitly be taken into account.

Hot interstellar gas and ionization of embedded clouds

NASA Technical Reports Server (NTRS)

Cheng, K.-P.; Bruhweiler, F.

1990-01-01

Researchers present detailed photoionization calculations for the instellar cloud in which the Sun is embedded. They consider the EUV radiation field with contribution from discrete stellar sources and from a thermal bremsstrahlung-radiative recombination spectrum emitted from the surrounding 10 to the 6th power k coronal substrate. They establish lower limits to the fractional ionization of hydrogen and helium of 0.17 and 0.29 respectively. The high He ionization fraction results primarily from very strong line emission below 500 A originating in the surrounding coronal substrate while the H ionization is dominated by the EUV radiation from the discrete stellar sources. The dual effects of thermal conduction and the EUV spectrum of the 10 to the 6th k plasma on ionization in the cloud skin are explored. The EUV radiation field and Auger ionization have insignificant effects on the resulting ionic column densities of Si IV, C IV, N V and O VI through the cloud skin. Calculations show that the abundances of these species are dominated by collisional ionization in the thermal conduction front. Because of a low charge exchange rate with hydrogen, the ionic column density ratios of N (CIII)/N (CII) and N (NII)/N (NI) are dominated by the EUV radiation field in the local interstellar medium. These ratios should be important diagnostics for the EUV radiation field and serve as surrogate indicators of the interstellar He and H ionization fraction respectively. Spacecraft such as Lyman which is designed to obtain high resolution spectral data down to the Lyman limit at 912 A could sample interstellar lines of these ions.

Prediction of the critical reduced electric field strength for carbon dioxide and its mixtures with copper vapor from Boltzmann analysis for a gas temperature range of 300 K to 4000 K at 0.4 MPa

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

Li, Xingwen, E-mail: xwli@mail.xjtu.edu.cn; Guo, Xiaoxue; Zhao, Hu

2015-04-14

The influence of copper vapor mixed in hot CO{sub 2} on dielectric breakdown properties of gas mixture at a fixed pressure of 0.4 MPa for a temperature range of 300 K–4000 K is numerically analyzed. First, the equilibrium composition of hot CO{sub 2} with different copper fractions is calculated using a method based on mass action law. The next stage is devoted to computing the electron energy distribution functions (EEDF) by solving the two-term Boltzmann equation. The reduced ionization coefficient, the reduced attachment coefficient, and the reduced effective ionization coefficient are then obtained based on the EEDF. Finally, the critical reduced electric fieldmore » (E/N){sub cr} is obtained. The results indicate that an increasing mole fraction of copper markedly reduces (E/N){sub cr} of the CO{sub 2}–Cu gas mixtures because of copper's low ionization potential and large ionization cross section. Additionally, the generation of O{sub 2} from the thermal dissociation of CO{sub 2} contributes to the increase of (E/N){sub cr} of CO{sub 2}–Cu hot gas mixtures from about 2000 K to 3500 K.« less

Accuracy of theory for calculating electron impact ionization of molecules

NASA Astrophysics Data System (ADS)

Chaluvadi, Hari Hara Kumar

The study of electron impact single ionization of atoms and molecules has provided valuable information about fundamental collisions. The most detailed information is obtained from triple differential cross sections (TDCS) in which the energy and momentum of all three final state particles are determined. These cross sections are much more difficult for theory since the detailed kinematics of the experiment become important. There are many theoretical approximations for ionization of molecules. One of the successful methods is the molecular 3-body distorted wave (M3DW) approximation. One of the strengths of the DW approximation is that it can be applied for any energy and any size molecule. One of the approximations that has been made to significantly reduce the required computer time is the OAMO (orientation averaged molecular orbital) approximation. In this dissertation, the accuracy of the M3DW-OAMO is tested for different molecules. Surprisingly, the M3DW-OAMO approximation yields reasonably good agreement with experiment for ionization of H2 and N2. On the other hand, the M3DW-OAMO results for ionization of CH4, NH3 and DNA derivative molecules did not agree very well with experiment. Consequently, we proposed the M3DW with a proper average (PA) calculation. In this dissertation, it is shown that the M3DW-PA calculations for CH4 and SF6 are in much better agreement with experimental data than the M3DW-OAMO results.

Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations.

PubMed

van Meer, R; Gritsenko, O V; Baerends, E J

2014-10-14

In recent years, several benchmark studies on the performance of large sets of functionals in time-dependent density functional theory (TDDFT) calculations of excitation energies have been performed. The tested functionals do not approximate exact Kohn-Sham orbitals and orbital energies closely. We highlight the advantages of (close to) exact Kohn-Sham orbitals and orbital energies for a simple description, very often as just a single orbital-to-orbital transition, of molecular excitations. Benchmark calculations are performed for the statistical average of orbital potentials (SAOP) functional for the potential [J. Chem. Phys. 2000, 112, 1344; 2001, 114, 652], which approximates the true Kohn-Sham potential much better than LDA, GGA, mGGA, and hybrid potentials do. An accurate Kohn-Sham potential does not only perform satisfactorily for calculated vertical excitation energies of both valence and Rydberg transitions but also exhibits appealing properties of the KS orbitals including occupied orbital energies close to ionization energies, virtual-occupied orbital energy gaps very close to excitation energies, realistic shapes of virtual orbitals, leading to straightforward interpretation of most excitations as single orbital transitions. We stress that such advantages are completely lost in time-dependent Hartree-Fock and partly in hybrid approaches. Many excitations and excitation energies calculated with local density, generalized gradient, and hybrid functionals are spurious. There is, with an accurate KS, or even the LDA or GGA potentials, nothing problematic about the "band gap" in molecules: the HOMO-LUMO gap is close to the first excitation energy (the optical gap).

Ionizing potential waves and high-voltage breakdown streamers.

NASA Technical Reports Server (NTRS)

Albright, N. W.; Tidman, D. A.

1972-01-01

The structure of ionizing potential waves driven by a strong electric field in a dense gas is discussed. Negative breakdown waves are found to propagate with a velocity proportional to the electric field normal to the wavefront. This causes a curved ionizing potential wavefront to focus down into a filamentary structure, and may provide the reason why breakdown in dense gases propagates in the form of a narrow leader streamer instead of a broad wavefront.

On the thermodynamic properties of thermal plasma in the flame kernel of hydrocarbon/air premixed gases

NASA Astrophysics Data System (ADS)

Askari, Omid; Beretta, Gian Paolo; Eisazadeh-Far, Kian; Metghalchi, Hameed

2016-07-01

Thermodynamic properties of hydrocarbon/air plasma mixtures at ultra-high temperatures must be precisely calculated due to important influence on the flame kernel formation and propagation in combusting flows and spark discharge applications. A new algorithm based on the complete chemical equilibrium assumption is developed to calculate the ultra-high temperature plasma composition and thermodynamic properties, including enthalpy, entropy, Gibbs free energy, specific heat at constant pressure, specific heat ratio, speed of sound, mean molar mass, and degree of ionization. The method is applied to compute the thermodynamic properties of H2/air and CH4/air plasma mixtures for different temperatures (1000-100 000 K), different pressures (10-6-100 atm), and different fuel/air equivalence ratios within flammability limit. In calculating the individual thermodynamic properties of the atomic species needed to compute the complete equilibrium composition, the Debye-Huckel cutoff criterion has been used for terminating the series expression of the electronic partition function so as to capture the reduction of the ionization potential due to pressure and the intense connection between the electronic partition function and the thermodynamic properties of the atomic species and the number of energy levels taken into account. Partition functions have been calculated using tabulated data for available atomic energy levels. The Rydberg and Ritz extrapolation and interpolation laws have been used for energy levels which are not observed. The calculated plasma properties are then presented as functions of temperature, pressure and equivalence ratio, in terms of a new set of thermodynamically self-consistent correlations that are shown to provide very accurate fits suitable for efficient use in CFD simulations. Comparisons with existing data for air plasma show excellent agreement.

Population sensitivities of animals to chronic ionizing radiation-model predictions from mice to elephant.

PubMed

Sazykina, Tatiana G

2018-02-01

Model predictions of population response to chronic ionizing radiation (endpoint 'morbidity') were made for 11 species of warm-blooded animals, differing in body mass and lifespan - from mice to elephant. Predictions were made also for 3 bird species (duck, pigeon, and house sparrow). Calculations were based on analytical solutions of the mathematical model, simulating a population response to low-LET ionizing radiation in an ecosystem with a limiting resource (Sazykina, Kryshev, 2016). Model parameters for different species were taken from biological and radioecological databases; allometric relationships were employed for estimating some parameter values. As a threshold of decreased health status in exposed populations ('health threshold'), a 10% reduction in self-repairing capacity of organisms was suggested, associated with a decline in ability to sustain environmental stresses. Results of the modeling demonstrate a general increase of population vulnerability to ionizing radiation in animal species of larger size and longevity. Populations of small widespread species (mice, house sparrow; body mass 20-50 g), which are characterized by intensive metabolism and short lifespan, have calculated 'health thresholds' at dose rates about 6.5-7.5 mGy day -1 . Widespread animals with body mass 200-500 g (rat, common pigeon) - demonstrate 'health threshold' values at 4-5 mGy day -1 . For populations of animals with body mass 2-5 kg (rabbit, fox, raccoon), the indicators of 10% health decrease are in the range 2-3.4 mGy day -1 . For animals with body mass 40-100 kg (wolf, sheep, wild boar), thresholds are within 0.5-0.8 mGy day -1 ; for herbivorous animals with body mass 200-300 kg (deer, horse) - 0.5-0.6 mGy day -1 . The lowest health threshold was estimated for elephant (body mass around 5000 kg) - 0.1 mGy day -1 . According to the model results, the differences in population sensitivities of warm-blooded animal species to ionizing radiation are generally depended on the metabolic rate and longevity of organisms, also on individual radiosensitivity of biological tissues. The results of 'health threshold' calculations are formulated as a graded scale of wildlife sensitivities to chronic radiation stress, ranging from potentially vulnerable to more resistant species. Further studies are needed to expand the scale of population sensitivities to radiation, including other groups of wildlife - cold-blooded species, invertebrates, and plants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ionization equilibrium and radiative energy loss rates for C, N, and O ions in low-density plasmas

NASA Technical Reports Server (NTRS)

Jacobs, V. L.; Davis, J.; Rogerson, J. E.; Blaha, M.

1978-01-01

The results of calculations of the ionization equilibrium and radiative energy loss rates for C, N and O ions in low-density plasmas are presented for electron temperatures in the range 10,000-10,000,000 K. The ionization structure is determined by using the steady-state corona model, in which electron impact ionization from the ground states is balanced by direct radiative and dielectronic recombination. With an improved theory, detailed calculations are carried out for the dielectronic recombination rates in which account is taken of all radiative and autoionization processes involving a single-electron electric-dipole transition of the recombining ion. The radiative energy loss processes considered are electron-impact excitation of resonance line emission, direct radiative recombination, dielectronic recombination, and electron-ion bremsstrahlung. For all three elements, resonance line emission resulting from 2s-2p transitions produces a broad maximum in the energy loss rate near 100,000 K.

Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

NASA Astrophysics Data System (ADS)

Schäfer, Julia M.; Inhester, Ludger; Son, Sang-Kil; Fink, Reinhold F.; Santra, Robin

2018-05-01

With the highly intense x-ray light generated by x-ray free-electron lasers (XFELs), molecular samples can be ionized many times in a single pulse. Here we report on a computational study of molecular spectroscopy at the high x-ray intensity provided by XFELs. Calculated photoelectron, Auger electron, and x-ray fluorescence spectra are presented for a single water molecule that reaches many electronic hole configurations through repeated ionization steps. The rich details shown in the spectra depend on the x-ray pulse parameters in a nonintuitive way. We discuss how the observed trends can be explained by the competition of microscopic electronic transition processes. A detailed comparison between spectra calculated within the independent-atom model and within the molecular-orbital framework highlights the chemical sensitivity of the spectral lines of multiple-hole configurations. Our results demonstrate how x-ray multiphoton ionization-related effects such as charge-rearrangement-enhanced x-ray ionization of molecules and frustrated absorption manifest themselves in the electron and fluorescence spectra.

Photoionization in the halo of the Galaxy

NASA Technical Reports Server (NTRS)

Bregman, Joel N.; Harrington, J. Patrick

1986-01-01

The ionizing radiation field in the halo is calculated and found to be dominated in the 13.6-45 eV range by light from O-B stars that escapes the disk, by planetary nebulae at 45-54 eV, by quasars and the Galactic soft X-ray background at 54-2000 eV, and by the extragalactic X-ray background at higher energies. Photoionization models are calculated with this radiation field incident on halo clouds of constant density for a variety of densities, for normal and depleted abundances, and with variations of the incident spectrum. For species at least triply ionized, such as Si IV, C IV, N V, and O VI, the line ratios are determined by intervening gas with the greatest volume, which is not necessarily the greatest mass component. Column densities from doubly ionized species like Si III should be greater than from triply ionized species. The role of photoionized gas in cosmic ray-supported halos and Galactic fountains is discussed. Observational tests of photoionization models are suggested.

Pseudostate methods and differential cross sections for antiproton ionization of atomic hydrogen and helium

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

McGovern, M.; Walters, H. R. J.; Assafrao, D.

2010-03-15

A relaxed form of a recent impact parameter coupled pseudostate approximation of McGovern et al. [Phys. Rev. A 79, 042707 (2009)] for calculating differential ionization cross sections is proposed. This greatly eases the computational burden in cases where a range of ejected electron energies has to be considered. The relaxed approximation is tested against exact first Born calculations for antiproton impact on H and nonperturbatively for the highly nonperturbative system of Au{sup 53+} incident upon He. The approximation performs well in these tests. It is shown how, with a little further approximation, the relaxed theory leads to a widely usedmore » prescription for the total ionization cross section. Results for differential ionization of H and He by antiprotons are presented. These reveal the growing dominance of the interaction between the antiproton and the target nucleus at low impact energies and show the changing importance of the role of the postcollisional interaction between the antiproton and the ejected electron.« less

A Corona Discharge Initiated Electrochemical Electrospray Ionization Technique

PubMed Central

Lloyd, John R.; Hess, Sonja

2009-01-01

We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe. Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source was robust and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique to increase the dynamic range, sensitivity and selectivity of ESI experiments. Synopsis Using a standard ESI source a corona discharge initiated electrochemical ionization technique was established resulting from the electrochemistry occurring at the CD electrode surface. PMID:19747843

A measurement of the relative cross sections for simultaneous ionization and excitation of the degenerate He(plus) n equals 4 levels

NASA Technical Reports Server (NTRS)

Sutton, J. F.; Kay, R. B.

1972-01-01

The relative cross sections for simultaneous ionization and excitation of helium by 200 eV electrons into the 4S, 4P, 4D and 4F levels have been measured via a fast delayed coincidence technique. Results are in poor agreement with Born approximation calculations for simultaneous ionization and excitation of helium, the 4P component being larger than expected.

Electron energy deposition in N2 gas

NASA Technical Reports Server (NTRS)

Fox, J. L.; Victor, G. A.

1988-01-01

The processes by which energetic electrons lose energy in a weakly ionized gas of molecular nitrogen are analyzed and calculations are carried out taking into account the discrete nature of the excitation processes. The excitation, ionization, dissociation and heating efficiencies are computed for energies up to 200 eV absorbed in a gas with fractional ionizations varying from 10(-6) to 10(-2). Individual vibrational excitations up to the seventh vibrational level are presented.

Collision cross sections of N2 by H+ impact at keV energies within time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Gao, C.-Z.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Wei, B.

2018-03-01

We calculate electron capture and ionization cross sections of N2 impacted by the H+ projectile at keV energies. To this end, we employ the time-dependent density-functional theory coupled nonadiabatically to molecular dynamics. To avoid the explicit treatment of the complex density matrix in the calculation of cross sections, we propose an approximate method based on the assumption of constant ionization rate over the period of the projectile passing the absorbing boundary. Our results agree reasonably well with experimental data and semi-empirical results within the measurement uncertainties in the considered energy range. The discrepancies are mainly attributed to the inadequate description of exchange-correlation functional and the crude approximation for constant ionization rate. Although the present approach does not predict the experiments quantitatively for collision energies below 10 keV, it is still helpful to calculate total cross sections of ion-molecule collisions within a certain energy range.

Large-scale fluctuations in the cosmic ionizing background: the impact of beamed source emission

NASA Astrophysics Data System (ADS)

Suarez, Teresita; Pontzen, Andrew

2017-12-01

When modelling the ionization of gas in the intergalactic medium after reionization, it is standard practice to assume a uniform radiation background. This assumption is not always appropriate; models with radiative transfer show that large-scale ionization rate fluctuations can have an observable impact on statistics of the Lyman α forest. We extend such calculations to include beaming of sources, which has previously been neglected but which is expected to be important if quasars dominate the ionizing photon budget. Beaming has two effects: first, the physical number density of ionizing sources is enhanced relative to that directly observed; and secondly, the radiative transfer itself is altered. We calculate both effects in a hard-edged beaming model where each source has a random orientation, using an equilibrium Boltzmann hierarchy in terms of spherical harmonics. By studying the statistical properties of the resulting ionization rate and H I density fields at redshift z ∼ 2.3, we find that the two effects partially cancel each other; combined, they constitute a maximum 5 per cent correction to the power spectrum P_{H I}(k) at k = 0.04 h Mpc-1. On very large scales (k < 0.01 h Mpc-1) the source density renormalization dominates; it can reduce, by an order of magnitude, the contribution of ionizing shot noise to the intergalactic H I power spectrum. The effects of beaming should be considered when interpreting future observational data sets.

Spectroscopic studies and quantum chemical investigations of (3,4-dimethoxybenzylidene) propanedinitrile

NASA Astrophysics Data System (ADS)

Gupta, Ujval; Kumar, Vinay; Singh, Vivek K.; Kant, Rajni; Khajuria, Yugal

2015-04-01

The Fourier Transform Infrared (FTIR), Ultra-Violet Visible (UV-Vis) spectroscopy and Thermogravimetric (TG) analysis of (3,4-dimethoxybenzylidene) propanedinitrile have been carried out and investigated using quantum chemical calculations. The molecular geometry, harmonic vibrational frequencies, Mulliken charges, natural atomic charges and thermodynamic properties in the ground state have been investigated by using Hartree Fock Theory (HF) and Density Functional Theory (DFT) using B3LYP functional with 6-311G(d,p) basis set. Both HF and DFT methods yield good agreement with the experimental data. Vibrational modes are assigned with the help of Vibrational Energy Distribution Analysis (VEDA) program. UV-Visible spectrum was recorded in the spectral range of 190-800 nm and the results are compared with the calculated values using TD-DFT approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results obtained from the studies of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are used to calculate molecular parameters like ionization potential, electron affinity, global hardness, electron chemical potential and global electrophilicity.

Detecting a heavy neutrino electric dipole moment at the LHC

NASA Astrophysics Data System (ADS)

Sher, Marc; Stevens, Justin R.

2018-02-01

The milliQan Collaboration has proposed to search for millicharged particles by looking for very weakly ionizing tracks in a detector installed in a cavern near the CMS experiment at the LHC. We note that another form of exotica can also yield weakly ionizing tracks. If a heavy neutrino has an electric dipole moment (EDM), then the milliQan experiment may be sensitive to it as well. In particular, writing the general dimension-5 operator for an EDM with a scale of a TeV and a one-loop factor, one finds a potential EDM as high as a few times 10-17 e-cm, and models exist where it is an order of magnitude higher. Redoing the Bethe calculation of ionization energy loss for an EDM, it is found that the milliQan detector is sensitive to EDMs as small as 10-17 e-cm. Using the production cross-section and analyzing the acceptance of the milliQan detector, we find the expected 95% exclusion and 3σ sensitivity over the range of neutrino masses from 5-1000 GeV for integrated luminosities of 300 and 3000 fb-1 at the LHC.

Photoionization Modeling and the K Lines of Iron

NASA Technical Reports Server (NTRS)

Kallman, T. R.; Palmeri, P.; Bautista, M. A.; Mendoza, C.; Krolik, J. H.

2004-01-01

We calculate the efficiency of iron K line emission and iron K absorption in photoionized models using a new set of atomic data. These data are more comprehensive than those previously applied to the modeling of iron K lines from photoionized gases, and allow us to systematically examine the behavior of the properties of line emission and absorption as a function of the ionization parameter, density and column density of model constant density clouds. We show that, for example, the net fluorescence yield for the highly charged ions is sensitive to the level population distribution produced by photoionization, and these yields are generally smaller than those predicted assuming the population is according to statistical weight. We demonstrate that the effects of the many strongly damped resonances below the K ionization thresholds conspire to smear the edge, thereby potentially affecting the astrophysical interpretation of absorption features in the 7-9 keV energy band. We show that the centroid of the ensemble of K(alpha) lines, the K(beta) energy, and the ratio of the K(alpha(sub 1)) to K(alpha(sub 2)) components are all diagnostics of the ionization parameter of our model slabs.

Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography.

PubMed

Winter, Gregory T; Wilhide, Joshua A; LaCourse, William R

2016-02-01

Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography

NASA Astrophysics Data System (ADS)

Winter, Gregory T.; Wilhide, Joshua A.; LaCourse, William R.

2016-02-01

Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

DFT-Supported Threshold Ionization Study of Chromium Biphenyl Complexes: Unveiling the Mechanisms of Substituent Influence on Redox Properties of Sandwich Compounds.

PubMed

Ketkov, Sergey Yu; Tzeng, Sheng-Yuan; Wu, Pei-Ying; Markin, Gennady V; Tzeng, Wen-Bih

2017-10-04

High-resolution mass-analyzed threshold ionization (MATI) spectra of (η 6 -Ph 2 ) 2 Cr and (η 6 -Ph 2 )(η 6 -PhMe)Cr demonstrate that the Ph groups work as electron donors, decreasing the ionization energy of the gas-phase bisarene complexes. In contrast to electrochemical data, a close similarity of the Ph and Me group effects on the oxidation of free sandwich molecules has been revealed. However, DFT calculations testify for the opposite shifts of the electron density caused by the Me and Ph substituents in the neutral complexes, the latter behaving as an electron-accepting fragment. On the contrary, in the bisarene cations, the Ph group becomes a stronger donor than methyl. This change provides the similar substituent effects observed with the MATI experiment. On the other hand, the well-documented opposite influence of the Me and Ph fragments on the redox potential of the (η 6 -arene) 2 Cr +/0 couple in solution appears to be a result of solvation effects but not intramolecular interactions as shown for the first time in this work. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurements of the energy distribution of a high brightness rubidium ion beam.

PubMed

Ten Haaf, G; Wouters, S H W; Nijhof, D F J; Mutsaers, P H A; Vredenbregt, E J D

2018-07-01

The energy distribution of a high brightness rubidium ion beam, which is intended to be used as the source for a focused ion beam instrument, is measured with a retarding field analyzer. The ions are created from a laser-cooled and compressed atomic beam by two-step photoionization in which the ionization laser power is enhanced in a build-up cavity. Particle tracing simulations are performed to ensure the analyzer is able to resolve the distribution. The lowest achieved full width 50% energy spread is (0.205 ± 0.006) eV, which is measured at a beam current of 9 pA. The energy spread originates from the variation in the ionization position of the ions which are created inside an extraction electric field. This extraction field is essential to limit disorder-induced heating which can decrease the ion beam brightness. The ionization position distribution is limited by a tightly focused excitation laser beam. Energy distributions are measured for various ionization and excitation laser intensities and compared with calculations based on numerical solutions of the optical Bloch equations including ionization. A good agreement is found between measurements and calculations. Copyright © 2018 Elsevier B.V. All rights reserved.

Developing hybrid approaches to predict pKa values of ionizable groups

PubMed Central

Witham, Shawn; Talley, Kemper; Wang, Lin; Zhang, Zhe; Sarkar, Subhra; Gao, Daquan; Yang, Wei

2011-01-01

Accurate predictions of pKa values of titratable groups require taking into account all relevant processes associated with the ionization/deionization. Frequently, however, the ionization does not involve significant structural changes and the dominating effects are purely electrostatic in origin allowing accurate predictions to be made based on the electrostatic energy difference between ionized and neutral forms alone using a static structure. On another hand, if the change of the charge state is accompanied by a structural reorganization of the target protein, then the relevant conformational changes have to be taken into account in the pKa calculations. Here we report a hybrid approach that first predicts the titratable groups, which ionization is expected to cause conformational changes, termed “problematic” residues, then applies a special protocol on them, while the rest of the pKa’s are predicted with rigid backbone approach as implemented in multi-conformation continuum electrostatics (MCCE) method. The backbone representative conformations for “problematic” groups are generated with either molecular dynamics simulations with charged and uncharged amino acid or with ab-initio local segment modeling. The corresponding ensembles are then used to calculate the pKa of the “problematic” residues and then the results are averaged. PMID:21744395

Double ionization of He(1[ital s][sup 2]) and He(1[ital s]2[ital s] [sup 3][ital S]) by a single high-energy photon

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

Teng, Z.; Shakeshaft, R.

1994-05-01

We have calculated the energy and angular distributions for double ionization of He(1[ital s][sup 2]) and He(1[ital s]2[ital s] [sup 3][ital S]) by one photon, over a range of photon energies up to a few keV. The calculations were based on using a fairly accurate initial-state wave function, determined so as to exactly satisfy the Kato cusp conditions, and a final-state wave function which is a product of three Coulomb wave functions modified by a short-range correction term. There are at least three different mechanisms for double ionization, and each one leaves a mark on the angular distribution. When themore » energies of the two electrons are equal, the contribution of each mechanism to the angular asymmetry parameter can be estimated on theoretical grounds; we compare these estimates with the calculated results to give a further indication of the roles of the various mechanisms. Concerning the shapes of the energy and angular distributions, we find significant differences between double ionization of singlet and triplet helium; in particular, the probability for one high-energy photon to eject two equal-energy electrons from triplet helium nearly vanishes owing to the Pauli exclusion principle and to interference effects resulting from antisymmetrization. In two appendixes we present some details of the integration involved in the calculations.« less

Absolute cross sections for the ionization-excitation of helium by electron impact

NASA Astrophysics Data System (ADS)

Bellm, S.; Lower, J.; Weigold, E.; Bray, I.; Fursa, D. V.; Bartschat, K.; Harris, A. L.; Madison, D. H.

2008-09-01

In a recent publication we presented detailed experimental and theoretical results for the electron-impact-induced ionization of ground-state helium atoms. The purpose of that work was to refine theoretical approaches and provide further insight into the Coulomb four-body problem. Cross section ratios were presented for transitions leading to excited states, relative to those leading to the ground state, of the helium ion. We now build on that study by presenting individual relative triple-differential ionization cross sections (TDCSs) for an additional body of experimental data measured at lower values of scattered-electron energies. This has been facilitated through the development of new electron-gun optics which enables us to accurately characterize the spectrometer transmission at low energies. The experimental results are compared to calculations resulting from a number of different approaches. For ionization leading to He+(1s2)1S , cross sections are calculated by the highly accurate convergent close-coupling (CCC) method. The CCC data are used to place the relative experimental data on to an absolute scale. TDCSs describing transitions to the excited states are calculated through three different approaches, namely, through a hybrid distorted- wave+R -matrix (close-coupling) model, through the recently developed four-body distorted-wave model, and by a first Born approximation calculation. Comparison of the first- and second-order theories with experiment allows for the accuracy of the different theoretical approaches to be assessed and gives insight into which physical aspects of the problem are most important to accurately model.

Oxygen ionization rates at Mars and Venus - Relative contributions of impact ionization and charge exchange

NASA Astrophysics Data System (ADS)

Zhang, M. H. G.; Luhmann, J. G.; Nagy, A. F.; Spreiter, J. R.; Stahara, S. S.

1993-02-01

Oxygen ion production rates above the ionopauses of Venus and Mars are calculated for photoionization, charge exchange, and solar wind electron impact ionization processes. The latter two require the use of the Spreiter and Stahara (1980) gas dynamic model to estimate magnetosheath velocities, densities, and temperatures. The results indicate that impact ionization is the dominant mechanism for the production of O(+) ions at both Venus and Mars. This finding might explain both the high ion escape rates measured by Phobos 2 and the greater mass loading rate inferred for Venus from the bow shock positions.

Prebreakdown characteristics of weakly ionized liquid and gaseous media in the strongly nonuniform electric field

NASA Astrophysics Data System (ADS)

Apfelbaum, M. S.; Syrovatka, R. A.; Vladimirov, V. I.

2018-01-01

A theoretical model of electrohydrodynamic prebreakdown phenomena in slightly ionized (weakly conductive) media is proposed. The electric high voltage conduction of weakly conductive liquids and slightly ionized gases in intense electric fields using this model is considered. The formula for the calculations of volt-ampere characteristics under high voltage spherical capacitor field is analytically obtained. The experimental corona discharge volt-ampere characteristics of air are presented. It was found that the size of the ionization region in the case of corona discharge in air increases monotonically with increasing discharge voltage.

Electron-Impact Total Ionization Cross Sections of CH and C2H2

PubMed Central

Kim, Yong-Ki; Ali, M. Asgar; Rudd, M. Eugene

1997-01-01

Electron-impact total ionization cross sections for the CH radical and C2H2 (acetylene) have been calculated using the Binary-Encounter-Bethe (BEB) model. The BEB model combines the Mott cross section and the asymptotic form of the Bethe theory, and has been shown to generate reliable ionization cross sections for a large variety of molecules. The BEB cross sections for CH and C2H2 are in good agreement with the available experimental data from ionization thresholds to hundreds of eV in incident energies. PMID:27805116

Continuum Electrostatics Approaches to Calculating pKas and Ems in Proteins

PubMed Central

Gunner, MR; Baker, Nathan A.

2017-01-01

Proteins change their charge state through protonation and redox reactions as well as through binding charged ligands. The free energy of these reactions are dominated by solvation and electrostatic energies and modulated by protein conformational relaxation in response to the ionization state changes. Although computational methods for calculating these interactions can provide very powerful tools for predicting protein charge states, they include several critical approximations of which users should be aware. This chapter discusses the strengths, weaknesses, and approximations of popular computational methods for predicting charge states and understanding their underlying electrostatic interactions. The goal of this chapter is to inform users about applications and potential caveats of these methods as well as outline directions for future theoretical and computational research. PMID:27497160

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

Builth-Williams, J. D.; Chiari, L.; Jones, D. B., E-mail: darryl.jones@flinders.edu.au, E-mail: michael.brunger@flinders.edu.au

We present experimental and theoretical results for the electron-impact ionization of the highest occupied molecular orbitals of tetrahydropyran and 1,4-dioxane. Using an (e,2e) technique in asymmetric coplanar kinematics, angular distributions of the slow ejected electron, with an energy of 20 eV, are measured when incident electrons at 250 eV ionize the target and scatter through an angle of either −10° or −15°. The data are compared with calculations performed at the molecular 3-body distorted wave level. Fair agreement between the theoretical model and the experimental measurements was observed. The similar structures for these targets provide key insights for assessing themore » limitations of the theoretical calculations. This study in turn facilitates an improved understanding of the dynamics in the ionization process.« less

Time-dependent calculations of transfer ionization by fast proton-helium collision in one-dimensional kinematics

NASA Astrophysics Data System (ADS)

Serov, Vladislav V.; Kheifets, A. S.

2014-12-01

We analyze a transfer ionization (TI) reaction in the fast proton-helium collision H++He →H0+He2 ++ e- by solving a time-dependent Schrödinger equation (TDSE) under the classical projectile motion approximation in one-dimensional kinematics. In addition, we construct various time-independent analogs of our model using lowest-order perturbation theory in the form of the Born series. By comparing various aspects of the TDSE and the Born series calculations, we conclude that the recent discrepancies of experimental and theoretical data may be attributed to deficiency of the Born models used by other authors. We demonstrate that the correct Born series for TI should include the momentum-space overlap between the double-ionization amplitude and the wave function of the transferred electron.

Electron- and proton-induced ionization of pyrimidine

DOE PAGES

Champion, Christophe; Quinto, Michele; Weck, Philippe F

2015-03-27

This present work describes a quantum-mechanically based model of the electron- and proton-induced ionization of isolated pyrimidine molecules. The impact energies range from the target ionization threshold up to ~1 keV for electrons and from 10 keV up to 10 MeV for protons. The cross-section calculations are performed within the 1st Born approximation in which the ejected electron is described by a Coulomb wave whereas the incident and the scattered projectiles are both described by plane waves. The pyrimidine target is described using the Gaussian 09 software package. Furthermore, our theoretical predictions obtained are in good agreement with experimental absolutemore » total cross sections, while large discrepancies are observed between existing semi-empirical models and the present calculations.« less

Vacuum ultraviolet photoionization of carbohydrates and nucleotides

NASA Astrophysics Data System (ADS)

Shin, Joong-Won; Bernstein, Elliot R.

2014-01-01

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5'-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C-C and C-O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

Numerical calculation of nonlinear ultrashort laser pulse propagation in transparent Kerr media

NASA Astrophysics Data System (ADS)

Arnold, Cord L.; Heisterkamp, Alexander; Ertmer, Wolfgang; Lubatschowski, Holger

2005-03-01

In the focal region of tightly focused ultrashort laser pulses, sufficient high intensities to initialize nonlinear ionization processes are easily achieved. Due to these nonlinear ionization processes, mainly multiphoton ionization and cascade ionization, free electrons are generated in the focus resulting in optical breakdown. A model including both nonlinear pulse propagation and plasma generation is used to calculate numerically the interaction of ultrashort pulses with their self-induced plasma in the vicinity of the focus. The model is based on a (3+1)-dimensional nonlinear Schroedinger equation describing the pulse propagation coupled to a system of rate equations covering the generation of free electrons. It is applicable to any transparent Kerr medium, whose linear and nonlinear optical parameters are known. Numerical calculations based on this model are used to understand nonlinear side effects, such as streak formation, occurring in addition to optical breakdown during short pulse refractive eye surgeries like fs-LASIK. Since the optical parameters of water are a good first-order approximation to those of corneal tissue, water is used as model substance. The free electron density distribution induced by focused ultrashort pulses as well as the pulses spatio-temporal behavior are studied in the low-power regime around the critical power for self-focusing.

Vacuum ultraviolet photoionization of carbohydrates and nucleotides.

PubMed

Shin, Joong-Won; Bernstein, Elliot R

2014-01-28

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5(')-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C-C and C-O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

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

Chang, Chong

The electrical potential difference has been estimated across the mixing region of two plasmas with different degrees of ionization. The estimation has been carried out in two different contexts of a charge neutral mixing region and a charge non-neutral sheath. Ion energy gained due to the potential difference has also been estimated. In both analyses, ion energy gain is proportional to the degree of ionization, and a fairly large ionization appears to be needed for overcoming the potential energy barrier of strongly coupled plasmas.

Renormalization group method based on the ionization energy theory

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

Arulsamy, Andrew Das, E-mail: sadwerdna@gmail.com; School of Physics, University of Sydney, Sydney, New South Wales 2006

2011-03-15

Proofs are developed to explicitly show that the ionization energy theory is a renormalized theory, which mathematically exactly satisfies the renormalization group formalisms developed by Gell-Mann-Low, Shankar and Zinn-Justin. However, the cutoff parameter for the ionization energy theory relies on the energy-level spacing, instead of lattice point spacing in k-space. Subsequently, we apply the earlier proofs to prove that the mathematical structure of the ionization-energy dressed electron-electron screened Coulomb potential is exactly the same as the ionization-energy dressed electron-phonon interaction potential. The latter proof is proven by means of the second-order time-independent perturbation theory with the heavier effective mass condition,more » as required by the electron-electron screened Coulomb potential. The outcome of this proof is that we can derive the heat capacity and the Debye frequency as a function of ionization energy, which can be applied in strongly correlated matter and nanostructures.« less

MO-FG-CAMPUS-IeP1-05: New Ionization Chamber Dosimetry of Absorbed Dose to Water in Diagnostic KV X-Ray Beams

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

Araki, F; Ohno, T

Purpose: To develop new ionization chamber dosimetry of absorbed dose to water in diagnostic kV x-ray beams, by using a beam quality conversion factor, kQ, for Co-60 to kV x-ray and an ionization conversion factor for a water-substitute plastic phantom. Methods: kQ was calculated for aluminum half value-layers (Al-HVLs) of 1.5 mm to 8 mm which were generated by kV x-ray beams of 50 to 120 kVp. Twenty-two energy spectra for ten effective energies (Eeff) were calculated by a SpecCalc program. Depth doses in water were calculated at 5 × 5 to 30 × 30 cm{sup 2} fields. Output factorsmore » were also obtained from the dose ratio for a 10 × 10 cm{sup 2} field. kQ was obtained for a PTW30013 Former ion chamber. In addition, an ionization conversion factor of the PWDT phantom to water was calculated. All calculations were performed with EGSnrc/cavity code and egs-chamber codes. Results: The x-ray beam energies for 1.5 mm to 8 mm Al-HVLs ranged in Eeff of 25.7 to 54.3 keV. kQ for 1.5 mm to 8 mm Al-HVLs were 0.831 to 0.897, at 1 and 2 cm depths for a 10 × 10 cm2 field. Similarly, output factors for 5 × 5 to 30 × 30 cm{sup 2} fields were 0.937 to 1.033 for 25.7 keV and 0.857 to 1.168 for 54.3 keV. The depth dose in a PWDT phantom decreased up to 5% compared to that in water at depth of ten percent of maximum dose for 1.5 mm Al-HVL. The ionization ratios of water/PWDT phantoms for the PTW30013 chamber were 1.012 to 1.007 for 1.5 mm to 8 mm Al-HVLs at 1 cm depth. Conclusion: It became possible to directly measure the absorbed dose to water with the ionization chamber in diagnostic kV x-ray beams, by using kQ and the PWDT phantom.« less

Electronic Structure of Helium Atom in a Quantum Dot

NASA Astrophysics Data System (ADS)

Saha, Jayanta K.; Bhattacharyya, S.; Mukherjee, T. K.

2016-03-01

Bound and resonance states of helium atom have been investigated inside a quantum dot by using explicitly correlated Hylleraas type basis set within the framework of stabilization method. To be specific, precise energy eigenvalues of bound 1sns (1Se) (n = 1-6) states and the resonance parameters i.e. positions and widths of 1Se states due to 2sns (n = 2-5) and 2pnp (n = 2-5) configurations of confined helium below N = 2 ionization threshold of He+ have been estimated. The two-parameter (Depth and Width) finite oscillator potential is used to represent the confining potential due to the quantum dot. It has been explicitly demonstrated that the electronic structural properties become sensitive functions of the dot size. It is observed from the calculations of ionization potential that the stability of an impurity ion within a quantum dot may be manipulated by varying the confinement parameters. A possibility of controlling the autoionization lifetime of doubly excited states of two-electron ions by tuning the width of the quantum cavity is also discussed here. TKM Gratefully Acknowledges Financial Support under Grant No. 37(3)/14/27/2014-BRNS from the Department of Atomic Energy, BRNS, Government of India. SB Acknowledges Financial Support under Grant No. PSW-160/14-15(ERO) from University Grants Commission, Government of India

Nonequilibrium evolution of strong-field anisotropic ionized electrons towards a delayed plasma-state.

PubMed

Pasenow, B; Moloney, J V; Koch, S W; Chen, S H; Becker, A; Jaroń-Becker, A

2012-01-30

Rigorous quantum calculations of the femtosecond ionization of hydrogen atoms in air lead to highly anisotropic electron and ion angular (momentum) distributions. A quantum Monte-Carlo analysis of the subsequent many-body dynamics reveals two distinct relaxation steps, first to a nearly isotropic hot nonequilibrium and then to a quasi-equilibrium configuration. The collective isotropic plasma state is reached on a picosecond timescale well after the ultrashort ionizing pulse has passed.

Evaluating Force Fields for the Computational Prediction of Ionized Arginine and Lysine Side-Chains Partitioning into Lipid Bilayers and Octanol.

PubMed

Sun, Delin; Forsman, Jan; Woodward, Clifford E

2015-04-14

Abundant peptides and proteins containing arginine (Arg) and lysine (Lys) amino acids can apparently permeate cell membranes with ease. However, the mechanisms by which these peptides and proteins succeed in traversing the free energy barrier imposed by cell membranes remain largely unestablished. Precise thermodynamic studies (both theoretical and experimental) on the interactions of Arg and Lys residues with model lipid bilayers can provide valuable clues to the efficacy of these cationic peptides and proteins. We have carried out molecular dynamics simulations to calculate the interactions of ionized Arg and Lys side-chains with the zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayer for 10 widely used lipid/protein force fields: CHARMM36/CHARMM36, SLIPID/AMBER99SB-ILDN, OPLS-AA/OPLS-AA, Berger/OPLS-AA, Berger/GROMOS87, Berger/GROMOS53A6, GROMOS53A6/GROMOS53A6, nonpolarizable MARTINI, polarizable MARTINI, and BMW MARTINI. We performed umbrella sampling simulations to obtain the potential of mean force for Arg and Lys side-chains partitioning from water to the bilayer interior. We found significant differences between the force fields, both for the interactions between side-chains and bilayer surface, as well as the free energy cost for placing the side-chain at the center of the bilayer. These simulation results were compared with the Wimley-White interfacial scale. We also calculated the free energy cost for transferring ionized Arg and Lys side-chains from water to both dry and wet octanol. Our simulations reveal rapid diffusion of water molecules into octanol whereby the equilibrium mole fraction of water in the wet octanol phase was ∼25%. Surprisingly, our free energy calculations found that the high water content in wet octanol lowered the water-to-octanol partitioning free energies for cationic residues by only 0.6 to 0.7 kcal/mol.

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

DOE PAGES

Hu, S. X.; Collins, Lee A.; Goncharov, V. N.; ...

2016-04-14

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations on the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm 3 and T = 15,625 to 500,000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which exhibits the correct behaviors of continuum lowering and pressure ionization. The thermal conductivities (κ QMD) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted withmore » a generalized Coulomb logarithm [(lnΛ) QMD] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Furthermore, hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted –20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.« less

Investigation of a Mercury-Argon Hot Cathode Discharge

NASA Astrophysics Data System (ADS)

Wamsley, Robert Charles

Classical absorption and laser induced fluorescence (LIF) experiments are used to investigate processes in the cathode region of a Hg-Ar hot cathode discharge. The absorption and LIF measurements are used to test the qualitative understanding and develop a quantitative model of a hot cathode discharge. The main contribution of this thesis is a model of the negative glow region that demonstrates the importance of Penning ionization to the ionization balance in the negative glow. We modeled the excited argon balance equation using a Monte Carlo simulation. In this simulation we used the trapped radiative decay rate of the resonance levels and the Penning ionization rate as the dominant loss terms in the balance equation. The simulated data is compared to and found to agree with absolute excited argon densities measured in a classical absorption experiment. We found the primary production rate per unit volume of excited Ar atoms in the simulation is sharply peaked near the cathode hot spot. We used the ion production rate from this simulation and a Green's function solution to the ambipolar diffusion equation to calculate the contribution of Penning ionization to the total ion density. We compared the results of this calculation to our experimental values of the Hg ^+ densities in the negative glow. We found that Penning ionization is an important and possibly the dominant ionization process in the negative glow.

Distinguishing between relaxation pathways by combining dissociative ionization pump probe spectroscopy and ab initio calculations: a case study of cytosine.

PubMed

Kotur, Marija; Weinacht, Thomas C; Zhou, Congyi; Kistler, Kurt A; Matsika, Spiridoula

2011-05-14

We present a general method for tracking molecular relaxation along different pathways from an excited state down to the ground state. We follow the excited state dynamics of cytosine pumped near the S(0)-S(1) resonance using ultrafast laser pulses in the deep ultraviolet and probed with strong field near infrared pulses which ionize and dissociate the molecules. The fragment ions are detected via time of flight mass spectroscopy as a function of pump probe delay and probe pulse intensity. Our measurements reveal that different molecular fragments show different timescales, indicating that there are multiple relaxation pathways down to the ground state. We interpret our measurements with the help of ab initio electronic structure calculations of both the neutral molecule and the molecular cation for different conformations en route to relaxation back down to the ground state. Our measurements and calculations show passage through two seams of conical intersections between ground and excited states and demonstrate the ability of dissociative ionization pump probe measurements in conjunction with ab initio electronic structure calculations to track molecular relaxation through multiple pathways.

Resonant ionization spectroscopy of autoionizing Rydberg states in cobalt and redetermination of its ionization potential

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

Liu, Yuan; Gottwald, T.; Mattolat, C.

We obtained multi-step resonance ionization spectroscopy of cobalt using a hot-cavity laser ion source and three Ti:Sapphire lasers. Furthermore, the photoionization spectra revealed members of five new autoionizing Rydberg series that originate from three different lower levels of 3d 74s5s h 4F 9/2, 3d 74s4d f 4G 11/2, and 3d 74s4d f 4H 13/2 and converge to the first four excited states of singly ionized Co. Our analyses of the Rydberg series yield 63564.689 0.036 cm -1 as the first ionization potential of Co, which is an order of magnitude more accurate than the previous estimation. Using a three-step resonancemore » ionization scheme that employs an autoinizing Rydberg state in the last transition, we obtained an overall ionization efficiency of about 18% for Co.« less

Resonant ionization spectroscopy of autoionizing Rydberg states in cobalt and redetermination of its ionization potential

DOE PAGES

Liu, Yuan; Gottwald, T.; Mattolat, C.; ...

2017-03-20

We obtained multi-step resonance ionization spectroscopy of cobalt using a hot-cavity laser ion source and three Ti:Sapphire lasers. Furthermore, the photoionization spectra revealed members of five new autoionizing Rydberg series that originate from three different lower levels of 3d 74s5s h 4F 9/2, 3d 74s4d f 4G 11/2, and 3d 74s4d f 4H 13/2 and converge to the first four excited states of singly ionized Co. Our analyses of the Rydberg series yield 63564.689 0.036 cm -1 as the first ionization potential of Co, which is an order of magnitude more accurate than the previous estimation. Using a three-step resonancemore » ionization scheme that employs an autoinizing Rydberg state in the last transition, we obtained an overall ionization efficiency of about 18% for Co.« less

Open Port Probe Sampling Interface for the Direct Coupling of Biocompatible Solid-Phase Microextraction to Atmospheric Pressure Ionization Mass Spectrometry.

PubMed

Gómez-Ríos, Germán Augusto; Liu, Chang; Tascon, Marcos; Reyes-Garcés, Nathaly; Arnold, Don W; Covey, Thomas R; Pawliszyn, Janusz

2017-04-04

In recent years, the direct coupling of solid phase microextraction (SPME) and mass spectrometry (MS) has shown its great potential to improve limits of quantitation, accelerate analysis throughput, and diminish potential matrix effects when compared to direct injection to MS. In this study, we introduce the open port probe (OPP) as a robust interface to couple biocompatible SPME (Bio-SPME) fibers to MS systems for direct electrospray ionization. The presented design consisted of minimal alterations to the front-end of the instrument and provided better sensitivity, simplicity, speed, wider compound coverage, and high-throughput in comparison to the LC-MS based approach. Quantitative determination of clenbuterol, fentanyl, and buprenorphine was successfully achieved in human urine. Despite the use of short extraction/desorption times (5 min/5 s), limits of quantitation below the minimum required performance levels (MRPL) set by the world antidoping agency (WADA) were obtained with good accuracy (≥90%) and linearity (R 2 > 0.99) over the range evaluated for all analytes using sample volumes of 300 μL. In-line technologies such as multiple reaction monitoring with multistage fragmentation (MRM 3 ) and differential mobility spectrometry (DMS) were used to enhance the selectivity of the method without compromising analysis speed. On the basis of calculations, once coupled to high throughput, this method can potentially yield preparation times as low as 15 s per sample based on the 96-well plate format. Our results demonstrated that Bio-SPME-OPP-MS efficiently integrates sampling/sample cleanup and atmospheric pressure ionization, making it an advantageous configuration for several bioanalytical applications, including doping in sports, in vivo tissue sampling, and therapeutic drug monitoring.

Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O.

PubMed

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-05

The crystal structure of (C 6 H 20 N 3 )SbCl 5 ·Cl·H 2 O is built up of [NH 3 (CH 2 ) 3 NH 2 (CH 2 ) 3 NH 3 ] 3+ cations, [SbCl 5 ] 2- anions, free Cl - anions and neutral water molecules connected together by NH⋯Cl, NH⋯O and OH⋯Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C 6 H 20 N 3 )SbCl 5 ·Cl·H 2 O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule. Copyright © 2017 Elsevier B.V. All rights reserved.

Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

NASA Astrophysics Data System (ADS)

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-01

The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

Ionization in the local interstellar and intergalactic media

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

Cheng, K.

1990-01-01

Detailed photoionization calculations for the local interstellar medium (LISM) and the intergalactic medium (IGM) are presented. Constraints in the LISM are imposed by H I column density derived from IUE and Copernicus data toward nearby B stars and hot white dwarfs. The EUV radiation field is modeled including contributions from discrete stellar sources and from a thermal bremsstrahlung-radiative recombination spectrum emitted from the surrounding 10(exp 6) K coronal substrate. Lower limits to the fractional ionization of hydrogen and helium of 0.17 and 0.30 respectively are established. The derived limits have important implications for the interpretation of the H I andmore » He I backscattering results. The high He ionization fraction results primarily from very strong line emission below 500 A originating in the surrounding coronal substrate while the H ionization is dominated by the EUV radiation from the discrete stellar sources. The dual effects of thermal conduction and the EUV spectrum of the 10(exp 6) K plasma on ionization in the cloud skin are explored. The EUV radiation field and Auger ionization have insignificant effects on the resulting ionic column densities of Si IV, C IV, N V and O VI through the cloud skin. Calculations show that the abundances of these species are dominated by collisional ionization in the thermal conduction front. Because of a low charge exchange rate with hydrogen, the ionic column density ratios of N(C III)/N(C II) and N(N II)/N(N I) are dominated by the EUV radiation field in the local interstellar medium. These ratios should be important diagnostics for the EUV radiation field and serve as surrogate indicators of the interstellar He and H ionization fraction respectively. The same photoionization model is applied to the intergalactic medium.« less

First-Principles Investigation to Ionization of Argon Under Conditions Close to Typical Sonoluminescence Experiments

PubMed Central

Kang, Wei; Zhao, Shijun; Zhang, Shen; Zhang, Ping; Chen, Q. F.; He, Xian-Tu

2016-01-01

Mott effect, featured by a sharp increase of ionization, is one of the unique properties of partially ionized plasmas, and thus of great interest to astrophysics and inertial confinement fusion. Recent experiments of single bubble sonoluminescence (SBSL) revealed that strong ionization took place at a density two orders lower than usual theoretical expectation. We show from the perspective of electronic structures that the strong ionization is unlikely the result of Mott effect in a pure argon plasma. Instead, first-principles calculations suggest that other ion species from aqueous environments can energetically fit in the gap between the continuum and the top of occupied states of argon, making the Mott effect possible. These results would help to clarify the relationship between SBSL and Mott effect, and further to gain an better understanding of partially ionized plasmas. PMID:26853107

Calculation of thermodynamic functions of aluminum plasma for high-energy-density systems

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

Shumaev, V. V., E-mail: shumaev@student.bmstu.ru

The results of calculating the degree of ionization, the pressure, and the specific internal energy of aluminum plasma in a wide temperature range are presented. The TERMAG computational code based on the Thomas–Fermi model was used at temperatures T > 105 K, and the ionization equilibrium model (Saha model) was applied at lower temperatures. Quantitatively similar results were obtained in the temperature range where both models are applicable. This suggests that the obtained data may be joined to produce a wide-range equation of state.

Electric dipole transitions for four-times ionized cerium (Ce V)

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

Usta, Betül Karaçoban, E-mail: bkaracoban@sakarya.edu.tr; Akgün, Elif, E-mail: elif.akgun@ogr.sakarya.edu.tr; Alparslan, Büşra, E-mail: busra.alparslan1@ogr.sakarya.edu.tr

2016-03-25

We have calculated the transition parameters, such as wavelengths, oscillator strengths, and transition probabilities (or rates), for the electric dipole (E1) transitions in four-times ionized cerium (Ce V, Z = 58) by using the multiconfiguration Hartree-Fock method within the framework of Breit-Pauli (MCHF+BP) relativistic corrections and the relativistic Hartree-Fock (HFR) method. The obtained results have been compared with other works available in literature. A discussion of these calculations for Ce V in this study has also been in view of the MCHF+BP and HFR methods.

CIFOG: Cosmological Ionization Fields frOm Galaxies

NASA Astrophysics Data System (ADS)

Hutter, Anne

2018-03-01

CIFOG is a versatile MPI-parallelised semi-numerical tool to perform simulations of the Epoch of Reionization. From a set of evolving cosmological gas density and ionizing emissivity fields, it computes the time and spatially dependent ionization of neutral hydrogen (HI), neutral (HeI) and singly ionized helium (HeII) in the intergalactic medium (IGM). The code accounts for HII, HeII, HeIII recombinations, and provides different descriptions for the photoionization rate that are used to calculate the residual HI fraction in ionized regions. This tool has been designed to be coupled to semi-analytic galaxy formation models or hydrodynamical simulations. The modular fashion of the code allows the user to easily introduce new descriptions for recombinations and the photoionization rate.

Evidence for unnatural-parity contributions to electron-impact ionization of laser-aligned atoms

DOE PAGES

Armstrong, Gregory S. J.; Colgan, James Patrick; Pindzola, M. S.; ...

2015-09-11

Recent measurements have examined the electron-impact ionization of excited-state laser-aligned Mg atoms. In this paper we show that the ionization cross section arising from the geometry where the aligned atom is perpendicular to the scattering plane directly probes the unnatural parity contributions to the ionization amplitude. The contributions from natural parity partial waves cancel exactly in this geometry. Our calculations resolve the discrepancy between the nonzero measured cross sections in this plane and the zero cross section predicted by distorted-wave approaches. Finally, we demonstrate that this is a general feature of ionization from p-state targets by additional studies of ionizationmore » from excited Ca and Na atoms.« less

Cross sections for direct and dissociative ionization of NH3 and CS2 by electron impact

NASA Technical Reports Server (NTRS)

Rao, M. V. V. S.; Srivastava, S. K.

1991-01-01

A crossed electron beam-molecular beam collision geometry is used to measure cross sections for the production of positive ions by electron impact on NH3 and CS2. Ionization cross-section data for NH3 and the values of various cross sections are presented, as well as ionization efficiency curves for CS2. Considerable differences are found between the various results on NH3. The present values are close to the data of Djuric et al. (1981). The semiempirical calculations of Hare and Meath (1987) differ considerably in the absolute values of cross sections. Discrepancies were observed in comparisons of cross sections of other fragment ions resulting from the ionization and dissociate ionization of NH3.

Hydration effects on the photoionization energy of 2‧-deoxyguanosine 5‧-phosphate and activation barriers for guanine methylation by carcinogenic methane diazonium ions

NASA Astrophysics Data System (ADS)

Eichler, Daniel R.; Hamann, Haley A.; Harte, Katherine A.; Papadantonakis, George A.

2017-07-01

Results from DFT calculations indicate that states originating from gas-phase ionization of the phosphate and the base are degenerate in syn-5‧-dGMP- and that bulk hydration lowers the base-localized ionization energy by <0.5 eV. Local ionization maps show that micro-hydration leads to the formation of donor and acceptor hydrogen bonds and the ionization energy decreases or increases in each case respectively. The SN2 transition states of the methylation reactions of guanine with methane diazonium ions are lower at the N7 than at the O6 sites and they are influenced by local ionization energy and steric interference.

Assessment of ionization chamber correction factors in photon beams using a time saving strategy with PENELOPE code.

PubMed

Reis, C Q M; Nicolucci, P

2016-02-01

The purpose of this study was to investigate Monte Carlo-based perturbation and beam quality correction factors for ionization chambers in photon beams using a saving time strategy with PENELOPE code. Simulations for calculating absorbed doses to water using full spectra of photon beams impinging the whole water phantom and those using a phase-space file previously stored around the point of interest were performed and compared. The widely used NE2571 ionization chamber was modeled with PENELOPE using data from the literature in order to calculate absorbed doses to the air cavity of the chamber. Absorbed doses to water at reference depth were also calculated for providing the perturbation and beam quality correction factors for that chamber in high energy photon beams. Results obtained in this study show that simulations with phase-space files appropriately stored can be up to ten times shorter than using a full spectrum of photon beams in the input-file. Values of kQ and its components for the NE2571 ionization chamber showed good agreement with published values in the literature and are provided with typical statistical uncertainties of 0.2%. Comparisons to kQ values published in current dosimetry protocols such as the AAPM TG-51 and IAEA TRS-398 showed maximum percentage differences of 0.1% and 0.6% respectively. The proposed strategy presented a significant efficiency gain and can be applied for a variety of ionization chambers and clinical photon beams. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Calculation on spectrum of direct DNA damage induced by low-energy electrons including dissociative electron attachment.

PubMed

Liu, Wei; Tan, Zhenyu; Zhang, Liming; Champion, Christophe

2017-03-01

In this work, direct DNA damage induced by low-energy electrons (sub-keV) is simulated using a Monte Carlo method. The characteristics of the present simulation are to consider the new mechanism of DNA damage due to dissociative electron attachment (DEA) and to allow determining damage to specific bases (i.e., adenine, thymine, guanine, or cytosine). The electron track structure in liquid water is generated, based on the dielectric response model for describing electron inelastic scattering and on a free-parameter theoretical model and the NIST database for calculating electron elastic scattering. Ionization cross sections of DNA bases are used to generate base radicals, and available DEA cross sections of DNA components are applied for determining DNA-strand breaks and base damage induced by sub-ionization electrons. The electron elastic scattering from DNA components is simulated using cross sections from different theoretical calculations. The resulting yields of various strand breaks and base damage in cellular environment are given. Especially, the contributions of sub-ionization electrons to various strand breaks and base damage are quantitatively presented, and the correlation between complex clustered DNA damage and the corresponding damaged bases is explored. This work shows that the contribution of sub-ionization electrons to strand breaks is substantial, up to about 40-70%, and this contribution is mainly focused on single-strand break. In addition, the base damage induced by sub-ionization electrons contributes to about 20-40% of the total base damage, and there is an evident correlation between single-strand break and damaged base pair A-T.

Theoretical determination of one-electron redox potentials for DNA bases, base pairs, and stacks.

PubMed

Paukku, Y; Hill, G

2011-05-12

Electron affinities, ionization potentials, and redox potentials for DNA bases, base pairs, and N-methylated derivatives are computed at the DFT/M06-2X/6-31++G(d,p) level of theory. Redox properties of a guanine-guanine stack model are explored as well. Reduction and oxidation potentials are in good agreement with the experimental ones. Electron affinities of base pairs were found to be negative. Methylation of canonical bases affects the ionization potentials the most. Base pair formation and base stacking lower ionization potentials by 0.3 eV. Pairing of guanine with the 5-methylcytosine does not seem to influence the redox properties of this base pair much.

Catalytic hydrodeoxygenation of methyl-substituted phenols: correlations of kinetic parameters with molecular properties.

PubMed

Massoth, F E; Politzer, P; Concha, M C; Murray, J S; Jakowski, J; Simons, Jack

2006-07-27

The hydrodeoxygenation of methyl-substituted phenols was carried out in a flow microreactor at 300 degrees C and 2.85 MPa hydrogen pressure over a sulfided CoMo/Al(2)O(3) catalyst. The primary reaction products were methyl-substituted benzene, cyclohexene, cyclohexane, and H(2)O. Analysis of the results suggests that two independent reaction paths are operative, one leading to aromatics and the other to partially or completely hydrogenated cyclohexanes. The reaction data were analyzed using Langmuir-Hinshelwood kinetics to extract the values of the reactant-to-catalyst adsorption constant and of the rate constants characterizing the two reaction paths. The adsorption constant was found to be the same for both reactions, suggesting that a single catalytic site center is operative in both reactions. Ab initio electronic structure calculations were used to evaluate the electrostatic potentials and valence orbital ionization potentials for all of the substituted phenol reactants. Correlations were observed between (a) the adsorption constant and the two reaction rate constants measured for various methyl-substitutions and (b) certain moments of the electrostatic potentials and certain orbitals' ionization potentials of the isolated phenol molecules. On the basis of these correlations to intrinsic reactant-molecule properties, a reaction mechanism is proposed for each pathway, and it is suggested that the dependencies of adsorption and reaction rates upon methyl-group substitution are a result of the substituents' effects on the electrostatic potential and orbitals rather than geometric (steric) effects.

Dissociative recombination of HCl+

NASA Astrophysics Data System (ADS)

Larson, Åsa; Fonseca dos Santos, Samantha; E. Orel, Ann

2017-08-01

The dissociative recombination of HCl+, including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0 , to the first three excited vibrational states, v = 1 , v = 2 , and v = 3 , are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

Dissociative recombination of HCl.

PubMed

Larson, Åsa; Fonseca Dos Santos, Samantha; E Orel, Ann

2017-08-28

The dissociative recombination of HCl + , including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0, to the first three excited vibrational states, v = 1, v = 2, and  v = 3, are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

Conformational responses to changes in the state of ionization of titrable groups in proteins

NASA Astrophysics Data System (ADS)

Richman, Daniel Eric

Electrostatic energy links the structural properties of proteins with some of their important biological functions, including catalysis, energy transduction, and binding and recognition. Accurate calculation of electrostatic energy is essential for predicting and for analyzing function from structure. All proteins have many ionizable residues at the protein-water interface. These groups tend to have ionization equilibria (pK a values) shifted slightly relative to their values in water. In contrast, groups buried in the hydrophobic interior usually have highly anomalous p Ka values. These shifts are what structure-based calculations have to reproduce to allow examination of contributions from electrostatics to stability, solubility and interactions of proteins. Electrostatic energies are challenging to calculate accurately because proteins are heterogeneous dielectric materials. Any individual ionizable group can experience very different local environments with different dielectric properties. The studies in this thesis examine the hypothesis that proteins reorganize concomitant with changes in their state of ionization. It appears that the pKa value measured experimentally reflects the average of pKa values experienced in the different electrostatic environments corresponding to different conformational microstates. Current computational models fail to sample conformational reorganization of the backbone correctly. Staphyloccocal nuclease (SNase) was used as a model protein in nuclear magnetic resonance (NMR) spectroscopy studies to characterize the conformational rearrangements of the protein coupled to changes in the ionization state of titrable groups. One set of experiments tests the hypothesis that proton binding to surface Asp and Glu side chains drives local unfolding by stabilizing less-native, more water-solvated conformations in which the side chains have normalized pKa values. Increased backbone flexibility in the ps-ns timescale, hydrogen bond (H-bond) breaking on at least the mus timescale, and segmental unfolding were detected near titrating groups as pH decreased into the acidic range. The study identified local structural features and stabilities that modulate the magnitude of electrostatic effects. The data demonstrate that computational approaches to pK a calculations for surface groups must account for local fluctuations spanning a wide range of timescales. A comparative NMR spectroscopy study with the L25K and L125K variants of SNase, each with a Lys residue buried in the hydrophobic interior of the protein, determined locations, timescales, and amplitudes of backbone conformational reorganization coupled with ionization of the buried Lys residues. The L25K protein exhibited an ensemble of local fluctuations of the beta barrel in the hundreds of mus timescale and an ensemble of subglobally unfolded beta-barrel states in the hundreds of ms timescale with strong pH dependence. The L125K protein exhibited fluctuations of the helix around site 125 in the mus timescale, with negligible pH dependence. These data illustrate the diverse timescales and local structural properties of conformational reorganization coupled to ionization of buried groups, and the challenge to structure-based electrostatics calculations, which must capture these long-timescale processes.

Air-kerma strength determination of a new directional (103)Pd source.

PubMed

Aima, Manik; Reed, Joshua L; DeWerd, Larry A; Culberson, Wesley S

2015-12-01

A new directional (103)Pd planar source array called a CivaSheet™ has been developed by CivaTech Oncology, Inc., for potential use in low-dose-rate (LDR) brachytherapy treatments. The array consists of multiple individual polymer capsules called CivaDots, containing (103)Pd and a gold shield that attenuates the radiation on one side, thus defining a hot and cold side. This novel source requires new methods to establish a source strength metric. The presence of gold material in such close proximity to the active (103)Pd region causes the source spectrum to be significantly different than the energy spectra of seeds normally used in LDR brachytherapy treatments. In this investigation, the authors perform air-kerma strength (S(K)) measurements, develop new correction factors for these measurements based on an experimentally verified energy spectrum, and test the robustness of transferring S(K) to a well-type ionization chamber. S(K) measurements were performed with the variable-aperture free-air chamber (VAFAC) at the University of Wisconsin Medical Radiation Research Center. Subsequent measurements were then performed in a well-type ionization chamber. To realize the quantity S(K) from a directional source with gold material present, new methods and correction factors were considered. Updated correction factors were calculated using the MCNP 6 Monte Carlo code in order to determine S(K) with the presence of gold fluorescent energy lines. In addition to S(K) measurements, a low-energy high-purity germanium (HPGe) detector was used to experimentally verify the calculated spectrum, a sodium iodide (NaI) scintillating counter was used to verify the azimuthal and polar anisotropy, and a well-type ionization chamber was used to test the feasibility of disseminating S(K) values for a directional source within a cylindrically symmetric measurement volume. The UW VAFAC was successfully used to measure the S(K) of four CivaDots with reproducibilities within 0.3%. Monte Carlo methods were used to calculate the UW VAFAC correction factors and the calculated spectrum emitted from a CivaDot was experimentally verified with HPGe detector measurements. The well-type ionization chamber showed minimal variation in response (<1.5%) as a function of source positioning angle, indicating that an American Association of Physicists in Medicine (AAPM) Accredited Dosimetry Calibration Laboratory calibrated well chamber would be a suitable device to transfer an S(K)-based calibration to a clinical user. S(K) per well-chamber ionization current ratios were consistent among the four dots measured. Additionally, the measurements and predictions of anisotropy show uniform emission within the solid angle of the VAFAC, which demonstrates the robustness of the S(K) measurement approach. This characterization of a new (103)Pd directional brachytherapy source helps to establish calibration methods that could ultimately be used in the well-established AAPM Task Group 43 formalism. Monte Carlo methods accurately predict the changes in the energy spectrum caused by the fluorescent x-rays produced in the gold shield.

Air-kerma strength determination of a new directional 103Pd source

PubMed Central

Reed, Joshua L.; DeWerd, Larry A.; Culberson, Wesley S.

2015-01-01

Purpose: A new directional 103Pd planar source array called a CivaSheet™ has been developed by CivaTech Oncology, Inc., for potential use in low-dose-rate (LDR) brachytherapy treatments. The array consists of multiple individual polymer capsules called CivaDots, containing 103Pd and a gold shield that attenuates the radiation on one side, thus defining a hot and cold side. This novel source requires new methods to establish a source strength metric. The presence of gold material in such close proximity to the active 103Pd region causes the source spectrum to be significantly different than the energy spectra of seeds normally used in LDR brachytherapy treatments. In this investigation, the authors perform air-kerma strength (SK) measurements, develop new correction factors for these measurements based on an experimentally verified energy spectrum, and test the robustness of transferring SK to a well-type ionization chamber. Methods: SK measurements were performed with the variable-aperture free-air chamber (VAFAC) at the University of Wisconsin Medical Radiation Research Center. Subsequent measurements were then performed in a well-type ionization chamber. To realize the quantity SK from a directional source with gold material present, new methods and correction factors were considered. Updated correction factors were calculated using the mcnp 6 Monte Carlo code in order to determine SK with the presence of gold fluorescent energy lines. In addition to SK measurements, a low-energy high-purity germanium (HPGe) detector was used to experimentally verify the calculated spectrum, a sodium iodide (NaI) scintillating counter was used to verify the azimuthal and polar anisotropy, and a well-type ionization chamber was used to test the feasibility of disseminating SK values for a directional source within a cylindrically symmetric measurement volume. Results: The UW VAFAC was successfully used to measure the SK of four CivaDots with reproducibilities within 0.3%. Monte Carlo methods were used to calculate the UW VAFAC correction factors and the calculated spectrum emitted from a CivaDot was experimentally verified with HPGe detector measurements. The well-type ionization chamber showed minimal variation in response (<1.5%) as a function of source positioning angle, indicating that an American Association of Physicists in Medicine (AAPM) Accredited Dosimetry Calibration Laboratory calibrated well chamber would be a suitable device to transfer an SK-based calibration to a clinical user. SK per well-chamber ionization current ratios were consistent among the four dots measured. Additionally, the measurements and predictions of anisotropy show uniform emission within the solid angle of the VAFAC, which demonstrates the robustness of the SK measurement approach. Conclusions: This characterization of a new 103Pd directional brachytherapy source helps to establish calibration methods that could ultimately be used in the well-established AAPM Task Group 43 formalism. Monte Carlo methods accurately predict the changes in the energy spectrum caused by the fluorescent x-rays produced in the gold shield. PMID:26632069

Electron-Impact Ionization Cross Section Database

National Institute of Standards and Technology Data Gateway

SRD 107 Electron-Impact Ionization Cross Section Database (Web, free access)   This is a database primarily of total ionization cross sections of molecules by electron impact. The database also includes cross sections for a small number of atoms and energy distributions of ejected electrons for H, He, and H2. The cross sections were calculated using the Binary-Encounter-Bethe (BEB) model, which combines the Mott cross section with the high-incident energy behavior of the Bethe cross section. Selected experimental data are included.

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

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

Poklonski, N. A., E-mail: poklonski@bsu.by; Vyrko, S. A.; Poklonskaya, O. N.

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator–metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atomsmore » with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature T{sub j} is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature T{sub j}, the concentration of “free” holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3T{sub j}/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to T{sub j} hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (−1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the range from 3 × 10{sup 17} to 3 × 10{sup 20 }cm{sup −3}, i.e., up to the Mott transition. The model uses no fitting parameters.« less

Fundamental studies in X-ray astrophysics

NASA Technical Reports Server (NTRS)

Lamb, D. Q.; Lightman, A. P.

1982-01-01

An analytical model calculation of the ionization structure of matter accreting onto a degenerate dwarf was carried out. Self-consistent values of the various parameters are used. The possibility of nuclear burning of the accreting matter is included. We find the blackbody radiation emitted from the stellar surface keeps hydrogen and helium ionized out to distances much larger than a typical binary separation. Except for low mass stars or high accretion rates, the assumption of complete ionization of the elements heavier than helium is a good first approximation. For low mass stars or high accretion rates the validity of assuming complete ionization depends sensitivity on the distribution of matter in the binary system.

SU-E-T-552: Monte Carlo Calculation of Correction Factors for a Free-Air Ionization Chamber in Support of a National Air-Kerma Standard for Electronic Brachytherapy

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

Mille, M; Bergstrom, P

2015-06-15

Purpose: To use Monte Carlo radiation transport methods to calculate correction factors for a free-air ionization chamber in support of a national air-kerma standard for low-energy, miniature x-ray sources used for electronic brachytherapy (eBx). Methods: The NIST is establishing a calibration service for well-type ionization chambers used to characterize the strength of eBx sources prior to clinical use. The calibration approach involves establishing the well-chamber’s response to an eBx source whose air-kerma rate at a 50 cm distance is determined through a primary measurement performed using the Lamperti free-air ionization chamber. However, the free-air chamber measurements of charge or currentmore » can only be related to the reference air-kerma standard after applying several corrections, some of which are best determined via Monte Carlo simulation. To this end, a detailed geometric model of the Lamperti chamber was developed in the EGSnrc code based on the engineering drawings of the instrument. The egs-fac user code in EGSnrc was then used to calculate energy-dependent correction factors which account for missing or undesired ionization arising from effects such as: (1) attenuation and scatter of the x-rays in air; (2) primary electrons escaping the charge collection region; (3) lack of charged particle equilibrium; (4) atomic fluorescence and bremsstrahlung radiation. Results: Energy-dependent correction factors were calculated assuming a monoenergetic point source with the photon energy ranging from 2 keV to 60 keV in 2 keV increments. Sufficient photon histories were simulated so that the Monte Carlo statistical uncertainty of the correction factors was less than 0.01%. The correction factors for a specific eBx source will be determined by integrating these tabulated results over its measured x-ray spectrum. Conclusion: The correction factors calculated in this work are important for establishing a national standard for eBx which will help ensure that dose is accurately and consistently delivered to patients.« less

Core Levels, Band Alignments, and Valence-Band States in CuSbS 2 for Solar Cell Applications

DOE PAGES

Whittles, Thomas J.; Veal, Tim D.; Savory, Christopher N.; ...

2017-11-10

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa (1-x)Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from themore » antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.« less

The 6-31B(d) basis set and the BMC-QCISD and BMC-CCSD multicoefficient correlation methods.

PubMed

Lynch, Benjamin J; Zhao, Yan; Truhlar, Donald G

2005-03-03

Three new multicoefficient correlation methods (MCCMs) called BMC-QCISD, BMC-CCSD, and BMC-CCSD-C are optimized against 274 data that include atomization energies, electron affinities, ionization potentials, and reaction barrier heights. A new basis set called 6-31B(d) is developed and used as part of the new methods. BMC-QCISD has mean unsigned errors in calculating atomization energies per bond and barrier heights of 0.49 and 0.80 kcal/mol, respectively. BMC-CCSD has mean unsigned errors of 0.42 and 0.71 kcal/mol for the same two quantities. BMC-CCSD-C is an equally effective variant of BMC-CCSD that employs Cartesian rather than spherical harmonic basis sets. The mean unsigned error of BMC-CCSD or BMC-CCSD-C for atomization energies, barrier heights, ionization potentials, and electron affinities is 22% lower than G3SX(MP2) at an order of magnitude less cost for gradients for molecules with 9-13 atoms, and it scales better (N6 vs N,7 where N is the number of atoms) when the size of the molecule is increased.

Core Levels, Band Alignments, and Valence-Band States in CuSbS2 for Solar Cell Applications.

PubMed

Whittles, Thomas J; Veal, Tim D; Savory, Christopher N; Welch, Adam W; de Souza Lucas, Francisco Willian; Gibbon, James T; Birkett, Max; Potter, Richard J; Scanlon, David O; Zakutayev, Andriy; Dhanak, Vinod R

2017-12-06

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuIn x Ga (1-x) Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.

Attachment of chloride anion to sugars: mechanistic investigation and discovery of a new dopant for efficient sugar ionization/detection in mass spectrometers.

PubMed

Boutegrabet, Lemia; Kanawati, Basem; Gebefügi, Istvan; Peyron, Dominique; Cayot, Philippe; Gougeon, Régis D; Schmitt-Kopplin, Philippe

2012-10-08

A new method for efficient ionization of sugars in the negative-ion mode of electrospray mass spectrometry is presented. Instead of using strongly hydrophobic dopants such as dichloromethane or chloroform, efficient ionization of sugars has been achieved by using aqueous HCl solution for the first time. This methodology makes it possible to use hydrophilic dopants, which are more appropriate for chromatographic separation techniques with efficient sugar ionization and detection in mass spectrometry. The interaction between chloride anions and monosaccharides (glucose and galactose) was studied by DFT in the gas phase and by implementing the polarizable continuum model (PCM) for calculations in solution at the high B3LYP/6-31+G(d,p)//B3LYP/6-311+G(2d,p) level of theory. In all optimized geometries of identified [M+Cl](-) anions, a non-covalent interaction exists. Differences were revealed between monodentate and bidentate complex anions, with the latter having noticeably higher binding energies. The calculated affinity of glucose and galactose toward the chloride anion in the gas phase and their chloride anion binding energies in solution are in excellent agreement with glucose and galactose [M+Cl](-) experimental intensity profiles that are represented as a function of the chloride ion concentration. Density functional calculations of gas-phase affinities toward chloride anion were also performed for the studied disaccharides sucrose and gentiobiose. All calculations are in excellent agreement with the experimental data. An example is introduced wherein HCl was used to effectively ionize sugars and form chlorinated adduct anions to detect sugars and glycosylated metabolites (anthocyanins) in real biological systems (Vitis vinifera grape extracts and wines), whereas they would not have been easily detectable under standard infusion electrospray mass spectrometry conditions as deprotonated species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Estimation of the influence of radical effect in the proton beams using a combined approach with physical data and gel data

NASA Astrophysics Data System (ADS)

Haneda, K.

2016-04-01

The purpose of this study was to estimate an impact on radical effect in the proton beams using a combined approach with physical data and gel data. The study used two dosimeters: ionization chambers and polymer gel dosimeters. Polymer gel dosimeters have specific advantages when compared to other dosimeters. They can measure chemical reaction and they are at the same time a phantom that can map in three dimensions continuously and easily. First, a depth-dose curve for a 210 MeV proton beam measured using an ionization chamber and a gel dosimeter. Second, the spatial distribution of the physical dose was calculated by Monte Carlo code system PHITS: To verify of the accuracy of Monte Carlo calculation, and the calculation results were compared with experimental data of the ionization chamber. Last, to evaluate of the rate of the radical effect against the physical dose. The simulation results were compared with the measured depth-dose distribution and showed good agreement. The spatial distribution of a gel dose with threshold LET value of proton beam was calculated by the same simulation code. Then, the relative distribution of the radical effect was calculated from the physical dose and gel dose. The relative distribution of the radical effect was calculated at each depth as the quotient of relative dose obtained using physical and gel dose. The agreement between the relative distributions of the gel dosimeter and Radical effect was good at the proton beams.

Research on plasma turbulence involving binary particle collisions and collective effects

NASA Technical Reports Server (NTRS)

Sandri, G.

1972-01-01

Plasmas in which binary collisions are important are studied by means of nonadiabatic methods. Two- and three-body correlations are calculated to determine the one-particle distribution for the ionization model. The general dispersion analysis is summarized, and examples of the ionization model and of the static fluctuations are discussed.

Electron impact excitation coefficients for laboratory and astrophysical plasmas

NASA Technical Reports Server (NTRS)

Davis, J.; Kepple, P. C.; Blaha, M.

1976-01-01

Electron impact excitation rate coefficients have been obtained for a number of transitions in highly ionized ions of interest to astrophysical and laboratory plasmas. The calculations were done using the method of distorted waves. Results are presented for various transitions in highly ionized Ne, Na, Al, Si, A, Ca, Ni and Fe.

Demystifying Introductory Chemistry. Part 3: Ionization Energies, Electronegativity, Polar Bonds, and Partial Charges.

ERIC Educational Resources Information Center

Spencer, James; And Others

1996-01-01

Shows how ionization energies provide a convenient method for obtaining electronegativity values that is simpler than the conventional methods. Demonstrates how approximate atomic charges can be calculated for polar molecules and how this method of determining electronegativities may lead to deeper insights than are typically possible for the…

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

Watanabe, N.; Takahashi, M.; Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577

The double processes of He in electron-impact ionization, single ionization with simultaneous excitation and double ionization, have been studied at large momentum transfer using an energy- and momentum-dispersive binary (e,2e) spectrometer. The experiment has been performed at an impact energy of 2080 eV in the symmetric noncoplanar geometry. In this way we have achieved a large momentum transfer of 9 a.u., a value that has never been realized so far for the study on double ionization. The measured (e,2e) and (e,3-1e) cross sections for transitions to the n=2 excited state of He{sup +} and to doubly ionized He{sup 2+} aremore » presented as normalized intensities relative to that to the n=1 ground state of He{sup +}. The results are compared with first-order plane-wave impulse approximation (PWIA) calculations using various He ground-state wave functions. It is shown that shapes of the momentum-dependent (e,2e) and (e,3-1e) cross sections are well reproduced by the PWIA calculations only when highly correlated wave functions are employed. However, noticeable discrepancies between experiment and theory remain in magnitude for both the double processes, suggesting the importance of higher-order effects under the experimental conditions examined as well as of acquiring more complete knowledge of electron correlation in the target.« less

Radiation hydrodynamical instabilities in cosmological and galactic ionization fronts

NASA Astrophysics Data System (ADS)

Whalen, Daniel J.; Norman, Michael L.

2011-11-01

Ionization fronts, the sharp radiation fronts behind which H/He ionizing photons from massive stars and galaxies propagate through space, were ubiquitous in the universe from its earliest times. The cosmic dark ages ended with the formation of the first primeval stars and galaxies a few hundred Myr after the Big Bang. Numerical simulations suggest that stars in this era were very massive, 25-500 solar masses, with H(II) regions of up to 30,000 light-years in diameter. We present three-dimensional radiation hydrodynamical calculations that reveal that the I-fronts of the first stars and galaxies were prone to violent instabilities, enhancing the escape of UV photons into the early intergalactic medium (IGM) and forming clumpy media in which supernovae later exploded. The enrichment of such clumps with metals by the first supernovae may have led to the prompt formation of a second generation of low-mass stars, profoundly transforming the nature of the first protogalaxies. Cosmological radiation hydrodynamics is unique because ionizing photons coupled strongly to both gas flows and primordial chemistry at early epochs, introducing a hierarchy of disparate characteristic timescales whose relative magnitudes can vary greatly throughout a given calculation. We describe the adaptive multistep integration scheme we have developed for the self-consistent transport of both cosmological and galactic ionization fronts.

Nighttime ionization by energetic particles at Wallops Island in the altitude region 120 to 200 km

NASA Technical Reports Server (NTRS)

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

1979-01-01

Five Nike Apache rockets, each including an energetic particle spectrometer and an electron density-electron temperature experiment, have been launched from Wallops Island (L = 2.6) near midnight under varying geomagnetic conditions. On the most recent of these (5 January 1978) an additional spectrometer with a broom magnet, and a 391.4 nm photometer were flown. The data from this flight indicate that the energetic particle flux consists predominantly of protons, neutral hydrogen and possibly other energetic nuclei. The energy spectrum becomes much softer and the flux more intense with increasing Kp for 10-100 keV. The pitch angle distribution at 180 km is asymmetrical with a peak at 90 deg indicating that the majority of particles are near their mirroring altitude. Ionization rates are calculated based on the measured energy spectrum and mirror height distribution. The resulting ionization rate profile is found to be nearly constant with altitude in the region 120 to 200 km. The measured energetic particle flux and calculated ionization rate from the five flights are found to vary with magnetic activity (based on the Kp and Dst indexes) in the same way as the independently derived ionization rates deduced from the electron density profile.

Calculating constants of the rates of the reactions of excitation, ionization, and atomic exchange: A model of a shock oscillator with a change of the Hamiltonian of the system

NASA Astrophysics Data System (ADS)

Tsyganov, D. L.

2017-11-01

A new model for calculating the rates of reactions of excitation, ionization, and atomic exchange is proposed. Diatomic molecule AB is an unstructured particle M upon the exchange of elastic-vibrational (VT) energy, i.e., a model of a shock forceful oscillator with a change in Hamiltonian (SFOH). The SFOH model is based on the quantum theory of strong perturbations. The SFOH model allows generalization in simulating the rates of the reactions of excitation, ionization, and atomic exchange in the vibrational-vibrational (VV) energy exchange of diatomic molecules, and the exchange of VV- and VT-energy of polyatomic molecules. The rate constants of the excitation of metastables A 3Σ u +, B 3Π g , W 3Δ u , B'3Σ u -, a'3Σ u -, and the ionization of a nitrogen molecules from ground state X2Σ g + upon a collision with a heavy structureless particle (a nitrogen molecule), are found as examples.

Numerical calculation of cosmic ray ionization rate profiles in the middle atmosphere and lower ionosphere with relation to characteristic energy intervals

NASA Astrophysics Data System (ADS)

Velinov, Peter; Asenovski, Simeon; Mateev, Lachezar

2013-04-01

Numerical calculations of galactic cosmic ray (GCR) ionization rate profiles are presented for the middle atmosphere and lower ionosphere altitudes (35-90 km) for the full GCR composition (protons, alpha particles, and groups of heavier nuclei: light L, medium M, heavy H, very heavy VH). This investigation is based on a model developed by Velinov et al. (1974) and Velinov and Mateev (2008), which is further improved in the present paper. Analytical expressions for energy interval contributions are provided. An approximation of the ionization function on three energy intervals is used and for the first time the charge decrease interval for electron capturing (Dorman 2004) is investigated quantitatively. Development in this field of research is important for better understanding the impact of space weather on the atmosphere. GCRs influence the ionization and electric parameters in the atmosphere and also the chemical processes (ozone creation and depletion in the stratosphere) in it. The model results show good agreement with experimental data (Brasseur and Solomon 1986, Rosenberg and Lanzerotti 1979, Van Allen 1952).

Atmospheric helium and geomagnetic field reversals.

NASA Technical Reports Server (NTRS)

Sheldon, W. R.; Kern, J. W.

1972-01-01

The problem of the earth's helium budget is examined in the light of recent work on the interaction of the solar wind with nonmagnetic planets. It is proposed that the dominant mode of helium (He4) loss is ion pumping by the solar wind during geomagnetic field reversals, when the earth's magnetic field is very small. The interaction of the solar wind with the earth's upper atmosphere during such a period is found to involve the formation of a bow shock. The penetration altitude of the shock-heated solar plasma is calculated to be about 700 km, and ionization rates above this level are estimated for a cascade ionization (electron avalanche) process to average 10 to the 9th power ions/sq cm/sec. The calculated ionization rates and the capacity of the solar wind to remove ionized helium (He4) from the upper atmosphere during geomagnetic dipole reversals are sufficient to yield a secular equilibrium over geologic time scales. The upward transport of helium from the lower atmosphere under these conditions is found to be adequate to sustain the proposed loss rate.

The formation of molecules in interstellar clouds from singly and multiply ionized atoms

NASA Technical Reports Server (NTRS)

Langer, W. D.

1978-01-01

The suggestion is considered that multiply ionized atoms produced by K- and L-shell X-ray ionization and cosmic-ray ionization can undergo ion-molecule reactions and also initiate molecule production. The role of X-rays in molecule production in general is discussed, and the contribution to molecule production of the C(+) radiative association with hydrogen is examined. Such gas-phase reactions of singly and multiply ionized atoms are used to calculate molecular abundances of carbon-, nitrogen-, and oxygen-bearing species. The column densities of the molecules are evaluated on the basis of a modified version of previously developed isobaric cloud models. It is found that reactions of multiply ionized carbon with H2 can contribute a significant fraction of the observed CH in diffuse interstellar clouds in the presence of diffuse X-ray structures or discrete X-ray sources and that substantial amounts of CH(+) can be produced under certain conditions.

The ionization length in plasmas with finite temperature ion sources

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

Jelic, N.; Kos, L.; Duhovnik, J.

2009-12-15

The ionization length is an important quantity which up to now has been precisely determined only in plasmas which assume that the ions are born at rest, i.e., in discharges known as 'cold ion-source' plasmas. Presented here are the results of our calculations of the ionization lengths in plasmas with an arbitrary ion source temperature. Harrison and Thompson (H and T) [Proc. Phys. Soc. 74, 145 (1959)] found the values of this quantity for the cases of several ion strength potential profiles in the well-known Tonks-Langmuir [Phys. Rev. 34, 876 (1929)] discharge, which is characterized by 'cold' ion temperature. Thismore » scenario is also known as the 'singular' ion-source discharge. The H and T analytic result covers cases of ion sources proportional to exp(betaPHI) with PHI the normalized plasma potential and beta=0,1,2 values, which correspond to particular physical scenarios. Many years following H and T's work, Bissell and Johnson (B and J) [Phys. Fluids 30, 779 (1987)] developed a model with the so-called 'warm' ion-source temperature, i.e., 'regular' ion source, under B and J's particular assumption that the ionization strength is proportional to the local electron density. However, it appears that B and J were not interested in determining the ionization length at all. The importance of this quantity to theoretical modeling was recognized by Riemann, who recently answered all the questions of the most advanced up-to-date plasma-sheath boundary theory with cold ions [K.-U. Riemann, Phys. Plasmas 13, 063508 (2006)] but still without the stiff warm ion-source case solution, which is highly resistant to solution via any available analytic method. The present article is an extension of H and T's results obtained for a single point only with ion source temperature T{sub n}=0 to arbitrary finite ion source temperatures. The approach applied in this work is based on the method recently developed by Kos et al. [Phys. Plasmas 16, 093503 (2009)].« less

High-Level ab Initio Predictions for the Ionization Energies, Bond Dissociation Energies, and Heats of Formation of Titanium Oxides and Their Cations (TiOn/TiOn+, n = 1 and 2).

PubMed

Pan, Yi; Luo, Zhihong; Chang, Yih-Chung; Lau, Kai-Chung; Ng, C Y

2017-01-26

The ionization energies (IEs) of TiO and TiO 2 and the 0 K bond dissociation energies (D 0 ) and the heats of formation at 0 K (ΔH° f0 ) and 298 K (ΔH° f298 ) for TiO/TiO + and TiO 2 /TiO 2 + are predicted by the wave-function-based CCSDTQ/CBS approach. The CCSDTQ/CBS calculations involve the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations along with the zero-point vibrational energy (ZPVE), high-order correlation (HOC), core-valence (CV) electronic, spin-orbit (SO) coupling, and scalar relativistic (SR) effect corrections. The present calculations yield IE(TiO) = 6.815 eV and are in good agreement with the experimental IE value of 6.819 80 ± 0.000 10 eV determined in a two-color laser-pulsed field ionization-photoelectron (PFI-PE) study. The CCSDT and MRCI+Q methods give the best predictions to the harmonic frequencies: ω e (ω e + ) = 1013 (1069) and 1027 (1059) cm -1 and the bond lengths r e (r e + ) = 1.625 (1.587) and 1.621 (1.588) Å, for TiO (TiO + ) compared with the experimental values. Two nearly degenerate, stable structures are found for TiO 2 cation: TiO 2 + (C 2v ) structure has two equivalent TiO bonds, while the TiO 2 + (C s ) structure features a long and a short TiO bond. The IEs for the TiO 2 + (C 2v )←TiO 2 and TiO 2 + (C s )←TiO 2 ionization transitions are calculated to be 9.515 and 9.525 eV, respectively, giving the theoretical adiabatic IE value in good agreement with the experiment IE(TiO 2 ) = 9.573 55 ± 0.000 15 eV obtained in the previous vacuum ultraviolet (VUV)-PFI-PE study of TiO 2 . The potential energy surface of TiO 2 + along the normal vibrational coordinates of asymmetric stretching mode (ω 3 + ) is nearly flat and exhibits a double-well potential with the well of TiO 2 + (C s ) situated around the central well of TiO 2 + (C 2v ). This makes the theoretical calculation of ω 3 + infeasible. For the symmetric stretching (ω 1 + ), the current theoretical predictions overestimate the experimental value of 829.1 ± 2.0 cm -1 by more than 100 cm -1 . This work together with the previous experimental and theoretical investigations supports the conclusion that the CCSDTQ/CBS approach is capable of providing reliable IE and D 0 predictions for TiO/TiO + and TiO 2 /TiO 2 + with error limits less than or equal to 60 meV. The CCSDTQ/CBS calculations give the predictions of D 0 (Ti + -O) - D 0 (Ti-O) = 0.004 eV and D 0 (O-TiO) - D 0 (O-TiO + ) = 2.699 eV, which are also consistent with the respective experimental determination of 0.008 32 ± 0.000 10 and 2.753 75 ± 0.000 18 eV.

Density-functional study on the equilibria in the ThDP activation.

PubMed

Delgado, Eduardo J; Alderete, Joel B; Jaña, Gonzalo A

2011-11-01

The equilibria among the various ionization and tautomeric states involved in the activation of ThDP is addressed using high level density functional theory calculations, X3LYP/6-311++G(d,p)//X3LYP(PB)/6-31++G(d,p). This study provides the first theoretically derived thermodynamic data for the internal equilibria in the activation of ThDP. The role of the medium polarity on the geometry and thermodynamics of the diverse equilibria of ThDP is addressed. The media chosen are cyclohexane and water, as paradigms of apolar and polar media. The results suggest that all ionization and tautomeric states are accessible during the catalytic cycle, even in the absence of substrate, being APH(+) the form required to interconvert the AP and IP tautomers; and the generation of the ylide proceeds via the formation of the IP form. Additionally, the calculated ΔG° values allow to calculate all the equilibrium constants, including the pK(C2) for the thiazolium C2 atom whose ionization is believed to initiate the catalytic cycle.

Vacuum ultraviolet photoionization of carbohydrates and nucleotides

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

Shin, Joong-Won, E-mail: jshin@govst.edu; Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872; Bernstein, Elliot R., E-mail: erb@lamar.colostate.edu

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5{sup ′}-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate,more » rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C–C and C–O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.« less

Electron Transport Coefficients and Effective Ionization Coefficients in SF6-O2 and SF6-Air Mixtures Using Boltzmann Analysis

NASA Astrophysics Data System (ADS)

Wei, Linsheng; Xu, Min; Yuan, Dingkun; Zhang, Yafang; Hu, Zhaoji; Tan, Zhihong

2014-10-01

The electron drift velocity, electron energy distribution function (EEDF), density-normalized effective ionization coefficient and density-normalized longitudinal diffusion velocity are calculated in SF6-O2 and SF6-Air mixtures. The experimental results from a pulsed Townsend discharge are plotted for comparison with the numerical results. The reduced field strength varies from 40 Td to 500 Td (1 Townsend=10-17 V·cm2) and the SF6 concentration ranges from 10% to 100%. A Boltzmann equation associated with the two-term spherical harmonic expansion approximation is utilized to gain the swarm parameters in steady-state Townsend. Results show that the accuracy of the Boltzmann solution with a two-term expansion in calculating the electron drift velocity, electron energy distribution function, and density-normalized effective ionization coefficient is acceptable. The effective ionization coefficient presents a distinct relationship with the SF6 content in the mixtures. Moreover, the E/Ncr values in SF6-Air mixtures are higher than those in SF6-O2 mixtures and the calculated value E/Ncr in SF6-O2 and SF6-Air mixtures is lower than the measured value in SF6-N2. Parametric studies conducted on these parameters using the Boltzmann analysis offer substantial insight into the plasma physics, as well as a basis to explore the ozone generation process.

Comparison of two equation-of-state models for partially ionized aluminum: Zel'dovich and Raizer's model versus the activity expansion code

NASA Astrophysics Data System (ADS)

Harrach, Robert J.; Rogers, Forest J.

1981-09-01

Two equation-of-state (EOS) models for multipy ionized matter are evaluated for the case of an aluminum plasma in the temperature range from about one eV to several hundred eV, spanning conditions of weak to strong ionization. Specifically, the simple analytical mode of Zel'dovich and Raizer and the more comprehensive model comprised by Rogers' plasma physics avtivity expansion code (ACTEX) are used to calculate the specific internal energy ɛ and average degree of ionization Z¯*, as functons of temperature T and density ρ. In the absence of experimental data, these results are compared against each other, covering almost five orders-of-magnitude variation in ɛ and the full range of Z¯* We find generally good agreement between the two sets of results, especially for low densities and for temperatures near the upper end of the rage. Calculated values of ɛ(T) agree to within ±30% over nearly the full range in T for densities below about 1 g/cm3. Similarly, the two models predict values of Z¯*(T) which track each other fairly well; above 20 eV the discrepancy is less than ±20% fpr ρ≲1 g/cm3. Where the calculations disagree, we expect the ACTEX code to be more accurate than Zel'dovich and Raizer's model, by virtue of its more detailed physics content.

Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2016-07-21

Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.

Validity of virial theorem in all-electron mixed basis density functional, Hartree–Fock, and GW calculations

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

Kuwahara, Riichi; Accelrys K. K., Kasumigaseki Tokyu Building 17F, 3-7-1 Kasumigaseki, Chiyoda-ku, Tokyo 100-0013; Tadokoro, Yoichi

In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree–Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is inmore » excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA.« less

Spectroscopic investigation, HOMO-LUMO and NLO studies on L-histidinium maleate based on DFT approach

NASA Astrophysics Data System (ADS)

Dhanavel, S.; Stephen, A.; Asirvatham, P. Samuel

2017-05-01

The molecular structure of the title compound L-Histidinium Maleate (LHM) was constructed and optimized based on Density Functional Theory method (DFT-B3LYP) with the 6-31G (d,p) basis set. The fundamental vibrational spectral assignment was analyzed with the aid of optimized structure of LHM. The study on electronic properties such as, HOMO-LUMO energies and absorption wavelength were performed using Time dependent DFT (TD-DFT) approach which reveals that energy transfer occur within the molecule. 13C NMR chemical shift values were measured using Gauge independent atomic orbital method (GIAO) and the obtained values are in good agreement with the reported experimental values. Hardness, ionization potential and electrophilicity index also calculated. The electric dipole moment (μtot) and hyperpolarizability (βtot) values of the investigated molecules were computed. The calculated value (β) was 3.7 times higher than that of urea, which confirms the LHM molecule is a potential candidate for NLO applications.

Measurements of the structure of an ionizing shock wave in a hydrogen-helium mixture

NASA Technical Reports Server (NTRS)

Leibowitz, L. P.

1972-01-01

Shock structure during ionization of a hydrogen-helium mixture was studied using hydrogen line and continuum emission measurements. A reaction scheme is proposed which includes hydrogen dissociation and a two-step excitation-ionization mechanism for hydrogen ionization by atom-atom and atom-electron collisions. Agreement was achieved between numerical calculations and measurements of emission intensity as a function of time for shock velocities from 13 to 20 km/sec in a 0.208 H2 - 0.792 He mixture. The electron temperature was found to be significantly different from the heavy particle temperature during much of the ionization process. Similar time histories for H beta and continuum emission indicate upper level populations of hydrogen in equilibrium with the electron concentration during the relaxation process.

Measurements of the structure of an ionizing shock wave in a hydrogen-helium mixture.

NASA Technical Reports Server (NTRS)

Leibowitz, L. P.

1973-01-01

Shock structure during ionization of a hydrogen-helium mixture has been followed using hydrogen line and continuum emission measurements. A reaction scheme is proposed which includes hydrogen dissociation and a two-step excitation-ionization mechanism for hydrogen ionization by atom-atom and atom-electron collisions. Agreement has been achieved between numerical calculations and measurements of emission intensity as a function of time for shock velocities from 13 to 20 km/sec in a 0.208 H2-0.792 He mixture. The electron temperature was found to be significantly different from the heavy particle temperature during much of the ionization process. Similar time histories for H beta and continuum emission indicate upper level populations of hydrogen in equilibrium with the electron concentration during the relaxation process.

Diagnostic studies of ion beam formation in inductively coupled plasma

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

Jacobs, Jenee L.

2015-01-01

This dissertation describes a variety of studies focused on the plasma and the ion beam in inductively coupled plasma mass spectrometry (ICP-MS). The ability to use ICP-MS for measurements of trace elements in samples requires the analytes to be efficiently ionized. Updated ionization efficiency tables are discussed for ionization temperatures of 6500 K and 7000 K with an electron density of 1 x 10 15 cm -3. These values are reflective of the current operating parameters of ICP-MS instruments. Calculations are also discussed for doubly charged (M 2+) ion formation, neutral metal oxide (MO) ionization, and metal oxide (MO +)more » ion dissociation for similar plasma temperature values. Ionization efficiency results for neutral MO molecules in the ICP have not been reported previously.« less

UV-visible degradation of boscalid--structural characterization of photoproducts and potential toxicity using in silico tests.

PubMed

Lassalle, Yannick; Kinani, Aziz; Rifai, Ahmad; Souissi, Yasmine; Clavaguera, Carine; Bourcier, Sophie; Jaber, Farouk; Bouchonnet, Stéphane

2014-05-30

Boscalid is a carboximide fungicide mainly used for vineyard protection as well as for tomato, apple, blueberry and various ornamental cultivations. The structural elucidation of by-products arising from the UV-visible photodegradation of boscalid has been investigated by gas chromatography/multi-stage mass spectrometry (GC/MS(n) ) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) couplings. The potential toxicities of transformation products were estimated by in silico calculations. Aqueous solutions of boscalid were irradiated up to 150 min in a self-made reactor equipped with a mercury lamp. Analyses were carried out using a gas chromatograph coupled with an ion trap mass spectrometer operated in both electron ionization (EI) and chemical ionization (CI) modes and a liquid chromatograph coupled with a quadrupole time-of-flight (Q-TOF) mass spectrometer operated in electrospray ionization (ESI) mode. Multiple-stage collision-induced dissociation (CID) experiments were performed to establish dissociation pathways of ions. The QSAR (Quantitative Structure-Activity Relationship) T.E.S.T. program allowed the estimation of the toxicities of the by-products. Eight photoproducts were investigated. Chemical structures were proposed not only on the interpretation of multi-stage CID experiments, but also on kinetics data. These structures led us to suggest photodegradation pathways. Three photoproducts were finally detected in Lebanon in a real sample of grape leaves for which routine analysis had led to the detection of boscalid at 4 mg kg(-1). With one exception, the structures proposed for the photoproducts on the basis of mass spectra interpretation have not been reported in previous studies. In silico toxicity predictions showed that two photoproducts are potentially more toxic than the parent compound considering oral rat LD50 while five photoproducts may induce mutagenic toxicity. With the exception of one compound, all photoproducts may potentially induce developmental toxicity. Copyright © 2014 John Wiley & Sons, Ltd.

Electron and hole stability in GaN and ZnO.

PubMed

Walsh, Aron; Catlow, C Richard A; Miskufova, Martina; Sokol, Alexey A

2011-08-24

We assess the thermodynamic doping limits of GaN and ZnO on the basis of point defect calculations performed using the embedded cluster approach and employing a hybrid non-local density functional for the quantum mechanical region. Within this approach we have calculated a staggered (type-II) valence band alignment between the two materials, with the N 2p states contributing to the lower ionization potential of GaN. With respect to the stability of free electron and hole carriers, redox reactions resulting in charge compensation by ionic defects are found to be largely endothermic (unfavourable) for electrons and exothermic (favourable) for holes, which is consistent with the efficacy of electron conduction in these materials. Approaches for overcoming these fundamental thermodynamic limits are discussed. © 2011 IOP Publishing Ltd

Cs 62 DJ Rydberg-atom macrodimers formed by long-range multipole interaction

NASA Astrophysics Data System (ADS)

Han, Xiaoxuan; Bai, Suying; Jiao, Yuechun; Hao, Liping; Xue, Yongmei; Zhao, Jianming; Jia, Suotang; Raithel, Georg

2018-03-01

Long-range macrodimers formed by D -state cesium Rydberg atoms are studied in experiments and calculations. Cesium [62DJ]2 Rydberg-atom macrodimers, bonded via long-range multipole interaction, are prepared by two-color photoassociation in a cesium atom trap. The first color (pulse A) resonantly excites seed Rydberg atoms, while the second (pulse B, detuned by the molecular binding energy) resonantly excites the Rydberg-atom macrodimers below the [62DJ]2 asymptotes. The molecules are measured by extraction of autoionization products and Rydberg-atom electric-field ionization, and ion detection. Molecular spectra are compared with calculations of adiabatic molecular potentials. From the dependence of the molecular signal on the detection delay time, the lifetime of the molecules is estimated to be 3 -6 μ s .

Continuum Electrostatics Approaches to Calculating pKas and Ems in Proteins.

PubMed

Gunner, M R; Baker, N A

2016-01-01

Proteins change their charge state through protonation and redox reactions as well as through binding charged ligands. The free energy of these reactions is dominated by solvation and electrostatic energies and modulated by protein conformational relaxation in response to the ionization state changes. Although computational methods for calculating these interactions can provide very powerful tools for predicting protein charge states, they include several critical approximations of which users should be aware. This chapter discusses the strengths, weaknesses, and approximations of popular computational methods for predicting charge states and understanding the underlying electrostatic interactions. The goal of this chapter is to inform users about applications and potential caveats of these methods as well as outline directions for future theoretical and computational research. © 2016 Elsevier Inc. All rights reserved.

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

Zhang, Shen; Kang, Wei, E-mail: weikang@pku.edu.cn; College of Engineering, Peking University, Beijing 100871

An extended first-principles molecular dynamics (FPMD) method based on Kohn-Sham scheme is proposed to elevate the temperature limit of the FPMD method in the calculation of dense plasmas. The extended method treats the wave functions of high energy electrons as plane waves analytically and thus expands the application of the FPMD method to the region of hot dense plasmas without suffering from the formidable computational costs. In addition, the extended method inherits the high accuracy of the Kohn-Sham scheme and keeps the information of electronic structures. This gives an edge to the extended method in the calculation of mixtures ofmore » plasmas composed of heterogeneous ions, high-Z dense plasmas, lowering of ionization potentials, X-ray absorption/emission spectra, and opacities, which are of particular interest to astrophysics, inertial confinement fusion engineering, and laboratory astrophysics.« less

The Interaction Between Accretion from the Interstellar Medium and Accretion from the Evolved Binary Component in Barium Stars

NASA Astrophysics Data System (ADS)

Jeong, Yeuncheol; Yushchenko, Alexander V.; Doikov, Dmytry N.

2018-03-01

The reanalysis of the previously published abundance pattern of mild barium star HD202109 (ζ Cyg) and the chemical compositions of 129 thin disk barium stars facilitated the search for possible correlations of different stellar parameters with second ionization potentials of chemical elements. Results show that three valuable correlations exist in the atmospheres of barium stars. The first is the relationship between relative abundances and second ionization potentials. The second is the age dependence of mean correlation coefficients of relative abundances vs. second ionization potentials, and the third one is the changes in correlation coefficients of relative abundances vs. second ionization potentials as a function of stellar spatial velocities and overabundances of s-process elements. These findings demonstrate the possibility of hydrogen and helium accretion from the interstellar medium on the atmospheres of barium stars.

Direct detection of sub-GeV dark matter with semiconductor targets

DOE PAGES

Essig, Rouven; Fernández-Serra, Marivi; Mardon, Jeremy; ...

2016-05-09

Dark matter in the sub-GeV mass range is a theoretically motivated but largely unexplored paradigm. Such light masses are out of reach for conventional nuclear recoil direct detection experiments, but may be detected through the small ionization signals caused by dark matter-electron scattering. Semiconductors are well-studied and are particularly promising target materials because their O(1 eV) band gaps allow for ionization signals from dark matter particles as light as a few hundred keV. Current direct detection technologies are being adapted for dark matter-electron scattering. In this paper, we provide the theoretical calculations for dark matter-electron scattering rate in semiconductors, overcomingmore » several complications that stem from the many-body nature of the problem. We use density functional theory to numerically calculate the rates for dark matter-electron scattering in silicon and germanium, and estimate the sensitivity for upcoming experiments such as DAMIC and SuperCDMS. We find that the reach for these upcoming experiments has the potential to be orders of magnitude beyond current direct detection constraints and that sub-GeV dark matter has a sizable modulation signal. We also give the first direct detection limits on sub-GeV dark matter from its scattering off electrons in a semiconductor target (silicon) based on published results from DAMIC. We make available publicly our code, QEdark, with which we calculate our results. Our results can be used by experimental collaborations to calculate their own sensitivities based on their specific setup. In conclusion, the searches we propose will probe vast new regions of unexplored dark matter model and parameter space.« less

The effect of surface charge, negative and bipolar ionization on the deposition of airborne bacteria.

PubMed

Meschke, S; Smith, B D; Yost, M; Miksch, R R; Gefter, P; Gehlke, S; Halpin, H A

2009-04-01

A series of experiments were conducted to evaluate the effect of surface charge and air ionization on the deposition of airborne bacteria. The interaction between surface electrostatic potential and the deposition of airborne bacteria in an indoor environment was investigated using settle plates charged with electric potentials of 0, +/-2.5kV and +/-5kV. Results showed that bacterial deposition on the plates increased proportionally with increased potential to over twice the gravitational sedimentation rate at +5kV. Experiments were repeated under similar conditions in the presence of either negative or bipolar air ionization. Bipolar air ionization resulted in reduction of bacterial deposition onto the charged surfaces to levels nearly equal to gravitational sedimentation. In contrast, diffusion charging appears to have occurred during negative air ionization, resulting in an even greater deposition onto the oppositely charged surface than observed without ionization. Static charges on fomitic surfaces may attract bacteria resulting in deposition in excess of that expected by gravitational sedimentation or simple diffusion. Implementation of bipolar ionization may result in reduction of bacterial deposition. Fomitic surfaces are important vehicles for the transmission of infectious organisms. This study has demonstrated a simple strategy for minimizing charge related deposition of bacteria on surfaces.

Plasma diagnostics from intensities of resonance line series of He-like ions

NASA Astrophysics Data System (ADS)

Ryazantsev, S. N.; Skobelev, I. Yu.; Faenov, A. Ya.; Grum-Grzhimailo, A. N.; Pikuz, T. A.; Pikuz, S. A.

2017-04-01

The possibility of using the relative intensities of the 1 snp 1P1-1 s 2 1S0 transitions with n = 3-6 in He-like multicharged ions to diagnose plasma in a nonstationary ionization state is considered. The calculations performed for F VIII ions show that, at electron temperatures of T e = 10-100 eV, the intensity ratios are sensitive to the plasma electron density in the range of N e = 1016-1020 cm-3. The universal calculated dependences can be used to diagnose various kinds of recombining or ionizing plasmas containing such ions.

Torsional energy levels of CH₃OH⁺/CH₃OD⁺/CD₃OD⁺ studied by zero-kinetic energy photoelectron spectroscopy and theoretical calculations.

PubMed

Dai, Zuyang; Gao, Shuming; Wang, Jia; Mo, Yuxiang

2014-10-14

The torsional energy levels of CH3OH(+), CH3OD(+), and CD3OD(+) have been determined for the first time using one-photon zero kinetic energy photoelectron spectroscopy. The adiabatic ionization energies for CH3OH, CH3OD, and CD3OD are determined as 10.8396, 10.8455, and 10.8732 eV with uncertainties of 0.0005 eV, respectively. Theoretical calculations have also been performed to obtain the torsional energy levels for the three isotopologues using a one-dimensional model with approximate zero-point energy corrections of the torsional potential energy curves. The calculated values are in good agreement with the experimental data. The barrier height of the torsional potential energy without zero-point energy correction was calculated as 157 cm(-1), which is about half of that of the neutral (340 cm(-1)). The calculations showed that the cation has eclipsed conformation at the energy minimum and staggered one at the saddle point, which is the opposite of what is observed in the neutral molecule. The fundamental C-O stretch vibrational energy level for CD3OD(+) has also been determined. The energy levels for the combinational excitation of the torsional vibration and the fundamental C-O stretch vibration indicate a strong torsion-vibration coupling.

Nonlinear optical response in narrow graphene nanoribbons

NASA Astrophysics Data System (ADS)

Karimi, Farhad; Knezevic, Irena

We present an iterative method to calculate the nonlinear optical response of armchair graphene nanoribbons (aGNRs) and zigzag graphene nanoribbons (zGNRs) while including the effects of dissipation. In contrast to methods that calculate the nonlinear response in the ballistic (dissipation-free) regime, here we obtain the nonlinear response of an electronic system to an external electromagnetic field while interacting with a dissipative environment (to second order). We use a self-consistent-field approach within a Markovian master-equation formalism (SCF-MMEF) coupled with full-wave electromagnetic equations, and we solve the master equation iteratively to obtain the higher-order response functions. We employ the SCF-MMEF to calculate the nonlinear conductance and susceptibility, as well as to calculate the dependence of the plasmon dispersion and plasmon propagation length on the intensity of the electromagnetic field in GNRs. The electron scattering mechanisms included in this work are scattering with intrinsic phonons, ionized impurities, surface optical phonons, and line-edge roughness. Unlike in wide GNRs, where ionized-impurity scattering dominates dissipation, in ultra-narrow nanoribbons on polar substrates optical-phonon scattering and ionized-impurity scattering are equally prominent. Support by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-SC0008712.

Electron- and proton-induced ionization of pyrimidine

NASA Astrophysics Data System (ADS)

Champion, Christophe; Quinto, Michele A.; Weck, Philippe F.

2015-05-01

The present work describes a quantum-mechanically based model of the electron- and proton-induced ionization of isolated pyrimidine molecules. The impact energies range from the target ionization threshold up to ~1 keV for electrons and from 10 keV up to 10 MeV for protons. The cross-section calculations are performed within the 1st Born approximation in which the ejected electron is described by a Coulomb wave whereas the incident and the scattered projectiles are both described by plane waves. The pyrimidine target is described using the Gaussian 09 software package. The theoretical predictions obtained are in good agreement with experimental absolute total cross sections, while large discrepancies are observed between existing semi-empirical models and the present calculations. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

Analysis of multiple scattering contributions in electron-impact ionization of molecular hydrogen

NASA Astrophysics Data System (ADS)

Ren, Xueguang; Hossen, Khokon; Wang, Enliang; Pindzola, M. S.; Dorn, Alexander; Colgan, James

2017-10-01

We report a combined experimental and theoretical study on the low-energy (E 0 = 31.5 eV) electron-impact ionization of molecular hydrogen (H2). Triple differential cross sections are measured for a range of fixed emission angles of one outgoing electron between {θ }1=-70^\\circ and -130° covering the full 4π solid angle of the second electron. The energy sharing of the outgoing electrons varies from symmetric ({E}1={E}2=8 eV) to highly asymmetric (E 1 = 1 eV and E 2 = 15 eV). In addition to the binary and recoil lobes, a structure is observed perpendicular to the incoming beam direction which is due to multiple scattering of the projectile inside the molecular potential. The absolutely normalized experimental cross sections are compared with results from the time-dependent close-coupling (TDCC) calculations. Molecular alignment dependent TDCC results demonstrate that these structures are only present if the molecule axis is lying in the scattering plane.

Ionic rotational branching ratios in resonant enhanced multiphoton ionization of NO via the A2Sigma(+)(3s sigma) and D2Sigma(+)(3p sigma) states

NASA Technical Reports Server (NTRS)

Rudolph, H.; Mckoy, V.; Dixit, S. N.; Huo, W. M.

1988-01-01

Results are presented for the rotationally resolved photoelectron spectra resulting from a (2 + 1) one-color resonant enhanced multiphoton ionization (REMPI) of NO via the rotationally clean S21(11.5) and mixed S11(15.5) + R21(15.5) branches of the 0-0 transition in the D-X band. The calculations were done in the fixed-nuclei frozen core approximation. The resulting photoionization spectra, convoluted with a Lorentzian detection function, agree qualitatively with experimental results of Viswanathan et al. (1986) and support their conclusion that the nonspherical nature of the molecular potential creates a substantial l-mixing in the continuum, which in turn leads to the intense Delta N = 0 peak. The rather strong photoelectron energy dependence of the rotational branching ratios of the D 2Sigma(+) S21(11.5) line was investigated and compared to the weak energy dependence of the A 2Sigma(+) R22(21.5) line.

Photochemical Escape of Atomic Carbon from Mars

NASA Astrophysics Data System (ADS)

Fox, J. L.; Hac, A. B.

2009-12-01

Determining the escape rate of C over time is necessary to reconstructing the time-dependent history of volatiles on Mars. We report initial results from a one-dimensional spherical Monte Carlo calculation of photochemical escape fluxes and rates of atomic carbon from the Martian atmosphere. This model has recently been used to estimate the photochemical escape flux of O from Mars. We include as sources photodissociation of CO, dissociative recombination of CO+, photoelectron-impact dissociation of CO, photodissociative ionization and photoelectron impact dissociative ionization. Dissociative recombination of CO2+ has been suggested as a source of C (in the channel that produces C + O2) but later studies have found that the yield of this channel is negligible. We test the potential importance of this reaction by comparing the final results produced by including it and excluding it. Finally we compare the range of the escape rate to that of C in ions that have been modeled or measured by ASPERA instruments on MEX and Phobos.

Development of a Computationally Efficient, High Fidelity, Finite Element Based Hall Thruster Model

NASA Technical Reports Server (NTRS)

Jacobson, David (Technical Monitor); Roy, Subrata

2004-01-01

This report documents the development of a two dimensional finite element based numerical model for efficient characterization of the Hall thruster plasma dynamics in the framework of multi-fluid model. Effect of the ionization and the recombination has been included in the present model. Based on the experimental data, a third order polynomial in electron temperature is used to calculate the ionization rate. The neutral dynamics is included only through the neutral continuity equation in the presence of a uniform neutral flow. The electrons are modeled as magnetized and hot, whereas ions are assumed magnetized and cold. The dynamics of Hall thruster is also investigated in the presence of plasma-wall interaction. The plasma-wall interaction is a function of wall potential, which in turn is determined by the secondary electron emission and sputtering yield. The effect of secondary electron emission and sputter yield has been considered simultaneously, Simulation results are interpreted in the light of experimental observations and available numerical solutions in the literature.

Some Dynamical Features of Molecular Fragmentation by Electrons and Swift Ions

NASA Astrophysics Data System (ADS)

Montenegro, E. C.; Sigaud, L.; Wolff, W.; Luna, H.; Natalia, Ferreira

To date, the large majority of studies on molecular fragmentation by swift charged particles have been carried out using simple molecules, for which reliable Potential Energy Curves are available to interpret the measured fragmentation yields. For complex molecules the scenario is quite different and such guidance is not available, obscuring even a simple organization of the data which are currently obtained for a large variety of molecules of biological or technological interest. In this work we show that a general and relatively simple methodology can be used to obtain a broader picture of the fragmentation pattern of an arbitrary molecule. The electronic ionization or excitation cross section of a given molecular orbital, which is the first part of the fragmentation process, can be well scaled by a simple and general procedure at high projectile velocities. The fragmentation fractions arising from each molecular orbital can then be achieved by matching the calculated ionization with the measured fragmentation cross sections. Examples for Oxygen, Chlorodifluoromethane and Pyrimidine molecules are presented.

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

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

Hu, S. X., E-mail: shu@lle.rochester.edu; Goncharov, V. N.; McCrory, R. L.

2016-04-15

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations of the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm{sup 3} and T = 15 625 to 500 000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which gives an increasing ionization as the CH density increases even at low temperatures (T < 50 eV). The orbital-free molecular dynamics method is only used to gauge the average ionization behavior of CH under the average-atommore » model in conjunction with the pressure-matching mixing rule. The thermal conductivities (κ{sub QMD}) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted with a generalized Coulomb logarithm [(lnΛ){sub QMD}] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted ∼20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.« less

Synthetic IRIS spectra of the solar transition region: Effect of high-energy tails

NASA Astrophysics Data System (ADS)

Dzifčáková, E.; Vocks, C.; Dudík, J.

2017-06-01

Aims: The solar transition region satisfies the conditions for presence of non-Maxwellian electron energy distributions with high-energy tails at energies corresponding to the ionization potentials of many ions emitting in the extreme-ultraviolet and ultraviolet portions of the spectrum. Methods: We calculate the synthetic Si iv, O iv, and S iv spectra in the far ultraviolet channel of the Interface Region Imaging Spectrograph (IRIS). Ionization, recombination, and excitation rates are obtained by integration of the cross-sections or their approximations over the model electron distributions considering particle propagation from the hotter corona. Results: The ionization rates are significantly affected by the presence of high-energy tails. This leads to the peaks of the relative abundance of individual ions to be broadened with pronounced low-temperature shoulders. As a result, the contribution functions of individual lines observable by IRIS also exhibit low-temperature shoulders, or their peaks are shifted to temperatures an order of magnitude lower than for the Maxwellian distribution. The integrated emergent spectra can show enhancements of Si iv compared to O iv by more than a factor of two. Conclusions: The high-energy particles can have significant impact on the emergent spectra and their presence needs to be considered even in situations without strong local acceleration.

Semiconductor detector with smoothly tunable effective thickness for the study of ionization loss by moderately relativistic electrons

NASA Astrophysics Data System (ADS)

Shchagin, A. V.; Shul'ga, N. F.; Trofymenko, S. V.; Nazhmudinov, R. M.; Kubankin, A. S.

2016-11-01

The possibility of measurement of electrons ionization loss in Si layer of smoothly tunable thickness is shown in the proof-of-principle experiment. The Si surface-barrier detector with the depleted layer thickness controlled by the value of high voltage power supply has been used. Ionization loss spectra for electrons emitted by radioactive source 207Bi are presented and discussed. Experimental results for the most probable ionization loss in the Landau spectral peak are compared with theoretical calculations. The possibility of research of evolution of electromagnetic field of ultra-relativistic particles traversing media interface with the use of detectors with smoothly tunable thickness is proposed.

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

Ionization of biomolecular targets by ion impact: input data for radiobiological applications

NASA Astrophysics Data System (ADS)

de Vera, Pablo; Abril, Isabel; Garcia-Molina, Rafael; Solov'yov, Andrey V.

2013-06-01

In this work we review and further develop a semiempirical model recently proposed for the ion impact ionization of complex biological media. The model is based on the dielectric formalism, and makes use of a semiempirical parametrization of the optical energy-loss function of bioorganic compounds, allowing the calculation of single and total ionization cross sections and related quantities for condensed biological targets, such as liquid water, DNA and its components, proteins, lipids, carbohydrates or cell constituents. The model shows a very good agreement with experimental data for water, adenine and uracil, and allows the comparison of the ionization efficiency of different biological targets, and also the average kinetic energy of the ejected secondary electrons.

Onset of space charge effects in liquid argon ionization chambers

NASA Astrophysics Data System (ADS)

Toggerson, B.; Newcomer, A.; Rutherfoord, J.; Walker, R. B.

2009-09-01

Using a thin-gap liquid argon ionization chamber and Strontium-90 beta sources we have measured ionization currents over a wide range of gap potentials. These precision "HV plateau curves" advance the understanding of liquid argon sampling calorimeter signals, particularly at high ionization rates. The order of magnitude differences in the activities of the beta sources allow us to estimate where the ionization chamber is driven into the space-charge dominated regime.

Summary of ionizing radiation analysis on the Long Duration Exposure Facility

NASA Technical Reports Server (NTRS)

Parnell, T. A.

1991-01-01

The Ionizing Radiation Special Investigation Group (IRSIG) for the Long Duration Exposure Facility (LDEF) was established to perform radiation measurements and analysis not planned in the original experiments, and to assure availability of LDEF analysis results in a form useful to future missions. The IRSIG has organized extensive induced radioactivity measurements throughout LDEF, and a comprehensive program to compare the LDEF radiation measurements to values calculated using environment models. The activities and present status of the Group is described. The ionizing radiation results presented is summarized.

Processes of ionization of atoms in nonstationary states by the field of an attosecond pulse

NASA Astrophysics Data System (ADS)

Makarov, D. N.; Matveev, V. I.

2015-02-01

Processes of ionization at the interaction of attosecond pulses of an electromagnetic field with atoms in nonstationary states have been considered. The probabilities and ionization cross section at the radiative relaxation of an excited state of a single-electron atom and at the Auger decay of the autoionization state of a two-electron atom have been calculated. The developed method allows the expansion to the case of more complex targets, including those in the collision state, and to various chemical reactions.

Physical parameters for proton induced K-, L-, and M-shell ionization processes

NASA Astrophysics Data System (ADS)

Shehla; Puri, Sanjiv

2016-10-01

The proton induced atomic inner-shell ionization processes comprising radiative and non-radiative transitions are characterized by physical parameters, namely, the proton ionization cross sections, X-ray emission rates, fluorescence yields and Coster-Kronig (CK) transition probabilities. These parameters are required to calculate the K/L/M shell X-ray production (XRP) cross sections and relative X-ray intensity ratios, which in turn are required for different analytical applications. The current status of different physical parameters is presented in this report for use in various applications.

Spectroscopic studies and quantum chemical investigations of (3,4-dimethoxybenzylidene) propanedinitrile.

PubMed

Gupta, Ujval; Kumar, Vinay; Singh, Vivek K; Kant, Rajni; Khajuria, Yugal

2015-04-05

The Fourier Transform Infrared (FTIR), Ultra-Violet Visible (UV-Vis) spectroscopy and Thermogravimetric (TG) analysis of (3,4-dimethoxybenzylidene) propanedinitrile have been carried out and investigated using quantum chemical calculations. The molecular geometry, harmonic vibrational frequencies, Mulliken charges, natural atomic charges and thermodynamic properties in the ground state have been investigated by using Hartree Fock Theory (HF) and Density Functional Theory (DFT) using B3LYP functional with 6-311G(d,p) basis set. Both HF and DFT methods yield good agreement with the experimental data. Vibrational modes are assigned with the help of Vibrational Energy Distribution Analysis (VEDA) program. UV-Visible spectrum was recorded in the spectral range of 190-800nm and the results are compared with the calculated values using TD-DFT approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results obtained from the studies of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are used to calculate molecular parameters like ionization potential, electron affinity, global hardness, electron chemical potential and global electrophilicity. Copyright © 2014 Elsevier B.V. All rights reserved.

Newly synthesized dihydroquinazoline derivative from the aspect of combined spectroscopic and computational study

NASA Astrophysics Data System (ADS)

El-Azab, Adel S.; Mary, Y. Sheena; Mary, Y. Shyma; Panicker, C. Yohannan; Abdel-Aziz, Alaa A.-M.; El-Sherbeny, Magda A.; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, Christian

2017-04-01

In this work, spectroscopic characterization of 2-(2-(4-oxo-3-phenethyl-3,4-dihydroquinazolin-2-ylthio)ethyl)isoindoline-1,3-dione have been obtained with experimentally and theoretically. Complete assignments of fundamental vibrations were performed on the basis of the potential energy distribution of the vibrational modes and good agreement between the experimental and scaled wavenumbers has been achieved. Frontier molecular orbitals have been used as indicators of stability and reactivity. Intramolecular interactions have been investigated by NBO analysis. The dipole moment, linear polarizability and first and second order hyperpolarizability values were also computed. In order to determine molecule sites prone to electrophilic attacks DFT calculations of average local ionization energy (ALIE) and Fukui functions have been performed as well. Intra-molecular non-covalent interactions have been determined and analyzed by the analysis of charge density. Stability of title molecule have also been investigated from the aspect of autoxidation, by calculations of bond dissociation energies (BDE), and hydrolysis, by calculations of radial distribution functions after molecular dynamics (MD) simulations. In order to assess the biological potential of the title compound a molecular docking study towards breast cancer type 2 complex has been performed.

Mass spectrometry. [review of techniques

NASA Technical Reports Server (NTRS)

Burlingame, A. L.; Kimble, B. J.; Derrick, P. J.

1976-01-01

Advances in mass spectrometry (MS) and its applications over the past decade are reviewed in depth, with annotated literature references. New instrumentation and techniques surveyed include: modulated-beam MS, chromatographic MS on-line computer techniques, digital computer-compatible quadrupole MS, selected ion monitoring (mass fragmentography), and computer-aided management of MS data and interpretation. Areas of application surveyed include: organic MS and electron impact MS, field ionization kinetics, appearance potentials, translational energy release, studies of metastable species, photoionization, calculations of molecular orbitals, chemical kinetics, field desorption MS, high pressure MS, ion cyclotron resonance, biochemistry, medical/clinical chemistry, pharmacology, and environmental chemistry and pollution studies.

Anomalous abundances of solar energetic particles and coronal gas: Coulomb effects and First Ionization Potential (FIP) ordering

NASA Technical Reports Server (NTRS)

Mullan, D. J.

1985-01-01

The first ionization potential (FIP) ordering of elemental abundances in solar energetic particles and in the corona which can both be explained Coulomb effects is discussed. Solar energetic particles (SEP) and coronal gas have anomalous abundances relative to the photosphere. The anomalies are similar in both cases: which led to the conclusion that SEP acceleration is not selective, but merely preserves the source abundances. It is argued that SEP acceleration can be selective, because identical selectivity operates to determine the coronal abundances. The abundance anomalies are ordered by first ionization potential (FIP).

Potential energy surfaces of LaH + and LaH + 2

NASA Astrophysics Data System (ADS)

Das, Kalyan K.; Balasubramanian, K.

1991-03-01

Using the complete active space multiconfiguration self-consistent field (CAS-MCSCF) followed by full second-order configuration interaction (SOCI) calculations, 16 electronic states of LaH+ and 8 electronic states of LaH+2 are investigated. The potential energy surface of these electronic states of LaH+2 and LaH+ are computed. These calculations show that the 3F(5d2) ground state of La+ ion forms a weak complex with H2. The La+(1D) excited state inserts into H2 with a small barrier (<8 kcal/mol) to form the 1A1 ground state of LaH+2 (re=2.057 Å, θe=106°). At the SOCI level of theory LaH+2 is found to be 11 kcal/mol more stable than La+(3F)+H2. Our calculations explain the experimental observations on La++H2→LaH++H reaction. The adiabatic ionization potential (IP) of LaH2 and LaH are calculated as 5.23 and 5.33 eV, respectively. The ground state of LaH+ was found to be a 2Δ state. We compute De(LaH+) and De(HLa-H+) as 2.54 eV in excellent agreement with the experimental De(LaH+)=2.57 eV measured by Armentrout and co-workers. The spin-orbit effects of LaH+ were also studied using the relativistic configuration interaction (RCI) method.

The influence of the N(2D) and N(2P) states in the ionization of the pink afterglow of the nitrogen flowing DC discharge

NASA Astrophysics Data System (ADS)

Levaton, J.; Klein, A. N.; Binder, C.

2018-01-01

In the present work, we extensively discuss the role of N(2D) and N(2P) atoms in the ionization processes of pink afterglow based on optical emission spectroscopy analysis and kinetic numerical modelling. We studied the pink afterglow generated by a nitrogen DC discharge operating at 0.6 Slm-1 flow rate, 45 mA discharge current and pressures ranging from 250 to 1050 Pa. The 391.4 nm nitrogen band was monitored along the afterglow furnishing the relative density of the N2+(B2Σ+u, v = 0) state. A numerical model developed to calculate the nitrogen species densities in the afterglow fits the excited ion density profiles well for the experimental conditions. From the modelling results, we determine the densities of the N+, N2+, N3+, and N4+ ions; the calculations show that the N3+ ion density predominates in the afterglow at the typical residence times of the pink afterglow. This behaviour has been observed experimentally and reported in the literature. Furthermore, we calculate the fractional contribution in the ionization for several physical-chemical mechanisms in the post-discharge. Even with the N3+ ion density being dominant in the afterglow, we find through the calculations that the ionization is dominated by the reactions N(2D) + N(2P) → N2+(X2Σ+g) + e and N2(a'1Σ-u) + N2(X 1Σg+, v > 24) → N4+ + e. The ion conversion mechanisms, or ion transfer reactions, which are responsible for the fact that the N3+ density dominates in the post-discharge, are investigated.

SU-E-T-525: Ionization Chamber Perturbation in Flattening Filter Free Beams

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

Czarnecki, D; Voigts-Rhetz, P von; Zink, K

2015-06-15

Purpose: Changing the characteristic of a photon beam by mechanically removing the flattening filter may impact the dose response of ionization chambers. Thus, perturbation factors of cylindrical ionization chambers in conventional and flattening filter free photon beams were calculated by Monte Carlo simulations. Methods: The EGSnrc/BEAMnrc code system was used for all Monte Carlo calculations. BEAMnrc models of nine different linear accelerators with and without flattening filter were used to create realistic photon sources. Monte Carlo based calculations to determine the fluence perturbations due to the presens of the chambers components, the different material of the sensitive volume (air insteadmore » of water) as well as the volume effect were performed by the user code egs-chamber. Results: Stem, central electrode, wall, density and volume perturbation factors for linear accelerators with and without flattening filter were calculated as a function of the beam quality specifier TPR{sub 20/10}. A bias between the perturbation factors as a function of TPR{sub 20/10} for flattening filter free beams and conventional linear accelerators could not be observed for the perturbations caused by the components of the ionization chamber and the sensitive volume. Conclusion: The results indicate that the well-known small bias between the beam quality correction factor as a function of TPR20/10 for the flattening filter free and conventional linear accelerators is not caused by the geometry of the detector but rather by the material of the sensitive volume. This suggest that the bias for flattening filter free photon fields is only caused by the different material of the sensitive volume (air instead of water)« less

Resonance-enhanced two-photon ionization spectroscopy and theoretical calculations of 3,5-difluoroanisole and its Ar-containing complex.

PubMed

Zhang, Lijuan; Dong, Changwu; Cheng, Min; Hu, Lili; Du, Yikui; Zhu, Qihe; Zhang, Cunhao

2012-10-01

The structure and vibrations of 3,5-difluoroanisole (3,5-DFA) in the first electronically excited (S(1)) state were studied by mass-analyzed resonant two-photon ionization (R2PI) technique as well as the quantum chemical calculations. The ab initio and density functional theory (DFT) calculations reveal that only one structure is stable for each of the S(0), S(1), and D(0) states. In the one color R2PI spectrum, the band origin of the S(1)←S(0) electronic transition (0(0) band) of 3,5-DFA is found to be 37,595±3 cm(-1). In the S(1) state, most of the bands observed are related to the in-plane ring deformation and out-of-plane bending vibrations. The adiabatic ionization energy (IE) of 3,5-DFA is determined to be 70,096±15 cm(-1) by the two color R2PI technique, in agreement with the values predicted by the DFT approaches. The dihalogen-substitution effects on the molecular structure, vibrational frequencies, and electronic transition and ionization energies were discussed in detail. The van der Waals complex of 3,5-DFA with argon (3,5-DFA···Ar) was also observed and studied. The 0(0) band of 3,5-DFA···Ar complex is red-shifted by about 9 cm(-1) with respect to that of 3,5-DFA. Both the experimental data and the calculated results indicate that the formation of 3,5-DFA···Ar complex gives only a weak influence on the properties of 3,5-DFA moiety. Copyright © 2012 Elsevier B.V. All rights reserved.

Atmospheric NLTE models for the spectroscopic analysis of blue stars with winds. III. X-ray emission from wind-embedded shocks

NASA Astrophysics Data System (ADS)

Carneiro, L. P.; Puls, J.; Sundqvist, J. O.; Hoffmann, T. L.

2016-05-01

Context. Extreme ultraviolet (EUV) and X-ray radiation emitted from wind-embedded shocks in hot, massive stars can affect the ionization balance in their outer atmospheres and can be the mechanism responsible for producing highly ionized atomic species detected in stellar wind UV spectra. Aims: To allow for these processes in the context of spectral analysis, we have implemented the emission from wind-embedded shocks and related physics into our unified, NLTE model atmosphere/spectrum synthesis code FASTWIND. Methods: The shock structure and corresponding emission is calculated as a function of user-supplied parameters (volume filling factor, radial stratification of shock strength, and radial onset of emission). We account for a temperature and density stratification inside the postshock cooling zones, calculated for radiative and adiabatic cooling in the inner and outer wind, respectively. The high-energy absorption of the cool wind is considered by adding important K-shell opacities, and corresponding Auger ionization rates have been included in the NLTE network. To test our implementation and to check the resulting effects, we calculated a comprehensive model grid with a variety of X-ray emission parameters. Results: We tested and verified our implementation carefully against corresponding results from various alternative model atmosphere codes, and studied the effects from shock emission for important ions from He, C, N, O, Si, and P. Surprisingly, dielectronic recombination turned out to play an essential role for the ionization balance of O iv/O v (particularly in dwarfs with Teff~ 45 000 K). Finally, we investigated the frequency dependence and radial behavior of the mass absorption coefficient, κν(r), which is important in the context of X-ray line formation in massive star winds. Conclusions: In almost all of the cases considered, direct ionization is of major influence because of the enhanced EUV radiation field, and Auger ionization only affects N vi and O vi significantly. The approximation of a radially constant κν is justified for r ≳ 1.2 R∗ and λ ≲ 18 Å and also for many models at longer wavelengths. To estimate the actual value of this quantity, however, the He II opacities need to be calculated from detailed NLTE modeling, at least for wavelengths longer than 18 to 20 Å, and information on the individual CNO abundances has to be present.

Calculated free and bioavailable vitamin D metabolite concentrations in vitamin D-deficient hip fracture patients after supplementation with cholecalciferol and ergocalciferol.

PubMed

Glendenning, Paul; Chew, Gerard T; Inderjeeth, Charles A; Taranto, Mario; Fraser, William D

2013-10-01

We previously showed that oral cholecalciferol and ergocalciferol have comparable effects in decreasing circulating parathyroid hormone (PTH), despite a greater increase in total serum 25-hydroxyvitamin D (25OHD) concentration with cholecalciferol supplementation. However, the effects of cholecalciferol and ergocalciferol on total serum 1,25-dihydroxyvitamin D (1,25(OH)2D), vitamin D-binding protein (DBP), free 25OHD and free 1,25(OH)2D concentrations have not been previously studied. We randomized 95 hip fracture patients (aged 83±8 years) with vitamin D deficiency (serum 25OHD <50 nmol/L) to oral supplementation with either cholecalciferol 1000 IU/day (n=47) or ergocalciferol 1000 IU/day (n=48) for three months. All were given matching placebos of the alternative treatment to maintain blinding. We measured serum 25OHD (high-pressure liquid chromatography), 1,25(OH)2D (Diasorin radioimmunoassay), DBP (immunonephelometry), ionized calcium (Bayer 800 ion-selective electrode) and albumin (bromocresol green) concentrations before and after treatment. We calculated free and bioavailable concentrations of the vitamin D metabolites using albumin and DBP, and calculated free vitamin D metabolite indices as the ratios between the molar concentrations of the vitamin D metabolites and DBP. Seventy participants (74%) completed the study with paired samples for analysis. Total serum 1,25(OH)2D did not change significantly with either treatment (p>0.05, post-treatment vs baseline). Both treatments were associated with comparable increases in DBP (cholecalciferol: +18%, ergocalciferol: +16%, p=0.32 between groups), albumin (cholecalciferol: +31%, ergocalciferol: +21%, p=0.29 between groups) and calculated free 25OHD (cholecalciferol: +46%, ergocalciferol: +36%, p=0.08), with comparable decreases in free 1,25(OH)2D (cholecalciferol: -17%, ergocalciferol: -19%, p=0.32 between groups). In the treatment-adherent subgroup the increase in ionized calcium was marginally greater with cholecalciferol compared with ergocalciferol (cholecalciferol: +8%, ergocalciferol: +5%, p=0.03 between groups). There were no significant differences between the treatments in their effects on the calculated bioavailable concentrations or free indices of the vitamin D metabolites (p>0.05 between groups). In vitamin D-deficient hip fracture patients, oral supplementation with cholecalciferol and ergocalciferol had no effect on total serum 1,25(OH)2D, and comparable effects on DBP and free vitamin D metabolite concentrations. This is despite cholecalciferol having greater effects than ergocalciferol in increasing total 25OHD, and in increasing ionized calcium in treatment-adherent subjects. These findings may explain why cholecalciferol and ergocalciferol supplementation result in similar magnitudes of PTH reduction, but implicate potential differences in other vitamin D metabolites, such as 24,25(OH)2D, that could explain their different effects on ionized calcium. Copyright © 2013 Elsevier Inc. All rights reserved.

Modeling of Plutonium Ionization Probabilities for Use in Nuclear Forensic Analysis by Resonance Ionization Mass Spectrometry

DTIC Science & Technology

2016-12-01

masses collide, they form a supercritical mass . Criticality refers to the neutron population within the system. A critical system is one that can...Spectrometry, no. 242, pp. 161–168, 2005. [9] S. Raeder, “Trace analysis of actinides in the environment by means of resonance ionization mass ...first ionization potential of actinide elements by resonance ionization mass spectrometry.” Spectrochimica Acta part B: Atomic Spectroscopy. vol. 52

Unraveling nonadiabatic ionization and Coulomb potential effect in strong-field photoelectron holography.

PubMed

Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; Liu, Peng; Chen, Zhangjin; Yang, Weifeng; Hu, Shilin; Lin, C D; Chen, Jing

2016-06-22

Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. In addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. We showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules.

Unraveling nonadiabatic ionization and Coulomb potential effect in strong-field photoelectron holography

PubMed Central

Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; Liu, Peng; Chen, Zhangjin; Yang, Weifeng; Hu, Shilin; Lin, C. D.; Chen, Jing

2016-01-01

Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. In addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. We showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules. PMID:27329071

Unraveling nonadiabatic ionization and Coulomb potential effect in strong-field photoelectron holography

DOE PAGES

Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; ...

2016-06-22

Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. Inmore » addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. Here, we showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules.« less

Estimating the risks of cancer mortality and genetic defects resulting from exposures to low levels of ionizing radiation

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

Buhl, T.E.; Hansen, W.R.

1984-05-01

Estimators for calculating the risk of cancer and genetic disorders induced by exposure to ionizing radiation have been recommended by the US National Academy of Sciences Committee on the Biological Effects of Ionizing Radiations, the UN Scientific Committee on the Effects of Atomic Radiation, and the International Committee on Radiological Protection. These groups have also considered the risks of somatic effects other than cancer. The US National Council on Radiation Protection and Measurements has discussed risk estimate procedures for radiation-induced health effects. The recommendations of these national and international advisory committees are summarized and compared in this report. Based onmore » this review, two procedures for risk estimation are presented for use in radiological assessments performed by the US Department of Energy under the National Environmental Policy Act of 1969 (NEPA). In the first procedure, age- and sex-averaged risk estimators calculated with US average demographic statistics would be used with estimates of radiation dose to calculate the projected risk of cancer and genetic disorders that would result from the operation being reviewed under NEPA. If more site-specific risk estimators are needed, and the demographic information is available, a second procedure is described that would involve direct calculation of the risk estimators using recommended risk-rate factors. The computer program REPCAL has been written to perform this calculation and is described in this report. 25 references, 16 tables.« less

Ion energies in high power impulse magnetron sputtering with and without localized ionization zones

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

Yang, Yuchen; Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720; Tanaka, Koichi

2015-03-23

High speed imaging of high power impulse magnetron sputtering discharges has revealed that ionization is localized in moving ionization zones but localization disappears at high currents for high yield targets. This offers an opportunity to study the effect ionization zones have on ion energies. We measure that ions have generally higher energies when ionization zones are present, supporting the concept that these zones are associated with moving potential humps. We propose that the disappearance of ionization zones is caused by an increased supply of atoms from the target which cools electrons and reduces depletion of atoms to be ionized.

Partial cross sections of helium satellites at medium photon energies

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

Wehlitz, R.; Sellin, I.A.; Hemmers, O.

1997-04-01

Still of current interest is the important role of single ionization with excitation compared to single ionization alone. The coupling between the electrons and the incoming photon is a single-particle operator. Thus, an excitation in addition to an ionization, leading to a so-called satellite line in a photoelectron spectrum, is entirely due to electron-electron interaction and probes the electron correlation in the ground and final state. Therefore the authors have undertaken the study of the intensity of helium satellites He{sup +}nl (n = 2 - 6) relative to the main photoline (n = 1) as a function of photon energymore » at photon energies well above threshold up to 900 eV. From these results they could calculate the partial cross-sections of the helium satellites. In order to test the consistency of their satellite-to-1s ratios with published double-to-single photoionization ratios, the authors calculated the double-to-single photoionization ratio from their measured ratios using the theoretical energy-distribution curves of Chang and Poe and Le Rouzo and Dal Cappello which proved to be valid for photon energies below 120 eV. These calculated double-to-single ionization ratios agree fairly well with recent ion measurements. In the lower photon energy range the authors ratios agree better with the ratios of Doerner et al. while for higher photon energies the agreement is better with the values of Levin et al.« less

Ionized and total magnesium concentrations in blood from dogs with naturally acquired parvoviral enteritis.

PubMed

Mann, F A; Boon, G D; Wagner-Mann, C C; Ruben, D S; Harrington, D P

1998-05-01

To determine whether pretreatment total and ionized blood magnesium concentrations were associated with outcome for dogs with parvoviral enteritis and whether ionized magnesium concentration was related to total magnesium concentration or other laboratory values. Prospective cohort study. 61 healthy dogs and 72 dogs with parvoviral enteritis. Total, ionized, and pH-normalized ionized magnesium concentrations, ionized and pH-normalized ionized calcium concentrations, pH, sodium and potassium concentrations, and Hct were measured prior to treatment. chi 2 Analyses were used to test for associations between outcome and age and between outcome and treatment with antiendotoxin antibody. Pearson's correlation coefficients were calculated to determine whether ionized magnesium concentration was linearly associated with other laboratory values. Total and ionized magnesium concentrations were not significantly different between healthy dogs and dogs with parvoviral enteritis or between dogs surviving and those not surviving parvoviral enteritis. The only laboratory value strongly correlated with ionized magnesium concentration was pH-normalized ionized magnesium concentration. Of the factors tested, none were significantly associated with outcome, except that dogs 16 weeks old or less treated with antiendotoxin antibody were significantly more likely to die than were dogs 16 weeks old or less that were not treated with antiendotoxin antibody. Total and ionized blood magnesium concentrations cannot be used to consistently predict outcome for dogs with parvoviral enteritis. Antiendotoxin antibody should be used with caution in dogs 16 weeks old or less.

Toward the accurate first-principles prediction of ionization equilibria in proteins.

PubMed

Khandogin, Jana; Brooks, Charles L

2006-08-08

The calculation of pK(a) values for ionizable sites in proteins has been traditionally based on numerical solutions of the Poisson-Boltzmann equation carried out using a high-resolution protein structure. In this paper, we present a method based on continuous constant pH molecular dynamics (CPHMD) simulations, which allows the first-principles description of protein ionization equilibria. Our method utilizes an improved generalized Born implicit solvent model with an approximate Debye-Hückel screening function to account for salt effects and the replica-exchange (REX) protocol for enhanced conformational and protonation state sampling. The accuracy and robustness of the present method are demonstrated by 1 ns REX-CPHMD titration simulations of 10 proteins, which exhibit anomalously large pK(a) shifts for the carboxylate and histidine side chains. The experimental pK(a) values of these proteins are reliably reproduced with a root-mean-square error ranging from 0.6 unit for proteins containing few buried ionizable side chains to 1.0 unit or slightly higher for proteins containing ionizable side chains deeply buried in the core and experiencing strong charge-charge interactions. This unprecedented level of agreement with experimental benchmarks for the de novo calculation of pK(a) values suggests that the CPHMD method is maturing into a practical tool for the quantitative prediction of protein ionization equilibria, and this, in turn, opens a door to atomistic simulations of a wide variety of pH-coupled conformational phenomena in biological macromolecules such as protein folding or misfolding, aggregation, ligand binding, membrane interaction, and catalysis.

A density functional for core-valence correlation energy

NASA Astrophysics Data System (ADS)

Ranasinghe, Duminda S.; Frisch, Michael J.; Petersson, George A.

2015-12-01

A density functional, ɛCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of ɛLY Pcorr(ρc), ɛV WN5corr(ρc, ρv), ɛPBEcorr(ρc, ρv), ɛSlaterex(ρc, ρv), ɛHCTHex(ρc, ρv), ɛHFex(ρc, ρv), and F CV -DFT (" separators=" N i , Z i ) , a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from ɛCV-DFT(ρc, ρv) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the ɛCV-DFT(ρc, ρv) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory.

Status of LDEF ionizing radiation measurements and analysis

NASA Technical Reports Server (NTRS)

Parnell, T. A.

1992-01-01

The LDEF-1 results from the particle astrophysics, radiation environments, and dosimetry measurements on LDEF-1 are summarized, including highlights from presentations at the 2nd symposium. Progress in using LDEF data to improve radiation environment models and calculation methods is reviewed. Radiation effects, or the lack thereof are discussed. Future plans of the LDEF Ionizing Radiation Special Investigation Group are presented.

Indirect contributions to electron-impact ionization of Li+ (1 s 2 s S31 ) ions: Role of intermediate double-K -vacancy states

NASA Astrophysics Data System (ADS)

Müller, A.; Borovik, A.; Huber, K.; Schippers, S.; Fursa, D. V.; Bray, I.

2018-02-01

Fine details of the cross section for electron-impact ionization of metastable two-electron Li+(1 s 2 s S31) ions are scrutinized by both experiment and theory. Beyond direct knockoff ionization, indirect ionization mechanisms proceeding via formation of intermediate double-K-vacancy (hollow) states either in a Li+ ion or in a neutral lithium atom and subsequent emission of one or two electrons, respectively, can contribute to the net production of Li2 + ions. The partial cross sections for such contributions are less than 4% of the total single-ionization cross section. The characteristic steps, resonances, and interference phenomena in the indirect ionization contribution are measured with an experimental energy spread of less than 0.9 eV and with a statistical relative uncertainty of the order of 1.7%, requiring a level of statistical uncertainty in the total single-ionization cross section of better than 0.05%. The measurements are accompanied by convergent-close-coupling calculations performed on a fine energy grid. Theory and experiment are in remarkable agreement concerning the fine details of the ionization cross section. Comparison with previous R-matrix results is less favorable.

Time-dependent quantum chemistry of laser driven many-electron molecules

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

Nguyen-Dang, Thanh-Tung; Couture-Bienvenue, Étienne; Viau-Trudel, Jérémy

2014-12-28

A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied tomore » calculate the detailed, sub-cycle electronic dynamics of BeH{sub 2}, treated in a 3–21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10{sup 15} W/cm{sup 2}), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics.« less

Energy Balance for a Sonoluminescence Bubble Yields a Measure of Ionization Potential Lowering

NASA Astrophysics Data System (ADS)

Kappus, B.; Bataller, A.; Putterman, S. J.

2013-12-01

Application of energy conservation between input sound and the microplasma which forms at the moment of sonoluminescence places bounds on the process, whereby the gas is ionized. Detailed pulsed Mie scattering measurements of the radius versus time for a xenon bubble in sulfuric acid provide a complete characterization of the hydrodynamics and minimum radius. For a range of emission intensities, the blackbody spectrum emitted during collapse matches the minimum bubble radius, implying opaque conditions are attained. This requires a degree of ionization >36%. Analysis reveals only 2.1±0.6eV/atom of energy available during light emission. In order to unbind enough charge, collective processes must therefore reduce the ionization potential by at least 75%. We interpret this as evidence that a phase transition to a highly ionized plasma is occurring during sonoluminescence.

Energy balance for a sonoluminescence bubble yields a measure of ionization potential lowering.

PubMed

Kappus, B; Bataller, A; Putterman, S J

2013-12-06

Application of energy conservation between input sound and the microplasma which forms at the moment of sonoluminescence places bounds on the process, whereby the gas is ionized. Detailed pulsed Mie scattering measurements of the radius versus time for a xenon bubble in sulfuric acid provide a complete characterization of the hydrodynamics and minimum radius. For a range of emission intensities, the blackbody spectrum emitted during collapse matches the minimum bubble radius, implying opaque conditions are attained. This requires a degree of ionization >36%. Analysis reveals only 2.1±0.6  eV/atom of energy available during light emission. In order to unbind enough charge, collective processes must therefore reduce the ionization potential by at least 75%. We interpret this as evidence that a phase transition to a highly ionized plasma is occurring during sonoluminescence.

Air-kerma strength determination of a new directional {sup 103}Pd source

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

Aima, Manik, E-mail: aima@wisc.edu; Reed, Joshua L.; DeWerd, Larry A.

2015-12-15

Purpose: A new directional {sup 103}Pd planar source array called a CivaSheet™ has been developed by CivaTech Oncology, Inc., for potential use in low-dose-rate (LDR) brachytherapy treatments. The array consists of multiple individual polymer capsules called CivaDots, containing {sup 103}Pd and a gold shield that attenuates the radiation on one side, thus defining a hot and cold side. This novel source requires new methods to establish a source strength metric. The presence of gold material in such close proximity to the active {sup 103}Pd region causes the source spectrum to be significantly different than the energy spectra of seeds normallymore » used in LDR brachytherapy treatments. In this investigation, the authors perform air-kerma strength (S{sub K}) measurements, develop new correction factors for these measurements based on an experimentally verified energy spectrum, and test the robustness of transferring S{sub K} to a well-type ionization chamber. Methods: S{sub K} measurements were performed with the variable-aperture free-air chamber (VAFAC) at the University of Wisconsin Medical Radiation Research Center. Subsequent measurements were then performed in a well-type ionization chamber. To realize the quantity S{sub K} from a directional source with gold material present, new methods and correction factors were considered. Updated correction factors were calculated using the MCNP 6 Monte Carlo code in order to determine S{sub K} with the presence of gold fluorescent energy lines. In addition to S{sub K} measurements, a low-energy high-purity germanium (HPGe) detector was used to experimentally verify the calculated spectrum, a sodium iodide (NaI) scintillating counter was used to verify the azimuthal and polar anisotropy, and a well-type ionization chamber was used to test the feasibility of disseminating S{sub K} values for a directional source within a cylindrically symmetric measurement volume. Results: The UW VAFAC was successfully used to measure the S{sub K} of four CivaDots with reproducibilities within 0.3%. Monte Carlo methods were used to calculate the UW VAFAC correction factors and the calculated spectrum emitted from a CivaDot was experimentally verified with HPGe detector measurements. The well-type ionization chamber showed minimal variation in response (<1.5%) as a function of source positioning angle, indicating that an American Association of Physicists in Medicine (AAPM) Accredited Dosimetry Calibration Laboratory calibrated well chamber would be a suitable device to transfer an S{sub K}-based calibration to a clinical user. S{sub K} per well-chamber ionization current ratios were consistent among the four dots measured. Additionally, the measurements and predictions of anisotropy show uniform emission within the solid angle of the VAFAC, which demonstrates the robustness of the S{sub K} measurement approach. Conclusions: This characterization of a new {sup 103}Pd directional brachytherapy source helps to establish calibration methods that could ultimately be used in the well-established AAPM Task Group 43 formalism. Monte Carlo methods accurately predict the changes in the energy spectrum caused by the fluorescent x-rays produced in the gold shield.« less

Electron-helium S-wave model benchmark calculations. II. Double ionization, single ionization with excitation, and double excitation

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.

2010-02-01

The propagating exterior complex scaling (PECS) method is extended to all four-body processes in electron impact on helium in an S-wave model. Total and energy-differential cross sections are presented with benchmark accuracy for double ionization, single ionization with excitation, and double excitation (to autoionizing states) for incident-electron energies from threshold to 500 eV. While the PECS three-body cross sections for this model given in the preceding article [Phys. Rev. A 81, 022715 (2010)] are in good agreement with other methods, there are considerable discrepancies for these four-body processes. With this model we demonstrate the suitability of the PECS method for the complete solution of the electron-helium system.

Thermal diffusion in partially ionized gases - The case of unequal temperatures. [in solar chromosphere

NASA Technical Reports Server (NTRS)

Geiss, J.; Burgi, A.

1987-01-01

Previous calculations of thermal diffusion coefficients in partially ionized gases are extended to the case of unequal neutral and ion temperatures and/or temperature gradients. Formulas are derived for the general case of a major gas as well as for minor atoms and ions. Strong enhancements of minor-ion thermal diffusion coefficients over their values in the fully ionized gas are found when the degree of ionization in the main gas is relatively low. However, compared to the case of equal temperatures, the enhancements are less strong when the neutrals are cooler than the ions. The specific case of the H-H(+) mixture, which is important in the study of solar and stellar atmospheres, is discussed as an application.

Bound and continuum energy distributions of nuclear fragments resulting from tunneling ionization of molecules

NASA Astrophysics Data System (ADS)

Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

2018-03-01

We present the theory of tunneling ionization of molecules with both electronic and nuclear motion treated quantum mechanically. The theory provides partial rates for ionization into the different final states of the molecular ion, including both bound vibrational and dissociative channels. The exact results obtained for a one-dimensional model of H2 and D2 are compared with two approximate approaches, the weak-field asymptotic theory and the Born-Oppenheimer approximation. The validity ranges and compatibility of the approaches are identified formally and illustrated by the calculations. The results quantify that at typical field strengths considered in strong-field physics, it is several orders of magnitude more likely to ionize into bound vibrational ionic channels than into the dissociative channel.

Contribution of Solar Hydrogen Lyα Line Emission in Total Ionization Rate in Ionospheric D-region During the Maximum of Solar X-flare

NASA Astrophysics Data System (ADS)

Nina, A.; Čadež, V. M.; Bajčetić, J.

2015-12-01

The solar Lyα line emission can be considered as the dominant source of ionization processes in the ionospheric D-region at altitudes above 70 km during unperturbed conditions. However, large sudden impacts of radiation in some other energy domains can also significantly influence the ionization rate and, in this paper, we present a study on the contribution of Lyα radiation to the ionization rate when the ionosphere is disturbed by solar X-flares. We give relevant analytical expressions and make calculations and numerical simulations for the low ionosphere using data collected by the VLF receiver located in Serbia for the VLF radio signal emitted by the DHO transmitter in Germany.

Evidence for intramolecular OH⋯π hydrogen bonding in unsaturated alcohols from UV photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Kowski, Klaus; Lüttke, Wolfgang; Rademacher, Paul

2001-06-01

The gas phase He(I) photoelectron (PE) spectra of several unsaturated alcohols (1-11) have been measured and analysed with respect to intramolecular OH⋯π hydrogen bonding. Evidence for such a hydrogen bond has been detected in the spectra of 2-allylphenol (1) and 2-phenylethan-1-ol (3). 1 exists as a conformational mixture of a hydrogen bonded form 1a and an open form 1b in a composition of roughly 2:1. A strong ionization band (IPv=10.01 eV; where IPv is the vertical ionization potential) is assigned to the ethylenic Cdbnd C double bond in the major conformer (1a) and a weak band (IPv=9.72 eV) to that of the minor conformer (1b). The latter IP coincides with the corresponding ionization of allylbenzene. In the series of ω-phenylalkan-1-ols, compound 3 exhibits an unusually low nπ(O) ionization indicating hydrogen bonding between the OH group and the π electron system of the phenyl ring. The higher homologs 4 and 5 prefer 'open' conformations without such interaction. The PE spectra of alkenols such as but-3-en-1-ol (7) and pent-4-en-1-ol (8) as well as of alkynols such as but-3-yn-1-ol (10) and pent-4-yn-1-ol (11) are consistent with OH⋯π hydrogen bonded conformers. The methanol/ethylene hetero-dimer has a T-shaped structure, as indicated by B3LYP/6-311++G(d) calculations, with a binding energy of 5.65 kJ mol-1.

Preventive or Potential Therapeutic Value of Nutraceuticals against Ionizing Radiation-Induced Oxidative Stress in Exposed Subjects and Frequent Fliers

PubMed Central

Giardi, Maria Teresa; Touloupakis, Eleftherios; Bertolotto, Delfina; Mascetti, Gabriele

2013-01-01

Humans are constantly exposed to ionizing radiation deriving from outer space sources or activities related to medical care. Absorption of ionizing radiation doses over a prolonged period of time can result in oxidative damage and cellular dysfunction inducing several diseases, especially in ageing subjects. In this report, we analyze the effects of ionizing radiation, particularly at low doses, in relation to a variety of human pathologies, including cancer, and cardiovascular and retinal diseases. We discuss scientific data in support of protection strategies by safe antioxidant formulations that can provide preventive or potential therapeutic value in response to long-term diseases that may develop following exposure. PMID:23965979

Effect of a finite ionization rate on the radiative heating of outer planet atmospheric entry probes

NASA Technical Reports Server (NTRS)

Nelson, H. F.

1981-01-01

The influence of finite rate ionization in the inviscid gas just behind the stagnation shock wave on the radiation heating of probes entering the hydrogen helium atmospere of the major planets was investigated. At the present time, there is disagreement as to whether the radiative flux increases or decreases relative to its equilibrium value when finite rate ionization is considered. Leibowitz and Kuo content that the finite rate ionization in the hydrogen gas just behind the shock wave reduces the radiative flux to the probe, whereas Tiwari and Szema predict that it increases the radiative flux. The radiation modeling used in the calculations of both pairs of these investigators was reviewed. It is concluded that finite rate ionization in the inviscid region of the shock layer should reduce the cold wall radiative heating below the values predicted by equilibrium chemistry assumptions.

Fine-scale structure in the -185 kilometers per second absorption by HCO(+) in the Galactic center

NASA Technical Reports Server (NTRS)

Marr, Jonathan M.; Rudolph, Alexander L.; Pauls, Thomas A.; Wright, Melvyn C. H.; Backer, Donald C.

1992-01-01

We present a high-resolution study of the HCO(+) (J = 1-0) absorption by the 'high-velocity gas' at velocities between -170 and -200 km/s in Sgr A West. The absorption against the continuum radiation from the ionized gas features in Sgr A West (in particular the 'bar') is stronger than it is against Sgr A which is separated from the ionized gas by a few arcseconds. The positions of peak HCO(+) opacity coincide with the positions of Ne II emission at these velocities. These observations suggest that, even though emission is detected from gas at these high velocities over several arcminutes, some of the absorbing molecular gas may be mixed in with the ionized gas close to Sgr A. Simple calculations show that sufficient shielding can exist in the ionized features to allow molecules to survive very close to the ionizing source.

The radiation environment on the surface of Mars - Summary of model calculations and comparison to RAD data

NASA Astrophysics Data System (ADS)

Matthiä, Daniel; Hassler, Donald M.; de Wet, Wouter; Ehresmann, Bent; Firan, Ana; Flores-McLaughlin, John; Guo, Jingnan; Heilbronn, Lawrence H.; Lee, Kerry; Ratliff, Hunter; Rios, Ryan R.; Slaba, Tony C.; Smith, Michael; Stoffle, Nicholas N.; Townsend, Lawrence W.; Berger, Thomas; Reitz, Günther; Wimmer-Schweingruber, Robert F.; Zeitlin, Cary

2017-08-01

The radiation environment at the Martian surface is, apart from occasional solar energetic particle events, dominated by galactic cosmic radiation, secondary particles produced in their interaction with the Martian atmosphere and albedo particles from the Martian regolith. The highly energetic primary cosmic radiation consists mainly of fully ionized nuclei creating a complex radiation field at the Martian surface. This complex field, its formation and its potential health risk posed to astronauts on future manned missions to Mars can only be fully understood using a combination of measurements and model calculations. In this work the outcome of a workshop held in June 2016 in Boulder, CO, USA is presented: experimental results from the Radiation Assessment Detector of the Mars Science Laboratory are compared to model results from GEANT4, HETC-HEDS, HZETRN, MCNP6, and PHITS. Charged and neutral particle spectra and dose rates measured between 15 November 2015 and 15 January 2016 and model results calculated for this time period are investigated.

QED effects on individual atomic orbital energies

NASA Astrophysics Data System (ADS)

Kozioł, Karol; Aucar, Gustavo A.

2018-04-01

Several issues, concerning QED corrections, that are important in precise atomic calculations are presented. The leading QED corrections, self-energy and vacuum polarization, to the orbital energy for selected atoms with 30 ≤ Z ≤ 118 have been calculated. The sum of QED and Breit contributions to the orbital energy is analyzed. It has been found that for ns subshells the Breit and QED contributions are of comparative size, but for np and nd subshells the Breit contribution takes a major part of the QED+Breit sum. It has also, been found that the Breit to leading QED contributions ratio for ns subshells is almost independent of Z. The Z-dependence of QED and Breit+QED contributions per subshell is shown. The fitting coefficients may be used to estimate QED effects on inner molecular orbitals. We present results of our calculations for QED contributions to orbital energy of valence ns-subshell for group 1 and 11 atoms and discuss about the reliability of these numbers by comparing them with experimental first ionization potential data.

Drifting potential humps in ionization zones: The “propeller blades” of high power impulse magnetron sputtering

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

Anders, André; Ni, Pavel; Panjan, Matjaž

2013-09-30

Ion energy distribution functions measured for high power impulse magnetron sputtering show features, such as a broad peak at several 10 eV with an extended tail, as well as asymmetry with respect to E×B, where E and B are the local electric and magnetic field vectors, respectively. Here it is proposed that those features are due to the formation of a potential hump of several 10 V in each of the traveling ionization zones. Potential hump formation is associated with a negative-positive-negative space charge that naturally forms in ionization zones driven by energetic drifting electrons.

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study.

PubMed

Elkechai, Aziz; Kias, Farida; Talbi, Fazia; Boucekkine, Abdou

2014-06-01

Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X =  F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) =  0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) =  0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) < IE(Cl) < IE(Br) < IE(I) is also well rationalized considering the frontier MO diagrams of these species. Finally, this work confirms the relevance of the Hirshfeld charges analysis which bring to light an excellent linear correlation (R(2) =  0.999) between the variations of the uranium charges and E1/2 in the reduction process of the U(V) species.

Measurement of the first ionization potential of lawrencium, element 103.

PubMed

Sato, T K; Asai, M; Borschevsky, A; Stora, T; Sato, N; Kaneya, Y; Tsukada, K; Düllmann, Ch E; Eberhardt, K; Eliav, E; Ichikawa, S; Kaldor, U; Kratz, J V; Miyashita, S; Nagame, Y; Ooe, K; Osa, A; Renisch, D; Runke, J; Schädel, M; Thörle-Pospiech, P; Toyoshima, A; Trautmann, N

2015-04-09

The chemical properties of an element are primarily governed by the configuration of electrons in the valence shell. Relativistic effects influence the electronic structure of heavy elements in the sixth row of the periodic table, and these effects increase dramatically in the seventh row--including the actinides--even affecting ground-state configurations. Atomic s and p1/2 orbitals are stabilized by relativistic effects, whereas p3/2, d and f orbitals are destabilized, so that ground-state configurations of heavy elements may differ from those of lighter elements in the same group. The first ionization potential (IP1) is a measure of the energy required to remove one valence electron from a neutral atom, and is an atomic property that reflects the outermost electronic configuration. Precise and accurate experimental determination of IP1 gives information on the binding energy of valence electrons, and also, therefore, on the degree of relativistic stabilization. However, such measurements are hampered by the difficulty in obtaining the heaviest elements on scales of more than one atom at a time. Here we report that the experimentally obtained IP1 of the heaviest actinide, lawrencium (Lr, atomic number 103), is 4.96(+0.08)(-0.07) electronvolts. The IP1 of Lr was measured with (256)Lr (half-life 27 seconds) using an efficient surface ion-source and a radioisotope detection system coupled to a mass separator. The measured IP1 is in excellent agreement with the value of 4.963(15) electronvolts predicted here by state-of-the-art relativistic calculations. The present work provides a reliable benchmark for theoretical calculations and also opens the way for IP1 measurements of superheavy elements (that is, transactinides) on an atom-at-a-time scale.

The fine nebula dust component: A key to chondrule formation by lightning

NASA Technical Reports Server (NTRS)

Wasson, J. T.; Rasmussen, K. L.

1994-01-01

Our assessment indicates that chondrule formation by lightning is indeed possible in the solar nebula. Previously the overriding objection to the lightning process of chondrule formation has been that low nebula pressures prevented the buildup of large potential differences. The breakdown potential is controlled by the mean free live distance of an electron. We calculate the mean free live distance in pure H2 gas at 2 AU to be approximately 500 m. A fine dust load constituting 4 wt% of the dust in the dusty midplane region leads to a reduced mean free live distance of only 7 m. Very conservatively we estimate the breakdown potential to be at least 10, 1.8, and 0.7 V/cm at 1, 2, and 3 AU respectively. We set the radius of the lightning bolt equal to the kinetic mean free path of the gas. Our calculations based on electron drift velocities in a fully ionized H2 gas show that first strike durations are 0.96, 3.4, and 7.0 ms at 1, 2, and 3 AU respectively, in much better accordance with the meteoritic evidence than previous estimates of 10-100 s.

Dissociative Ionization of Pyridine by Electron Impact

NASA Technical Reports Server (NTRS)

Dateo, Christopher; Huo, Winifred; Kwak, Dochan (Technical Monitor)

2002-01-01

In order to understand the damage of biomolecules by electrons, a process important in radiation damage, we undertake a study of the dissociative ionization (DI) of pyridine (C5H5N) from the low-lying ionization channels. The methodology used is the same as in the benzene study. While no experimental DI data are available, we compare the dissociation products from our calculations with the dissociative photoionization measurements of Tixier et al. using dipole (e, e(+) ion) coincidence spectroscopy. Comparisons with the DI of benzene is also made so as to understand the difference in DI between a heterocyclic and an aromatic molecule.

Novel Application of Density Estimation Techniques in Muon Ionization Cooling Experiment

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

Mohayai, Tanaz Angelina; Snopok, Pavel; Neuffer, David

The international Muon Ionization Cooling Experiment (MICE) aims to demonstrate muon beam ionization cooling for the first time and constitutes a key part of the R&D towards a future neutrino factory or muon collider. Beam cooling reduces the size of the phase space volume occupied by the beam. Non-parametric density estimation techniques allow very precise calculation of the muon beam phase-space density and its increase as a result of cooling. These density estimation techniques are investigated in this paper and applied in order to estimate the reduction in muon beam size in MICE under various conditions.

Photoionization using the xchem approach: Total and partial cross sections of Ne and resonance parameters above the 2 s22 p5 threshold

NASA Astrophysics Data System (ADS)

Marante, Carlos; Klinker, Markus; Kjellsson, Tor; Lindroth, Eva; González-Vázquez, Jesús; Argenti, Luca; Martín, Fernando

2017-08-01

The XCHEM approach interfaces well established quantum chemistry packages with scattering numerical methods in order to describe single-ionization processes in atoms and molecules. This should allow one to describe electron correlation in the continuum at the same level of accuracy as quantum chemistry methods do for bound states. Here we have applied this method to study multichannel photoionization of Ne in the vicinity of the autoionizing states lying between the 2 s22 p5 and 2 s 2 p6 ionization thresholds. The calculated total photoionization cross sections are in very good agreement with the absolute measurement of Samson et al. [J. Electron Spectrosc. Relat. Phenom. 123, 265 (2002), 10.1016/S0368-2048(02)00026-9], and with independent benchmark calculations performed at the same level of theory. From these cross sections, we have extracted resonance positions, total autoionization widths, Fano profile parameters, and correlation parameters for the lowest three autoionizing states. The values of these parameters are in good agreement with those reported in earlier theoretical and experimental work. We have also evaluated β asymmetry parameter and partial photoionization cross sections and, from the latter, partial autoionization widths and Starace parameters for the same resonances, not yet available in the literature. Resonant features in the calculated β parameter are in good agreement with the experimental observations. We have found that the three lowest resonances preferentially decay into the 2 p-1ɛ d continuum rather than into the 2 p-1ɛ s one [Phys. Rev. A 89, 043415 (2014), 10.1103/PhysRevA.89.043415], in agreement with previous expectations, and that in the vicinity of the resonances the partial 2 p-1ɛ s cross section can be larger than the 2 p-1ɛ d one, in contrast with the accepted idea that the latter should amply dominate in the whole energy range. These results show the potential of the XCHEM approach to describe highly correlated process in the ionization continuum of many-electron systems, in particular molecules, for which the XCHEM code has been specifically designed.

Subcycle dynamics of Coulomb asymmetry in strong elliptical laser fields.

PubMed

Li, Min; Liu, Yunquan; Liu, Hong; Ning, Qicheng; Fu, Libin; Liu, Jie; Deng, Yongkai; Wu, Chengyin; Peng, Liang-You; Peng, Liangyou; Gong, Qihuang

2013-07-12

We measure photoelectron angular distributions of noble gases in intense elliptically polarized laser fields, which indicate strong structure-dependent Coulomb asymmetry. Using a dedicated semiclassical model, we have disentangled the contribution of direct ionization and multiple forward scattering on Coulomb asymmetry in elliptical laser fields. Our theory quantifies the roles of the ionic potential and initial transverse momentum on Coulomb asymmetry, proving that the small lobes of asymmetry are induced by direct ionization and the strong asymmetry is induced by multiple forward scattering in the ionic potential. Both processes are distorted by the Coulomb force acting on the electrons after tunneling. Lowering the ionization potential, the relative contribution of direct ionization on Coulomb asymmetry substantially decreases and Coulomb focusing on multiple rescattering is more important. We do not observe evident initial longitudinal momentum spread at the tunnel exit according to our simulation.

Sampling and analyte enrichment strategies for ambient mass spectrometry.

PubMed

Li, Xianjiang; Ma, Wen; Li, Hongmei; Ai, Wanpeng; Bai, Yu; Liu, Huwei

2018-01-01

Ambient mass spectrometry provides great convenience for fast screening, and has showed promising potential in analytical chemistry. However, its relatively low sensitivity seriously restricts its practical utility in trace compound analysis. In this review, we summarize the sampling and analyte enrichment strategies coupled with nine modes of representative ambient mass spectrometry (desorption electrospray ionization, paper vhspray ionization, wooden-tip spray ionization, probe electrospray ionization, coated blade spray ionization, direct analysis in real time, desorption corona beam ionization, dielectric barrier discharge ionization, and atmospheric-pressure solids analysis probe) that have dramatically increased the detection sensitivity. We believe that these advances will promote routine use of ambient mass spectrometry. Graphical abstract Scheme of sampling stretagies for ambient mass spectrometry.

Taurine Protects Mouse Spermatocytes from Ionizing Radiation-Induced Damage Through Activation of Nrf2/HO-1 Signaling.

PubMed

Yang, Wenjun; Huang, Jinfeng; Xiao, Bang; Liu, Yan; Zhu, Yiqing; Wang, Fang; Sun, Shuhan

2017-01-01

The increasing prevalence of ionizing radiation exposure has inevitably raised public concern over the potential detrimental effects of ionizing radiation on male reproductive system function. The detection of drug candidates to prevent reproductive system from damage caused by ionizing radiation is urgent. We aimed to investigate the protective role of taurine on the injury of mouse spermatocyte-derived cells (GC-2) subjected to ionizing radiation. mouse spermatocytes (GC-2 cells) were exposed to ionizing radiation with or without treatment of Taurine. The effect of ionizing radiation and Taurine treatment on GC-2 cells were evaluated by cell viability assay (CCK8), cell cycle and apoptosis. The relative protein abundance change was determined by Western blotting. The siRNA was used to explore whether Nrf2 signaling was involved in the cytoprotection of Taurine. Taurine significantly inhibited the decrease of cell viability, percentage of apoptotic cells and cell cycle arrest induced by ionizing radiation. Western blot analysis showed that taurine significantly limited the ionizing radiation-induced down-regulation of CyclinB1 and CDK1, and suppressed activation of Fas/FasL system pathway. In addition, taurine treatment significantly increased the expression of Nrf2 and HO-1 in GC-2 cells exposed to ionizing radiation, two components in antioxidant pathway. The above cytoprotection of Taurine was blocked by siNrf2. Our results demonstrate that taurine has the potential to effectively protect GC-2 cells from ionizing radiation- triggered damage via upregulation of Nrf2/HO-1 signaling. © 2017 The Author(s). Published by S. Karger AG, Basel.

Energetic particle-induced enhancements of stratospheric nitric acid

NASA Technical Reports Server (NTRS)

Aikin, Arthur C.

1994-01-01

Inclusion of complete ion chemistry in the calculation of minor species production during energetic particle deposition events leads to significant enhancement in the calculated nitric acid concentration during precipitation. An ionization rate of 1.2 x 10(exp 3)/cu cm/s imposed for 1 day increases HNO3 from 3 x 10(exp 5) to 6 x 10(exp 7)/cu cm at 50 km. With an ionization rate of 600 cu cm/s, the maximum HNO3 is 3 x 10(exp 7)/cu cm. Calculations which neglect negative ions predict the nitric acid will fall during precipitation events. The decay time for converting HNO3 into odd nitrogen and hydrogen is more than 1 day for equinoctial periods at 70 deg latitude. Examination of nitric acid data should yield important information on the magnitude and frequency of charged particle events.

Ab initio calculations on the positive ions of the alkaline-earth oxides, fluorides, and hydroxides

NASA Technical Reports Server (NTRS)

Partridge, H.; Langhoff, S. R.; Bauschlicher, C. W., Jr.

1986-01-01

Theoretical dissociation energies are presented for the alkaline-earth fluoride, hydroxide, and oxide positive ions that are considered to be accurate to 0.1-0.2 eV. The r(e) for the positive ions are found to be consistently shorter than the corresponding neutrals by 0.07 + or -0.02 A. The bonding in the ground states is demonstrated to be of predominantly M + 2 X - character. The a 3 Pi and A 1 Pi are found to lie considerably above the X 1 Sigma + ground states of the alkaline-earth fluoride and hydroxide positive ions. The overall agreement of the theoretical ionization potentials with the available experimental appearance potentials is satisfactory; these values should represent the most accurate and consistent set available.

Influence of Rb/Cs Cation-Exchange on Inorganic Sn Halide Perovskites: From Chemical Structure to Physical Properties.

PubMed

Jung, Young-Kwang; Lee, Ji-Hwan; Walsh, Aron; Soon, Aloysius

2017-04-11

CsSnI 3 is a potential lead-free inorganic perovskite for solar energy applications due to its nontoxicity and attractive optoelectronic properties. Despite these advantages, photovoltaic cells using CsSnI 3 have not been successful to date, in part due to low stability. We demonstrate how gradual substitution of Rb for Cs influences the structural, thermodynamic, and electronic properties on the basis of first-principles density functional theory calculations. By examining the effect of the Rb:Cs ratio, we reveal a correlation between octahedral distortion and band gap, including spin-orbit coupling. We further highlight the cation-induced variation of the ionization potential (work function) and the importance of surface termination for tin-based halide perovskites for engineering high-performance solar cells.