td n4 excited: Topics by Science.gov

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Theoretical Studies of Possible Synthetic Routes for the High Energy Density Material Td N4: Excited Electronic States

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

2001-01-01

Vertical electronic excitation energies for single states have been computed for the high energy density material (HEDM) Td N4 in order to assess possible synthetic routes that originate from excited electronic states of N2 molecules. Several ab initio theoretical approaches have been used, including complete active space self-consistent field (CASSCF), state averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D)) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD), which is the highest level of theory employed. Standard double zeta polarized (DZP) and triple zeta double polarized (TZ2P) one-particle basis sets were used. The CASSCF calculations are found to overestimate the excitation energies, while the SA-CASSCF approach rectifies this error to some extent, but not completely. The accuracy of the CIS calculations varied depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results are in generally good agreement. Based on the LRCCSD calculations, the lowest six excited singlet states are 9.35(l(sup)T1), 10.01(l(sup)T2), 10.04(1(sup)A2), 10.07(1(sup)E), 10.12(2(sup)T1), and 10.42(2(sup)T2) eV above the ground state, respectively. Comparison of these excited state energies with the energies of possible excited states of N2+N2 fragments, leads us to propose that the most likely synthetic route for Td N4 involving this mechanism arises from combination of two bound quintet states of N2.
Describing excited state relaxation and localization in TiO 2 nanoparticles using TD-DFT

DOE PAGES

Berardo, Enrico; Hu, Han -Shi; van Dam, Hubertus J. J.; ...

2014-02-26

We have investigated the description of excited state relaxation in naked and hydrated TiO 2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to bemore » the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO 2 nanoparticles is predicted to be associated with a large Stokes’ shift.« less
Describing excited state relaxation and localization in TiO 2 nanoparticles using TD-DFT

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

Berardo, Enrico; Hu, Han -Shi; van Dam, Hubertus J. J.

We have investigated the description of excited state relaxation in naked and hydrated TiO 2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to bemore » the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO 2 nanoparticles is predicted to be associated with a large Stokes’ shift.« less
Theoretical Studies of Routes to Synthesis of Tetrahedral N4

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

2007-01-01

A paper [Chem. Phys. Lett. 345, 295 (2001)] describes theoretical studies of excited electronic states of nitrogen molecules, with a view toward utilizing those states in synthesizing tetrahedral N4, or Td N4 a metastable substance under consideration as a high-energy-density rocket fuel. Several ab initio theoretical approaches were followed in these studies, including complete active space self-consistent field (CASSCF), state-averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD). Standard double zeta polarized and triple zeta double polarized one-particle basis sets were used. The CASSCF calculations overestimated the excitation energies, while SACASSCF calculations partly corrected these overestimates. The accuracy of the CIS calculations varied, depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results were in generally good agreement. The energies of the lowest six excited singlet states of Td N4 as calculated by the LRCCSD were compared with the energies of possible excited states of N2 + N2 fragments, leading to the conclusion that the most likely route for synthesis of Td N4 would involve a combination of two bound quintet states of N2.
Modeling Excited States in TiO2 Nanoparticles: On the Accuracy of a TD-DFT Based Description

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

Berardo, Enrico; Hu, Hanshi; Shevlin, S. A.

2014-03-11

We have investigated the suitability of Time-Dependent Density Functional Theory (TD-DFT) to describe vertical low-energy excitations in naked and hydrated titanium dioxide nanoparticles through a comparison with results from Equation-of-Motion Coupled Cluster (EOM-CC) quantum chemistry methods. We demonstrate that for most TiO2 nanoparticles TD-DFT calculations with commonly used exchange-correlation (XC-)potentials (e.g. B3LYP) and EOM-CC methods give qualitatively similar results. Importantly, however, we also show that for an important subset of structures, TD-DFT gives qualitatively different results depending upon the XC-potential used and that in this case only TD-CAM-B3LYP and TD-BHLYP calculations yield results that are consistent with those obtained usingmore » EOM-CC theory. Moreover, we demonstrate that the discrepancies for such structures arise from a particular combination of defects, excitations involving which are charge-transfer excitations and hence are poorly described by XC-potentials that contain no or low fractions of Hartree-Fock like exchange. Finally, we discuss that such defects are readily healed in the presence of ubiquitously present water and that as a result the description of vertical low-energy excitations for hydrated TiO2 nanoparticles is hence non-problematic.« less
Valence and charge-transfer optical properties for some SinCm (m, n ≤ 12) clusters: Comparing TD-DFT, complete-basis-limit EOMCC, and benchmarks from spectroscopy.

PubMed

Lutz, Jesse J; Duan, Xiaofeng F; Ranasinghe, Duminda S; Jin, Yifan; Margraf, Johannes T; Perera, Ajith; Burggraf, Larry W; Bartlett, Rodney J

2018-05-07

Accurate optical characterization of the closo-Si 12 C 12 molecule is important to guide experimental efforts toward the synthesis of nano-wires, cyclic nano-arrays, and related array structures, which are anticipated to be robust and efficient exciton materials for opto-electronic devices. Working toward calibrated methods for the description of closo-Si 12 C 12 oligomers, various electronic structure approaches are evaluated for their ability to reproduce measured optical transitions of the SiC 2 , Si 2 C n (n = 1-3), and Si 3 C n (n = 1, 2) clusters reported earlier by Steglich and Maier [Astrophys. J. 801, 119 (2015)]. Complete-basis-limit equation-of-motion coupled-cluster (EOMCC) results are presented and a comparison is made between perturbative and renormalized non-iterative triples corrections. The effect of adding a renormalized correction for quadruples is also tested. Benchmark test sets derived from both measurement and high-level EOMCC calculations are then used to evaluate the performance of a variety of density functionals within the time-dependent density functional theory (TD-DFT) framework. The best-performing functionals are subsequently applied to predict valence TD-DFT excitation energies for the lowest-energy isomers of Si n C and Si n-1 C 7-n (n = 4-6). TD-DFT approaches are then applied to the Si n C n (n = 4-12) clusters and unique spectroscopic signatures of closo-Si 12 C 12 are discussed. Finally, various long-range corrected density functionals, including those from the CAM-QTP family, are applied to a charge-transfer excitation in a cyclic (Si 4 C 4 ) 4 oligomer. Approaches for gauging the extent of charge-transfer character are also tested and EOMCC results are used to benchmark functionals and make recommendations.
Valence and charge-transfer optical properties for some SinCm (m, n ≤ 12) clusters: Comparing TD-DFT, complete-basis-limit EOMCC, and benchmarks from spectroscopy

NASA Astrophysics Data System (ADS)

Lutz, Jesse J.; Duan, Xiaofeng F.; Ranasinghe, Duminda S.; Jin, Yifan; Margraf, Johannes T.; Perera, Ajith; Burggraf, Larry W.; Bartlett, Rodney J.

2018-05-01

Accurate optical characterization of the closo-Si12C12 molecule is important to guide experimental efforts toward the synthesis of nano-wires, cyclic nano-arrays, and related array structures, which are anticipated to be robust and efficient exciton materials for opto-electronic devices. Working toward calibrated methods for the description of closo-Si12C12 oligomers, various electronic structure approaches are evaluated for their ability to reproduce measured optical transitions of the SiC2, Si2Cn (n = 1-3), and Si3Cn (n = 1, 2) clusters reported earlier by Steglich and Maier [Astrophys. J. 801, 119 (2015)]. Complete-basis-limit equation-of-motion coupled-cluster (EOMCC) results are presented and a comparison is made between perturbative and renormalized non-iterative triples corrections. The effect of adding a renormalized correction for quadruples is also tested. Benchmark test sets derived from both measurement and high-level EOMCC calculations are then used to evaluate the performance of a variety of density functionals within the time-dependent density functional theory (TD-DFT) framework. The best-performing functionals are subsequently applied to predict valence TD-DFT excitation energies for the lowest-energy isomers of SinC and Sin-1C7-n (n = 4-6). TD-DFT approaches are then applied to the SinCn (n = 4-12) clusters and unique spectroscopic signatures of closo-Si12C12 are discussed. Finally, various long-range corrected density functionals, including those from the CAM-QTP family, are applied to a charge-transfer excitation in a cyclic (Si4C4)4 oligomer. Approaches for gauging the extent of charge-transfer character are also tested and EOMCC results are used to benchmark functionals and make recommendations.
The properties of 4'-N,N-dimethylaminoflavonol in the ground and excited states

NASA Astrophysics Data System (ADS)

Moroz, V. V.; Chalyi, A. G.; Roshal, A. D.

2008-09-01

The mechanism of protonation of 4-N,N-dimethylaminoflavonol and the structure of its protolytic forms in the ground and excited states were studied by electron absorption and fluorescence (steady-state and time-resolved) spectroscopy and with the use of the RM1 quantum-chemical method. A comparison of equilibrium constants and the theoretical enthalpies of formation showed that excitation should be accompanied by the inversion of the basicity of the electron acceptor groups of this compound and, as a consequence, changes in the structure of its monocationic form. An analysis of the spectral parameters of the protolytic 4-N,N-dimethylaminoflavonol forms, however, showed that their structure and the sequence of protonation in the excited state were the same as in the ground state. Changes in the structure of the monocation in the excited state were not observed because of the fast radiationless deactivation of this form and the occurrence of excited state intramolecular proton transfer in aprotic solvents.
Is the Bethe–Salpeter Formalism Accurate for Excitation Energies? Comparisons with TD-DFT, CASPT2, and EOM-CCSD

PubMed Central

2017-01-01

Developing ab initio approaches able to provide accurate excited-state energies at a reasonable computational cost is one of the biggest challenges in theoretical chemistry. In that framework, the Bethe–Salpeter equation approach, combined with the GW exchange-correlation self-energy, which maintains the same scaling with system size as TD-DFT, has recently been the focus of a rapidly increasing number of applications in molecular chemistry. Using a recently proposed set encompassing excitation energies of many kinds [J. Phys. Chem. Lett.2016, 7, 586–591], we investigate here the performances of BSE/GW. We compare these results to CASPT2, EOM-CCSD, and TD-DFT data and show that BSE/GW provides an accuracy comparable to the two wave function methods. It is particularly remarkable that the BSE/GW is equally efficient for valence, Rydberg, and charge-transfer excitations. In contrast, it provides a poor description of triplet excited states, for which EOM-CCSD and CASPT2 clearly outperform BSE/GW. This contribution therefore supports the use of the Bethe–Salpeter approach for spin-conserving transitions. PMID:28301726
The Efficiency of Delone Coverings of the Canonical Tilings 4)) -> T^*(A4) and T}(*(D_6)) -> T^*(D6)

NASA Astrophysics Data System (ADS)

Papadopolos, Zorka; Kasner, Gerald

This chapter is devoted to the coverings of the two quasiperiodic canonical tilings 4)) -> T^*(A4) and T}(*(D_6)) equiv {cal T}(*(2F)) -> T^*(D6) T^*(2F), obtained by projection from the root lattices A4 and D6, respectively. In the first major part of this chapter, in Sect. 5.2, we shall introduce a Delone covering 4)}) -> C^sT^*(A4) of the 2-dimensional decagonal tiling 4)) -> T^*(A4). In the second major part of this chapter, Sect. 5.3, we summarize the results related to the Delone covering of the icosahedral tiling T}(*(D_6)) -> T^*(D6), T}(*(D_6)}) -> CT^*(D6) and determine the zero-, single-, and double- deckings and the resulting thickness of the covering. In the conclusions section, we give some suggestions as to how the definition of the Delone covering might be changed in order to reach some real (full) covering of the icosahedral tiling T}(*(D_6)) -> T^*(D6). In Section 5.2 the definition of the Delone covering is also changed in order to avoid an unnecessary large thickness of the covering.
Long-range correction for tight-binding TD-DFT

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

Humeniuk, Alexander; Mitrić, Roland, E-mail: roland.mitric@uni-wuerzburg.de

2015-10-07

We present two improvements to the tight-binding approximation of time-dependent density functional theory (TD-DFTB): First, we add an exact Hartree-Fock exchange term, which is switched on at large distances, to the ground state Hamiltonian and similarly to the coupling matrix that enters the linear response equations for the calculation of excited electronic states. We show that the excitation energies of charge transfer states are improved relative to the standard approach without the long-range correction by testing the method on a set of molecules from the database in Peach et al. [J. Chem. Phys. 128, 044118 (2008)] which are known tomore » exhibit problematic charge transfer states. The degree of spatial overlap between occupied and virtual orbitals indicates where TD-DFTB and long-range corrected TD-DFTB (lc-TD-DFTB) can be expected to produce large errors. Second, we improve the calculation of oscillator strengths. The transition dipoles are obtained from Slater Koster files for the dipole matrix elements between valence orbitals. In particular, excitations localized on a single atom, which appear dark when using Mulliken transition charges, acquire a more realistic oscillator strength in this way. These extensions pave the way for using lc-TD-DFTB to describe the electronic structure of large chromophoric polymers, where uncorrected TD-DFTB fails to describe the high degree of conjugation and produces spurious low-lying charge transfer states.« less
Absorption and emission spectroscopic characteristics of dipterex and its molecularly imprinted recognition: A TD-DFT investigation

NASA Astrophysics Data System (ADS)

Cheng, Xueli; Li, Liqing; Zhao, Yanyun; Wang, Chang'an

2016-05-01

By using G09 program package, the absorption and fluorescence/phosphorescence spectra of dipterex were explored, and its spectroscopic characters were altered by methacrylic acid (MAA) as the imprinted molecule. The TD-DFT results revealed that: (1) All absorption and emission excitations of dipterex are assigned to the nσ∗ transition; (2) without MAA as imprinted molecule, one of the dipterex Csbnd Cl bonds is extended significantly and dipterex is almost destroyed in transition states; (3) dipterex is connected to methacrylic acid via two hydrogen bonds; (4) for the dipterex-MAA complex, the electronic excitation (ππ∗ excitation) in absorption spectra is dominated by the configuration HOMO → LUMO.
Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules.

PubMed

Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Adamo, Carlo

2009-09-08

Extensive Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out in order to obtain a statistically meaningful analysis of the merits of a large number of functionals. To reach this goal, a very extended set of molecules (∼500 compounds, >700 excited states) covering a broad range of (bio)organic molecules and dyes have been investigated. Likewise, 29 functionals including LDA, GGA, meta-GGA, global hybrids, and long-range-corrected hybrids have been considered. Comparisons with both theoretical references and experimental measurements have been carried out. On average, the functionals providing the best match with reference data are, one the one hand, global hybrids containing between 22% and 25% of exact exchange (X3LYP, B98, PBE0, and mPW1PW91) and, on the other hand, a long-range-corrected hybrid with a less-rapidly increasing HF ratio, namely LC-ωPBE(20). Pure functionals tend to be less consistent, whereas functionals incorporating a larger fraction of exact exchange tend to underestimate significantly the transition energies. For most treated cases, the M05 and CAM-B3LYP schemes deliver fairly small deviations but do not outperform standard hybrids such as X3LYP or PBE0, at least within the vertical approximation. With the optimal functionals, one obtains mean absolute deviations smaller than 0.25 eV, though the errors significantly depend on the subset of molecules or states considered. As an illustration, PBE0 and LC-ωPBE(20) provide a mean absolute error of only 0.14 eV for the 228 states related to neutral organic dyes but are completely off target for cyanine-like derivatives. On the basis of comparisons with theoretical estimates, it also turned out that CC2 and TD-DFT errors are of the same order of magnitude, once the above-mentioned hybrids are selected.
Many-Body Perturbation Theory (MBPT) and Time-Dependent Density-Functional Theory (TD-DFT): MBPT Insights About What Is Missing In, and Corrections To, the TD-DFT Adiabatic Approximation.

PubMed

Casida, Mark E; Huix-Rotllant, Miquel

2016-01-01

In their famous paper, Kohn and Sham formulated a formally exact density-functional theory (DFT) for the ground-state energy and density of a system of N interacting electrons, albeit limited at the time by certain troubling representability questions. As no practical exact form of the exchange-correlation (xc) energy functional was known, the xc-functional had to be approximated, ideally by a local or semilocal functional. Nowadays, however, the realization that Nature is not always so nearsighted has driven us up Perdew's Jacob's ladder to find increasingly nonlocal density/wavefunction hybrid functionals. Time-dependent (TD-) DFT is a younger development which allows DFT concepts to be used to describe the temporal evolution of the density in the presence of a perturbing field. Linear response (LR) theory then allows spectra and other information about excited states to be extracted from TD-DFT. Once again the exact TD-DFT xc-functional must be approximated in practical calculations and this has historically been done using the TD-DFT adiabatic approximation (AA) which is to TD-DFT very similar to what the local density approximation (LDA) is to conventional ground-state DFT. Although some of the recent advances in TD-DFT focus on what can be done within the AA, others explore ways around the AA. After giving an overview of DFT, TD-DFT, and LR-TD-DFT, this chapter focuses on many-body corrections to LR-TD-DFT as one way to build hybrid density-functional/wavefunction methodology for incorporating aspects of nonlocality in time not present in the AA.
Electronic spectroscopy of HRe(CO) 5: a CASSCF/CASPT2 and TD-DFT study

NASA Astrophysics Data System (ADS)

Bossert, J.; Ben Amor, N.; Strich, A.; Daniel, C.

2001-07-01

The low-lying excited states of HRe(CO) 5 have been calculated at the CASSCF/CASPT2 and TD-DFT level of theory using relativistic effective core potentials (ECP) or ab initio model potentials (AIMP). The theoretical absorption spectrum is compared to the experimental one. Despite the similarity between the experimental absorption spectra of HMn(CO) 5 and HRe(CO) 5 in the UV/visible energy domain it is shown that the assignment differs significantly between the two molecules. The low-lying excited states of HRe(CO) 5 correspond to 5d→π *CO excitations whereas the spectrum of HMn(CO) 5 consists mainly of 3d→3d and 3d→ σ*Mn-H excitations. If the CASPT2 and TD-DFT results are quite comparable for the lowest excited states, the upper part assignment is more problematic with the TD-DFT method.
Effect of methyl substituents on the electronic transitions in simple meso-aniline-BODIPY based dyes: RI-CC2 and TD-CAM-B3LYP computational investigation

NASA Astrophysics Data System (ADS)

Petrushenko, Igor K.; Petrushenko, Konstantin B.

2018-02-01

The S0 → Si, i = 1-5 electronic transitions of four 8-(4-aniline)-BODIPY and four 8-(N,N-dimethyl)-BODIPY dyes, differ by number and position of methyl substituents in the BODIPY frame, were investigated theoretically using ab initio the coupled cluster doubles (CC2) and TD-CAM-B3LYP methods. Methyl substituents in the BODIPY frame and the aniline fragment at the meso position disturb energy of local excitations S0 → S1, S0 → S3, and S0 → S4 weakly in comparison with the fully unsubstituted BODIPY molecule. These transitions in experimental spectra form the most long-wave absorption bands at ca. 500 nm as well as absorption bands in the region of 300-400 nm. At the same time, the presence of aniline fragments leads to the appearance of new S0 → S2 transitions of the charge transfer character in electronic spectra of BODIPYs. We also found a linear relationship between vertical energy of these charge transfer transitions and the electron donating power of an aniline fragment and electron accepting power of the BODIPY core depending on the number and position of methyl groups. The CC2 method provides the best overall description of the excitation energies in line with the experimental observations. On average, the quality of TD-CAM-B3LYP is almost equal to that of CC2, however the TD method with the CAM-B3LYP functional slightly underestimates the CT excitation energy.
Dynamics of the solute-solvent interactions of electronically excited 4-N,N-dimethylaminobenzonitrile (DMABN) and of 3,5,N,N-tetramethyl-4-aminobenzonitrile (TMABN) dissolved in viscous alcohols and in a viscous nitrile

NASA Astrophysics Data System (ADS)

Weisenborn, Petra C. M.; Huizer, A. Herbert; Varma, Cyril A. G. O.

1989-06-01

The time dependence of the fluorescence of solutions of 4-N,N-dimethylaminobenzonitrile (DMABN) and 3,5,N,N-tetramethyl-4-aminobenzonitrile (TMA BN) in neat polar solvents has been investigated, using a 25 ps UV-laser pulse for excitation and a streak camera for detection. Both the compounds DMABN and TMABN exhibit normal fluorescence F N and anomalous fluorescence F A, but all the solutions of TMABN show merely a single band in the fluorescence spectrum, which is a superposition of the bands F N and F A. In the case of DMABN the fluorescence in the region λ < 400 nm, where F N dominates, the fluorescence decays tri-exponentially due to fluorescence from three types of species, namely excited solute-solvent complexes, excited bare solutes and solute-solvent exciplexes. Within the lifetime of these emitting species there is probably no reverse reaction from exciplexes to excited solute-solvent complexes or excited bare solutes. This is in contrast with a previously presented picture, which includes such a reverse reaction. In the case of the solution of DMABN in n-butanol, the fluorescence at λ < 400 nm is bi-exponential. We show that this is due to an accidental degeneracy of two lifetimes. In contrast to a previous conclusion, we find that DMABN exists partially in the form of ground state solute-solvent complexes also in the solution in nitriles. The anomalous fluorescence develops in two phases, in the first one solute-solvent exciplexes are formed and in the second one the dielectric polarization of the solvent around the exciplex builds up. The rate constant for the formation of the anomalously fluorescing species, i.e. solute-solvent exciplexes, bears no relation with the longitudinal relaxation time, as claimed to have been shown previously.
TD-CI simulation of the electronic optical response of molecules in intense fields II: comparison of DFT functionals and EOM-CCSD.

PubMed

Sonk, Jason A; Schlegel, H Bernhard

2011-10-27

Time-dependent configuration interaction (TD-CI) simulations can be used to simulate molecules in intense laser fields. TD-CI calculations use the excitation energies and transition dipoles calculated in the absence of a field. The EOM-CCSD method provides a good estimate of the field-free excited states but is rather expensive. Linear-response time-dependent density functional theory (TD-DFT) is an inexpensive alternative for computing the field-free excitation energies and transition dipoles needed for TD-CI simulations. Linear-response TD-DFT calculations were carried out with standard functionals (B3LYP, BH&HLYP, HSE2PBE (HSE03), BLYP, PBE, PW91, and TPSS) and long-range corrected functionals (LC-ωPBE, ωB97XD, CAM-B3LYP, LC-BLYP, LC-PBE, LC-PW91, and LC-TPSS). These calculations used the 6-31G(d,p) basis set augmented with three sets of diffuse sp functions on each heavy atom. Butadiene was employed as a test case, and 500 excited states were calculated with each functional. Standard functionals yield average excitation energies that are significantly lower than the EOM-CC, while long-range corrected functionals tend to produce average excitation energies slightly higher. Long-range corrected functionals also yield transition dipoles that are somewhat larger than EOM-CC on average. The TD-CI simulations were carried out with a three-cycle Gaussian pulse (ω = 0.06 au, 760 nm) with intensities up to 1.26 × 10(14) W cm(-2) directed along the vector connecting the end carbons. The nonlinear response as indicated by the residual populations of the excited states after the pulse is far too large with standard functionals, primarily because the excitation energies are too low. The LC-ωPBE, LC-PBE, LC-PW91, and LC-TPSS long-range corrected functionals produce responses comparable to EOM-CC.
Role of electronic excited N2 in vibrational excitation of the N2 ground state at high latitudes

NASA Astrophysics Data System (ADS)

Campbell, L.; Cartwright, D. C.; Brunger, M. J.; Teubner, P. J. O.

2006-09-01

Vibrationally excited N2 is important in determining the ionospheric electron density and has also been proposed to play a role in the production of NO in disturbed atmospheres. We report here predictions of the absolute vibrational distributions in the ground electronic state of N2 produced by electron impact excitation, at noon and midnight under quiet geomagnetic conditions and disturbed conditions corresponding to the aurora IBCII+ and IBCIII+ at 60°N latitude and 0° longitude, at altitudes between 130 and 350 km. These predictions were obtained from a model which includes thermal excitation and direct electron impact excitation of the vibrational levels of the N2 ground state and its excited electronic states; radiative cascade from all excited electronic states to all vibrational levels of the ground electronic state; quenching by O, O2, and N2; molecular and ambipolar diffusion; and the dominant chemical reactions. Results from this study show that for both aurora and daytime electron environments: (1) cascade from the higher electronic states of N2 determines the population of the higher vibrational levels in the N2 ground state and (2) the effective ground state vibrational temperature for levels greater than 4 in N2 is predicted to be in the range 4000-13000 K for altitudes greater than 200 km. Correspondingly, the associated enhancement factor for the O+ reaction with vibrationally excited N2 to produce NO+ is predicted to increase with increasing altitude (up to a maximum at a height which increases with auroral strength) for both aurora and daytime environments and to increase with increasing auroral strength. The contribution of the cascade from the excited electronic states was evaluated and found to be relatively minor compared to the direct excitation process.
Excitation wavelength dependence of excited state intramolecular proton transfer reaction of 4'-N,N-diethylamino-3-hydroxyflavone in room temperature ionic liquids studied by optical Kerr gate fluorescence measurement.

PubMed

Suda, Kayo; Terazima, Masahide; Sato, Hirofumi; Kimura, Yoshifumi

2013-10-17

Excited state intramolecular proton transfer reactions (ESIPT) of 4'-N,N-diethylamino-3-hydroxyflavone (DEAHF) in ionic liquids have been studied by steady-state and time-resolved fluorescence measurements at different excitation wavelengths. Steady-state measurements show the relative yield of the tautomeric form to the normal form of DEAHF decreases as excitation wavelength is increased from 380 to 450 nm. The decrease in yield is significant in ionic liquids that have cations with long alkyl chains. The extent of the decrease is correlated with the number of carbon atoms in the alkyl chains. Time-resolved fluorescence measurements using optical Kerr gate spectroscopy show that ESIPT rate has a strong excitation wavelength dependence. There is a large difference between the spectra at a 200 ps delay from different excitation wavelengths in each ionic liquid. The difference is pronounced in ionic liquids having a long alkyl chain. The equilibrium constant in the electronic excited state obtained at a 200 ps delay and the average reaction rate are also correlated with the alkyl chain length. Considering the results of the steady-state fluorescence and time-resolved measurements, the excitation wavelength dependence of ESIPT is explained by state selective excitation due to the difference of the solvation, and the number of alkyl chain carbon atoms is found to be a good indicator of the effect of inhomogeneity for this reaction.

Pump-probe photoelectron velocity-map imaging of autoionizing singly excited 4s{sup 1}4p{sup 6}np{sup 1}(n=7,8) and doubly excited 4s{sup 2}4p{sup 4}5s{sup 1}6p{sup 1} resonances in atomic krypton

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

Doughty, Benjamin; Haber, Louis H.; Leone, Stephen R.

2011-10-15

Pump-probe photoelectron velocity-map imaging, using 27-eV high-harmonic excitation and 786-nm ionization, is used to resolve overlapping autoionizing resonances in atomic krypton, obtaining two-photon photoelectron angular distributions (PADs) for singly and doubly excited states. Two features in the photoelectron spectrum are assigned to singly excited 4s{sup 1}4p{sup 6}np{sup 1} (n = 7,8) configurations and four features provide information about double excitation configurations. The anisotropy parameters for the singly excited 7p configuration are measured to be {beta}{sub 2} = 1.61 {+-} 0.06 and {beta}{sub 4} = 1.54 {+-} 0.16 while the 8p configuration gives {beta}{sub 2} = 1.23 {+-} 0.19 and {beta}{submore » 4} = 0.60 {+-} 0.15. These anisotropies most likely represent the sum of overlapping PADs from states of singlet and triplet spin multiplicities. Of the four bands corresponding to ionization of doubly excited states, two are assigned to 4s{sup 2}4p{sup 4}5s{sup 1}6p{sup 1} configurations that are probed to different J-split ion states. The two remaining doubly excited states are attributed to a previously observed, but unassigned, resonance in the vacuum-ultraviolet photoabsorption spectrum. The PADs from each of the double excitation states are also influenced by overlap from neighboring states that are not completely spectrally resolved. The anisotropies of the observed double excitation states are reported, anticipating future theoretical and experimental work to separate the overlapping PADs into the state resolved PADs. The results can be used to test theories of excited state ionization.« less
Tetanus, Diphtheria (Td) Vaccine

MedlinePlus

... Headache (about 1 person in 4) Tiredness (about 1 person in 4) Moderate Problems following Td vaccine:(Interfered with activities, but did not require medical attention)Fever over 102°F (rare) Severe Problems following ...
Energetic ion, atom, and molecule reactions and excitation in low-current H2 discharges: H(alpha) Doppler profiles.

PubMed

Petrović, Z Lj; Phelps, A V

2009-12-01

Absolute spectral emissivities for Doppler broadened H(alpha) profiles are measured and compared with predictions of energetic hydrogen ion, atom, and molecule behavior in low-current electrical discharges in H2 at very high electric field E to gas density N ratios E/N and low values of Nd , where d is the parallel-plate electrode separation. These observations reflect the energy and angular distributions for the excited atoms and quantitatively test features of multiple-scattering kinetic models in weakly ionized hydrogen in the presence of an electric field that are not tested by the spatial distributions of H(alpha) emission. Absolute spectral intensities agree well with predictions. Asymmetries in Doppler profiles observed parallel to the electric field at 4NTd result primarily from excitation by fast H atoms directed toward the cathode and diffusely reflected from the cathode. (1 Td=10(-21) V m(2)) The effects of reflection of hydrogen particles and of changes with cathode material are modeled accurately without adjustable parameters. Maximum measured wavelength shifts result from acceleration of H+ ions and charge transfer to fast H atoms. The Doppler profiles are consistent with models of reactions among H+, H2+, H3 , H, and H2 leading to fast H atoms and then fast excited H(n=3) atoms.
Multiresolution quantum chemistry in multiwavelet bases: excited states from time-dependent Hartree–Fock and density functional theory via linear response

DOE PAGES

Yanai, Takeshi; Fann, George I.; Beylkin, Gregory; ...

2015-02-25

Using the fully numerical method for time-dependent Hartree–Fock and density functional theory (TD-HF/DFT) with the Tamm–Dancoff (TD) approximation we use a multiresolution analysis (MRA) approach to present our findings. From a reformulation with effective use of the density matrix operator, we obtain a general form of the HF/DFT linear response equation in the first quantization formalism. It can be readily rewritten as an integral equation with the bound-state Helmholtz (BSH) kernel for the Green's function. The MRA implementation of the resultant equation permits excited state calculations without virtual orbitals. Moreover, the integral equation is efficiently and adaptively solved using amore » numerical multiresolution solver with multiwavelet bases. Our implementation of the TD-HF/DFT methods is applied for calculating the excitation energies of H 2, Be, N 2, H 2O, and C 2H 4 molecules. The numerical errors of the calculated excitation energies converge in proportion to the residuals of the equation in the molecular orbitals and response functions. The energies of the excited states at a variety of length scales ranging from short-range valence excitations to long-range Rydberg-type ones are consistently accurate. It is shown that the multiresolution calculations yield the correct exponential asymptotic tails for the response functions, whereas those computed with Gaussian basis functions are too diffuse or decay too rapidly. Finally, we introduce a simple asymptotic correction to the local spin-density approximation (LSDA) so that in the TDDFT calculations, the excited states are correctly bound.« less
Assessment of TD-DFT and LF-DFT for study of d − d transitions in first row transition metal hexaaqua complexes

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

Vlahović, Filip; Perić, Marko; Zlatar, Matija, E-mail: matijaz@chem.bg.ac.rs

2015-06-07

Herein, we present the systematic, comparative computational study of the d − d transitions in a series of first row transition metal hexaaqua complexes, [M(H{sub 2}O){sub 6}]{sup n+} (M{sup 2+/3+} = V {sup 2+/3+}, Cr{sup 2+/3+}, Mn{sup 2+/3+}, Fe{sup 2+/3+}, Co{sup 2+/3+}, Ni{sup 2+}) by the means of Time-dependent Density Functional Theory (TD-DFT) and Ligand Field Density Functional Theory (LF-DFT). Influence of various exchange-correlation (XC) approximations have been studied, and results have been compared to the experimental transition energies, as well as, to the previous high-level ab initio calculations. TD-DFT gives satisfactory results in the cases of d{sup 2}, d{supmore » 4}, and low-spin d{sup 6} complexes, but fails in the cases when transitions depend only on the ligand field splitting, and for states with strong character of double excitation. LF-DFT, as a non-empirical approach to the ligand field theory, takes into account in a balanced way both dynamic and non-dynamic correlation effects and hence accurately describes the multiplets of transition metal complexes, even in difficult cases such as sextet-quartet splitting in d{sup 5} complexes. Use of the XC functionals designed for the accurate description of the spin-state splitting, e.g., OPBE, OPBE0, or SSB-D, is found to be crucial for proper prediction of the spin-forbidden excitations by LF-DFT. It is shown that LF-DFT is a valuable alternative to both TD-DFT and ab initio methods.« less
Spectral densities for Frenkel exciton dynamics in molecular crystals: A TD-DFTB approach

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Megow, Jörg; Niehaus, Thomas; Kühn, Oliver

2017-02-01

Effects of thermal fluctuations on the electronic excitation energies and intermonomeric Coulomb couplings are investigated for a perylene-tetracarboxylic-diimide crystal. To this end, time dependent density functional theory based tight binding (TD-DFTB) in the linear response formulation is used in combination with electronic ground state classical molecular dynamics. As a result, a parametrized Frenkel exciton Hamiltonian is obtained, with the effect of exciton-vibrational coupling being described by spectral densities. Employing dynamically defined normal modes, these spectral densities are analyzed in great detail, thus providing insight into the effect of specific intramolecular motions on excitation energies and Coulomb couplings. This distinguishes the present method from approaches using fixed transition densities. The efficiency by which intramolecular contributions to the spectral density can be calculated is a clear advantage of this method as compared with standard TD-DFT.
Structure and properties of the anions MF4-, MCl4- and MBr4- (M = C, Si, Ge)

NASA Astrophysics Data System (ADS)

Grein, Friedrich

2015-04-01

Density functional theory (DFT), Møller-Plesset (MP2) and coupled cluster with single and double substitutions including non-iterative triple excitations (CCSD(T)) calculations on the anions MX4-, with M = C, Si, Ge and X = F, Cl, Br, show that GeF4-, SiCl4-, GeCl4- and SiBr4- prefer a C2v conformation, but CCl4- is an elongated C3v structure. CBr4- has Td symmetry in MP2, but is slightly more stable in elongated C3v form with DFT and CCSD(T). GeBr4- has Td symmetry. CF4- and SiF4- are unstable with respect to loss of an electron. Vertical electron affinities (EAs) are negative also for CCl4 and SiCl4, and close to zero for GeF4 and SiBr4. Adiabatic EAs range from 0.47 eV for SiCl4 to 1.78 eV for GeBr4. The lowest excited states at Td symmetry are 2T2 resonances with energies of 2.1-3.5 eV, resulting from excitation of the a1 singly occupied molecular orbital to vacant t2 orbitals. Vertical excitation energies (VEEs) and vibrational frequencies are given for the most stable anionic geometries. Comparison with experimental VEEs for CCl4- is made. From dissociation energies of MX4, MX4-, MX3 and MX3-, appearance energies of X-, MX3-, X2- and MX2- were calculated. Most were found to be in reasonable agreement with experimental values. Theoretical spin densities and g-factors have been compared with experimental results available for CCl4-, SiCl4- and GeCl4-.
Synthesis, structure characterization, photoluminescence properties and TD-DFT calculations for two new borates.

PubMed

Hadjadj, Nasreddine; Dems, Mohamed AbdEsselem; Merazig, Hocine; Bendjeddou, Lamia

2018-04-01

Due to their rich structural chemistry and wide variety of applications, borate materials have provided a rich area of research. In a continuation of this research, diethylammonium bis(2-oxidobenzoato-κ 2 O 1 ,O 2 )borate, C 4 H 12 N + ·BO 4 (C 7 H 4 O) 2 - , (1), and propylammonium bis(2-oxidobenzoato-κ 2 O 1 ,O 2 )borate, C 3 H 10 N + ·BO 4 (C 7 H 4 O) 2 - , (2), have been synthesized by the reaction of boric acid with salicylic acid under ambient conditions. In both structures, the B atom exhibits a slightly distorted tetrahedral environment formed by the bidentate coordination of two salicylate anions via the O atoms of the central carboxylate and oxide groups. In the crystals of salts (1) and (2), mixed cation-anion layers lying parallel to the (101) plane are formed through N-H...O, C-H...O and C-H...π/N-H...O hydrogen-bonding interactions, resulting, in each case, in a two-dimensional supramolecular architecture in the solid state. The photoluminescence properties of the salts were studied using the as-synthesized samples and reveal that salts (1) and (2) both display a strong blue-light emission, with maxima at 489 and 491 nm, respectively. In DFT/TD-DFT (time-dependent density functional theory) studies, the blue emission appears to be derived from an intramolecular charge transfer (ICT) excited state. In addition, IR and UV-Vis spectroscopies were used to investigate the title salts.
Multisite constrained model of trans-4-(N,N-dimethylamino)-4'-nitrostilbene for structural elucidation of radiative and nonradiative excited states.

PubMed

Lin, Cheng-Kai; Wang, Yu-Fu; Cheng, Yuan-Chung; Yang, Jye-Shane

2013-04-18

A constrained model compound of trans-4-(N,N-dimethylamino)-4'-nitrostilbene (DNS), namely, compound DNS-B3 that is limited to torsions about the phenyl-nitro C-N bond and the central C═C bond, was prepared to investigate the structural nature of the radiative and nonradiative states of electronically excited DNS. The great similarities in solvent-dependent electronic spectra, fluorescence decay times, and quantum yields for fluorescence (Φf) and trans → cis photoisomerization (Φtc) between DNS and DNS-B3 indicate that the fluorescence is from a planar charge-transfer state and torsion of the nitro group is sufficient to account for the nonradiative decay of DNS. This conclusion is supported by TDDFT calculations on DNS-B3 in dichloromethane. The structure at the conical intersection for internal conversion is associated with not only a twisting but also a pyramidalization of the nitro group. The mechanism of the NO2 torsion is discussed in terms of the effects of solvent polarity, the substituents, and the volume demand. The differences and analogies of the NO2- vs amino-twisted intramolecular charge-transfer (TICT) state of trans-aminostilbenes are also discussed.
Complete Genome Sequences of Lactobacillus johnsonii Strain N6.2 and Lactobacillus reuteri Strain TD1.

PubMed

Leonard, Michael T; Valladares, Ricardo B; Ardissone, Alexandria; Gonzalez, Claudio F; Lorca, Graciela L; Triplett, Eric W

2014-05-08

We report here the complete genome sequences of Lactobacillus johnsonii strain N6.2, a homofermentative lactic acid intestinal bacterium, and Lactobacillus reuteri strain TD1, a heterofermentative lactic acid intestinal bacterium, both isolated from a type 1 diabetes-resistant rat model.
TdT activity in acute myeloid leukemias defined by monoclonal antibodies.

PubMed

San Miguel, J F; González, M; Cañizo, M C; Anta, J P; Portero, J A; López-Borrasca, A

1986-09-01

Blast cells from eight out of 71 patients diagnosed with acute myeloid leukemia (AML) by morphological, cytochemical, and immunological criteria showed TdT activity. Their distribution according to the FAB classification was one M1, one M2, one M4, two M5a, one M5b, one M6, and one undifferentiated case. The TdT+ AML cases did not show major clinical and hematological differences when compared with the classical TdT- AML patients. Other phenotypical aberrations in the expression of membrane antigens, apart from the presence of nuclear TdT, were not observed in these TdT+ cases after study with a large panel of monoclonal antibodies. A higher incidence of TdT+ cases was found among the monocytic variants of AML (M4 and M5)--four cases--than in the granulocytic variants (M1, M2, and M3)--2 cases. These TdT+ cases should be distinguished from mixed leukemias by double labeling techniques, assessing in the TdT+ AML the coexpression of TdT and myeloid markers in individual cells as shown in four of our cases.
A novel thiazolidinedione derivative TD118 showing selective algicidal effects for red tide control.

PubMed

Wu, Ying; Lee, Yew; Jung, Seul-Gi; Kim, Minju; Eom, Chi-Yong; Kim, Si Wouk; Cho, Hoon; Jin, Eonseon

2014-05-01

Thiazolidinedione (TD) derivatives have been found to have an algicidal effect on harmful algal bloom microalgae. In this study, 75 TD derivatives were synthesized and analyzed for algicidal activity. Among these synthetic TDs, 18 TD derivatives showed specific algicidal activity on two strains belonging to the classes Raphidophyceae (Chattonella marina and Heterosigma akashiwo) and Dinophyceae (Cochlodinium polykrikoides). Two strains belonging to Bacillariophyceae (Navicula pelliculosa and Phaeodactylum EPV), one strain belonging to Dinophyceae (Amphidinium sp.), and a Eustigmatophycean microalga (Nannochloropsis oculata) showed less sensitivity to the TD derivatives than the other two phyla. The most reactive TD derivative, compound 2 (TD118), was selected and tested for morphological and physiological changes. TD118 effectively damaged the cell membrane of C. marina, H. akashiwo and C. polykrikoides. The O₂ evolution and photosystem II efficiency (F(v)/F(m)) of C. marina, H. akashiwo and C. polykrikoides were also severely reduced by TD118 treatment. Amphidinium sp., N. pelliculosa, Phaeodactylum EPV and N. oculata showed less reduction of O₂ evolution and the F(v)/F(m) by TD118. These results imply that the species-specific TD structure relationship may be due to structural and/or physiological differences among microalgal species.
Temperature dependent fluorescence spectra arise from change in excited-state intramolecular proton transfer potential of 4‧-N,N-dimethylamino-3-hydroxyflavone-doped acetonitrile crystals

NASA Astrophysics Data System (ADS)

Furukawa, Kazuki; Yamamoto, Norifumi; Hino, Kazuyuki; Sekiya, Hiroshi

2016-01-01

The effect of intermolecular interaction on excited-state intramolecular proton transfer (ESIPT) in 4‧-N,N-dimethylamino-3-hydroxyflavone (DMHF) doped in acetonitrile crystals was investigated by measuring the temperature dependence of fluorescence excitation and fluorescence spectra. A solid/solid phase transition of DMHF-doped acetonitrile crystals occurred in the temperature between 210 and 218 K. Significant differences in the spectral profiles and shifts in the fluorescence spectra were observed in the low- and high-temperature regions of the phase transition. The temperature dependence of the ESIPT potential of DMHF is discussed.
Tree Data (TD)

Treesearch

Robert E. Keane

2006-01-01

The Tree Data (TD) methods are used to sample individual live and dead trees on a fixed-area plot to estimate tree density, size, and age class distributions before and after fire in order to assess tree survival and mortality rates. This method can also be used to sample individual shrubs if they are over 4.5 ft tall. When trees are larger than the user-specified...
Extended Lagrangian Excited State Molecular Dynamics.

PubMed

Bjorgaard, J A; Sheppard, D; Tretiak, S; Niklasson, A M N

2018-02-13

An extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. The XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree-Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).
Fast Nitrogen Atoms from Dissociative Excitation of N2 by Electron Impact

NASA Technical Reports Server (NTRS)

Ajello, Joseph M.; Ciocca, Marco

1996-01-01

The Doppler profiles of one of the fine structure lines of the N I (1200 A) g (sup 4)S(sup 0)-(sup 4)P multiplet and of the N II (1085 A) g (sup 3)p(sup O)-(sup 3)D multiplet have been measured. Excitation of the multiplets is produced by electron impact dissociative excitation of N2. The experimental line profiles are evaluated by fast Fourier transform (FFT) techniques and analysis of the profiles yields the kinetic energy distribution of fragments. The full width at half maximum (FWHM) of N I (1200 A) increases from 27+/-6 mA at 30 eV to 37+/-4 mA at 100 eV as the emission cross section of the dissociative ionization excitation process becomes more important relative to the dissociative excitation process. The FWHM of the N II (1085 A) line is 36+/-4 mA at 100 eV. For each multiplet the kinetic energy distribution function of each of the two fragment N atoms (ions) is much broader than thermal with a mean energy above 1.0 eV. The dissociation process with the largest cross section is predissociation and predominantly produces N atoms with kinetic energy distributions having mean energies above 0.5 eV. Dissociative processes can lead to a substantial escape flux of N I atoms from the satellites, Titan and Triton of the outer planets.
Excitation mechanisms of Er optical centers in GaN epilayers

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

George, D. K.; Hawkins, M. D.; McLaren, M.

2015-10-26

We report direct evidence of two mechanisms responsible for the excitation of optically active Er{sup 3+} ions in GaN epilayers grown by metal-organic chemical vapor deposition. These mechanisms, resonant excitation via the higher-lying inner 4f shell transitions and band-to-band excitation of the semiconductor host, lead to narrow emission lines from isolated and the defect-related Er optical centers. However, these centers have different photoluminescence spectra, local defect environments, decay dynamics, and excitation cross sections. The photoluminescence at 1.54 μm from the isolated Er optical center which can be excited by either mechanism has the same decay dynamics, but possesses a much highermore » excitation cross-section under band-to-band excitation. In contrast, the photoluminescence at 1.54 μm from the defect-related Er optical center can only be observed through band-to-band excitation but has the largest excitation cross-section. These results explain the difficulty in achieving gain in Er doped GaN and indicate approaches for realization of optical amplification, and possibly lasing, at room temperature.« less
Application of Hermitian time-dependent coupled-cluster response Ansätze of second order to excitation energies and frequency-dependent dipole polarizabilities

NASA Astrophysics Data System (ADS)

Wälz, Gero; Kats, Daniel; Usvyat, Denis; Korona, Tatiana; Schütz, Martin

2012-11-01

Linear-response methods, based on the time-dependent variational coupled-cluster or the unitary coupled-cluster model, and truncated at the second order according to the Møller-Plesset partitioning, i.e., the TD-VCC[2] and TD-UCC[2] linear-response methods, are presented and compared. For both of these methods a Hermitian eigenvalue problem has to be solved to obtain excitation energies and state eigenvectors. The excitation energies thus are guaranteed always to be real valued, and the eigenvectors are mutually orthogonal, in contrast to response theories based on “traditional” coupled-cluster models. It turned out that the TD-UCC[2] working equations for excitation energies and polarizabilities are equivalent to those of the second-order algebraic diagrammatic construction scheme ADC(2). Numerical tests are carried out by calculating TD-VCC[2] and TD-UCC[2] excitation energies and frequency-dependent dipole polarizabilities for several test systems and by comparing them to the corresponding values obtained from other second- and higher-order methods. It turns out that the TD-VCC[2] polarizabilities in the frequency regions away from the poles are of a similar accuracy as for other second-order methods, as expected from the perturbative analysis of the TD-VCC[2] polarizability expression. On the other hand, the TD-VCC[2] excitation energies are systematically too low relative to other second-order methods (including TD-UCC[2]). On the basis of these results and an analysis presented in this work, we conjecture that the perturbative expansion of the Jacobian converges more slowly for the TD-VCC formalism than for TD-UCC or for response theories based on traditional coupled-cluster models.
Analytical excited state forces for the time-dependent density-functional tight-binding method.

PubMed

Heringer, D; Niehaus, T A; Wanko, M; Frauenheim, Th

2007-12-01

An analytical formulation for the geometrical derivatives of excitation energies within the time-dependent density-functional tight-binding (TD-DFTB) method is presented. The derivation is based on the auxiliary functional approach proposed in [Furche and Ahlrichs, J Chem Phys 2002, 117, 7433]. To validate the quality of the potential energy surfaces provided by the method, adiabatic excitation energies, excited state geometries, and harmonic vibrational frequencies were calculated for a test set of molecules in excited states of different symmetry and multiplicity. According to the results, the TD-DFTB scheme surpasses the performance of configuration interaction singles and the random phase approximation but has a lower quality than ab initio time-dependent density-functional theory. As a consequence of the special form of the approximations made in TD-DFTB, the scaling exponent of the method can be reduced to three, similar to the ground state. The low scaling prefactor and the satisfactory accuracy of the method makes TD-DFTB especially suitable for molecular dynamics simulations of dozens of atoms as well as for the computation of luminescence spectra of systems containing hundreds of atoms. (c) 2007 Wiley Periodicals, Inc.
Semiempirical modeling of Ag nanoclusters: New parameters for optical property studies enable determination of double excitation contributions to plasmonic excitation

DOE PAGES

Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.

2016-06-03

Quantum mechanical studies of Ag nanoclusters have shown that plasmonic behavior can be modeled in terms of excited states where collectivity among single excitations leads to strong absorption. However, new computational approaches are needed to provide understanding of plasmonic excitations beyond the single-excitation level. We show that semiempirical INDO/CI approaches with appropriately selected parameters reproduce the TD-DFT optical spectra of various closed-shell Ag clusters. The plasmon-like states with strong optical absorption comprise linear combinations of many singly excited configurations that contribute additively to the transition dipole moment, whereas all other excited states show significant cancellation among the contributions to themore » transition dipole moment. The computational efficiency of this approach allows us to investigate the role of double excitations at the INDO/SDCI level. The Ag cluster ground states are stabilized by slight mixing with doubly excited configurations, but the plasmonic states generally retain largely singly excited character. The consideration of double excitations in all cases improves the agreement of the INDO/CI absorption spectra with TD-DFT, suggesting that the SDCI calculation effectively captures some of the ground-state correlation implicit in DFT. Furthermore, these results provide the first evidence to support the commonly used assumption that single excitations are in many cases sufficient to describe the optical spectra of plasmonic excitations quantum mechanically.« less

Extended Lagrangian Excited State Molecular Dynamics

DOE PAGES

Bjorgaard, Josiah August; Sheppard, Daniel Glen; Tretiak, Sergei; ...

2018-01-09

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both formore » the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).« less
Extended Lagrangian Excited State Molecular Dynamics

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

Bjorgaard, Josiah August; Sheppard, Daniel Glen; Tretiak, Sergei

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both formore » the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).« less
Particle identification using digital pulse shape discrimination in a nTD silicon detector with a 1 GHz sampling digitizer

NASA Astrophysics Data System (ADS)

Mahata, K.; Shrivastava, A.; Gore, J. A.; Pandit, S. K.; Parkar, V. V.; Ramachandran, K.; Kumar, A.; Gupta, S.; Patale, P.

2018-06-01

In beam test experiments have been carried out for particle identification using digital pulse shape analysis in a 500 μm thick Neutron Transmutation Doped (nTD) silicon detector with an indigenously developed FPGA based 12 bit resolution, 1 GHz sampling digitizer. The nTD Si detector was used in a low-field injection setup to detect light heavy-ions produced in reactions of ∼ 5 MeV/A 7Li and 12C beams on different targets. Pulse height, rise time and current maximum have been obtained from the digitized charge output of a high bandwidth charge and current sensitive pre-amplifier. Good isotopic separation have been achieved using only the digitized charge output in case of light heavy-ions. The setup can be used for charged particle spectroscopy in nuclear reactions involving light heavy-ions around the Coulomb barrier energies.
TdKT, a new killer toxin produced by Torulaspora delbrueckii effective against wine spoilage yeasts.

PubMed

Villalba, María Leticia; Susana Sáez, Julieta; Del Monaco, Silvana; Lopes, Christian Ariel; Sangorrín, Marcela Paula

2016-01-18

Microbiological spoilage is a major concern throughout the wine industry, and control tools are limited. This paper addresses the identification and partial characterization of a new killer toxin from Torulaspora delbrueckii with potential biocontrol activity of Brettanomyces bruxellensis, Pichia guilliermondii, Pichia manshurica and Pichia membranifaciens wine spoilage. A panel of 18 different wine strains of T. delbrueckii killer yeasts was analysed, and the strain T. delbrueckii NPCC 1033 (TdKT producer) showed a significant inhibitory effect on the growth of all different spoilage yeasts evaluated. The TdKT toxin was then subjected to a partial biochemical characterization. Its estimated molecular weight was N30 kDa and it showed glucanase and chitinase enzymatic activities. The killer activity was stable between pH 4.2 and 4.8 and inactivated at temperature above 40 °C. Pustulan and chitin — but not other cell wall polysaccharides — prevented sensitive yeast cells from being killed by TdKT, suggesting that those may be the first toxin targets in the cell wall. TdKT provoked an increase in necrosis cell death after 3 h treatment and apoptotic cell death after 24 h showing time dependence in its mechanisms of action. Killer toxin extracts were active at oenological conditions, confirming their potential use as a biocontrol tool in winemaking.
Transceiver Multiplexers TD-1288( )/GRC and TD-1289( )(V)/GRC.

DTIC Science & Technology

1982-02-01

TRASITCAS TD-1289( )iV)1/GRC C.76 IR BANPAS FLER TERMINATION UNIT CU26()/GRC] G -42 RC MX-10080t )/GRC F’igure l-l. X1liF’ MultipleXer amily Tree. F1- CU-2266...the equations become: Y G o t Q 1Q+/Qu C o s 0 = j2 + Q QU L° l~ Qu I+j L=010 log 4 + j 2 Qt The passband loss expression may be simplified to read: 4...a character istic impedance of 50 oims. The linle len,_tli was 16i.5 inches and was tet oiinated inl a -ohio If load. The tap pointt was nojusted to g
Dissociative excitation of the N(+)(5S) state by electron impact on N2 - Excitation function and quenching

NASA Technical Reports Server (NTRS)

Erdman, P. W.; Zipf, E. C.

1986-01-01

Metastable N(+)(5S) ions were produced in the laboratory by dissociative excitation of N2 with energetic electrons. The resulting radiative decay of the N(+)(5S) state was observed with sufficient resolution to completely resolve the doublet from the nearby N2 molecular radiation. The excitation function was measured from threshold to 500 eV. The cross section peaks at a high electron energy and also exhibits a high threshold energy both of which are typical of dissociative excitation-ionization processes. This finding complicates the explanation of electron impact on N2 as the mechanism for the source of the 2145 A 'auroral mystery feature' by further increasing the required peak cross section. It is suggested that the apparent N(+)(5S) quenching in auroras may be an artifact due to the softening of the electron energy spectrum in the auroral E region.
Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations

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

Webster, R., E-mail: ross.webster07@imperial.ac.uk; Harrison, N. M.; Bernasconi, L.

2015-06-07

We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features ofmore » the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green’s function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional c{sub HF} and show that there exists one value of c{sub HF} (∼0.32) that reproduces at least semi-quantitatively the optical gap of this material.« less
TD-1792 versus Vancomycin for Treatment of Complicated Skin and Skin Structure Infections

PubMed Central

Potgieter, Peter D.; Li, Yu-Ping; Barriere, Steven L.; Churukian, Allan; Kingsley, Jeff; Corey, G. Ralph

2012-01-01

TD-1792 is a first-in-class glycopeptide-cephalosporin heterodimer that exhibits bactericidal activity against Gram-positive pathogens. We conducted a randomized, double-blind, active-control, phase II trial in patients with complicated skin and skin structure infections caused by suspected or confirmed Gram-positive organisms. Patients 18 to 65 years old were randomized to receive 7 to 14 days of either TD-1792 (2 mg/kg of body weight intravenously [i.v.] every 24 h [q24h]) or vancomycin (1 g i.v. q12h, with dosage regimens adjusted per site-specific procedures). A total of 197 patients were randomized and received at least one dose of study medication. Rates of clinical success at the test-of-cure evaluation were similar in all analysis populations. Among 170 clinically evaluable patients, cure rates were 91.7% and 90.7% in the TD-1792 and vancomycin groups, respectively (95% confidence interval [CI] of −7.9 to 9.7 for the difference). In microbiologically evaluable patients with methicillin-resistant Staphylococcus aureus at baseline (n = 75), cure rates were 94.7% in the TD-1792 group and 91.9% in the vancomycin group. Microbiological eradication of Gram-positive pathogens (n = 126) was achieved in 93.7% and 92.1% of patients in the TD-1792 and vancomycin groups, respectively. Seven patients were discontinued from study medication due to an adverse event (AE): 2 and 5 in the TD-1792 and vancomycin groups, respectively. AEs were of similar types and severities between the two groups, other than pruritus, which was more common in patients who received vancomycin. No patients in the TD-1792 group experienced a serious AE. This study supports further clinical development of TD-1792 in patients with Gram-positive infection. PMID:22869571
The Importance of Short- and Long-Range Exchange on Various Excited State Properties of DNA Monomers, Stacked Complexes, and Watson-Crick Pairs.

PubMed

Raeber, Alexandra E; Wong, Bryan M

2015-05-12

We present a detailed analysis of several time-dependent DFT (TD-DFT) methods, including conventional hybrid functionals and two types of nonempirically tuned range-separated functionals, for predicting a diverse set of electronic excitations in DNA nucleobase monomers and dimers. This large and extensive set of excitations comprises a total of 50 different transitions (for each tested DFT functional) that includes several n → π and π → π* valence excitations, long-range charge-transfer excitations, and extended Rydberg transitions (complete with benchmark calculations from high-level EOM-CCSD(T) methods). The presence of localized valence excitations as well as extreme long-range charge-transfer excitations in these systems poses a serious challenge for TD-DFT methods that allows us to assess the importance of both short- and long-range exchange contributions for simultaneously predicting all of these various transitions. In particular, we find that functionals that do not have both short- and full long-range exchange components are unable to predict the different types of nucleobase excitations with the same accuracy. Most importantly, the current study highlights the importance of both short-range exchange and a nonempirically tuned contribution of long-range exchange for accurately predicting the diverse excitations in these challenging nucleobase systems.
Excitation energies from range-separated time-dependent density and density matrix functional theory.

PubMed

Pernal, Katarzyna

2012-05-14

Time-dependent density functional theory (TD-DFT) in the adiabatic formulation exhibits known failures when applied to predicting excitation energies. One of them is the lack of the doubly excited configurations. On the other hand, the time-dependent theory based on a one-electron reduced density matrix functional (time-dependent density matrix functional theory, TD-DMFT) has proven accurate in determining single and double excitations of H(2) molecule if the exact functional is employed in the adiabatic approximation. We propose a new approach for computing excited state energies that relies on functionals of electron density and one-electron reduced density matrix, where the latter is applied in the long-range region of electron-electron interactions. A similar approach has been recently successfully employed in predicting ground state potential energy curves of diatomic molecules even in the dissociation limit, where static correlation effects are dominating. In the paper, a time-dependent functional theory based on the range-separation of electronic interaction operator is rigorously formulated. To turn the approach into a practical scheme the adiabatic approximation is proposed for the short- and long-range components of the coupling matrix present in the linear response equations. In the end, the problem of finding excitation energies is turned into an eigenproblem for a symmetric matrix. Assignment of obtained excitations is discussed and it is shown how to identify double excitations from the analysis of approximate transition density matrix elements. The proposed method used with the short-range local density approximation (srLDA) and the long-range Buijse-Baerends density matrix functional (lrBB) is applied to H(2) molecule (at equilibrium geometry and in the dissociation limit) and to Be atom. The method accounts for double excitations in the investigated systems but, unfortunately, the accuracy of some of them is poor. The quality of the other
Singlet-triplet splittings from the virial theorem and single-particle excitation energies

NASA Astrophysics Data System (ADS)

Becke, Axel D.

2018-01-01

The zeroth-order (uncorrelated) singlet-triplet energy difference in single-particle excited configurations is 2Kif, where Kif is the Coulomb self-energy of the product of the transition orbitals. Here we present a non-empirical, virial-theorem argument that the correlated singlet-triplet energy difference should be half of this, namely, Kif. This incredibly simple result gives vertical HOMO-LUMO excitation energies in small-molecule benchmarks as good as the popular TD-B3LYP time-dependent approach to excited states. For linear acenes and nonlinear polycyclic aromatic hydrocarbons, the performance is significantly better than TD-B3LYP. In addition to the virial theorem, the derivation borrows intuitive pair-density concepts from density-functional theory.
Synthesis, crystal structure and DFT studies of a dual fluorescent ketamine: Structural changes in the ground and excited states

NASA Astrophysics Data System (ADS)

Latha, V.; Balakrishnan, C.; Neelakantan, M. A.

2015-07-01

A fluorescent probe 2Z,2‧Z-3,3‧-(4,4‧-methylenebis(4,1-phenylene) bis(azanediyl))bis (1,3-diphenylprop-2-en-1-one) (L) was synthesized and characterized by IR, 1H NMR, ESI-mass, UV-visible and fluorescence spectral techniques. The single crystal analysis illustrates the existence of L in ketamine form. The crystal structure is stabilized by intramolecular and intermolecular hydrogen bonding. The thermal stability of L was studied by TG analysis. The fluorescence spectrum of L shows dual emission, and is due to excited state intramolecular proton transfer (ESIPT) process. This is supported by the high Stokes shift value. Electronic structure calculations of L in the ground and excited state have been carried out using DFT and TD-DFT at B3LYP/6-31G (d,p) level, respectively. The vibrational spectrum was computed at this level and compared with experimental values. Major orbital contributions for the electronic transitions were assigned with the help of TD-DFT. The changes in the Mulliken charge, bond lengths and bond angles between the ground and excited states of the tautomers demonstrate that twisted intramolecular charge transfer (TICT) process occurs along with ESIPT in the excited state.
Broadband sensitized white light emission of g-C{sub 3}N{sub 4}/Y{sub 2}MoO{sub 6}:Eu{sup 3+} composite phosphor under near ultraviolet excitation

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

Han, Bing, E-mail: hanbing@zzuli.edu.cn; Xue, Yongfei; Li, Pengju

2015-12-15

The g-C{sub 3}N{sub 4}/Y{sub 2}MoO{sub 6}:Eu{sup 3+} composite phosphors were synthesized and characterized by X-ray diffraction, Fourier transform-infrared spectroscopy, ultraviolet visible diffuse reflection spectra, photoluminescence spectra and luminescence decay curves. Under the excitation of 360 nm near ultraviolet light, these composite phosphors show tunable emission from blue to red region, in which white light emission can be obtained in term of appropriate quality proportion of Y{sub 2}MoO{sub 6}:Eu{sup 3+} relative to g-C{sub 3}N{sub 4}/Y{sub 2}MoO{sub 6}:Eu{sup 3+}. In addition, the emission color can be also dependent on the excitation wavelength in g-C{sub 3}N{sub 4}/Y{sub 2}MoO{sub 6}:Eu{sup 3+} composite phosphor. -more » Graphical abstract: Under the excitation of 360 nm near ultraviolet light, the g-C{sub 3}N{sub 4}/Y{sub 2}MoO{sub 6}:Eu{sup 3+} composite phosphors show tunable emission from blue to red region, in which white light emission can be obtained. - Highlights: • The g-C3N4/Y2MoO6:Eu{sup 3+} composite phosphors were synthesized and characterized. • White light emission was realized in the g-C3N4/Y2MoO6:Eu{sup 3+} composites under UV excitation. • A novel idea to realize the broadband sensitized white light emission in phosphors was provided.« less
Interdiffusion in the Ni/TD-NiCr and Cr/TD-NiCr systems

NASA Technical Reports Server (NTRS)

Pawar, A. V.; Tenney, D. R.

1974-01-01

The diffusion of Ni and Cr into TD-NiCr has been studied over the 900 to 1100 C temperature range. The diffusion couples were prepared by electroplating Cr and Ni on polished TD-NiCr wafers. Concentration profiles produced as a result of isothermal diffusion at 905, 1000, and 1100 C were determined by electron microprobe analysis. The Boltzmann-Matano analysis was used to determine concentration-dependent diffusion coefficients which were found to compare favorably with previously reported values. These data suggest that 2 vol % ThO2 distribution has no appreciable effect on the rates of diffusion in TD-NiCr with a large grain size. This supports the view that an inert dispersoid in an alloy matrix will not in itself lead to enhanced diffusion unless a short-circuit diffusion structure is stabilized.
A G protein-coupled receptor (GPCR) in red: live cell imaging of the kappa opioid receptor-tdTomato fusion protein (KOPR-tdT) in neuronal cells

PubMed Central

Huang, Peng; Chiu, Yi-Ting; Chen, Chongguang; Wang, Yujun; Liu-Chen, Lee-Yuan

2013-01-01

Introduction In contrast to green fluorescent protein and variants (GFPs), red fluorescent proteins (RFPs) have rarely been employed for generation of GPCR fusion proteins, likely because of formation of aggregates and cell toxicity of some RFPs. Among all the RFPs available, tdTomato (tdT), one of the non-aggregating RFP, has the highest brightness score (about 3 times that of eGFP) and unsurpassed photostability. Methods We fused tdT to the KOPR C-terminus. The KOPR-tdT cDNA construct was transfected into Neuro2A mouse neuroblastoma cell line (Neuro2A cells) and rat cortical primary neurons for characterization of pharmacological properties and imaging studies on KOPR trafficking. Results KOPR-tdT retained KOPR properties (cell surface expression, ligand binding, agonist-induced signaling and internalization) when expressed in Neuro2A cells and rat primary cortical neurons. Live cell imaging of KOPR-tdT enables visualization of time course of agonist-induced internalization of KOPR in real time for 60 min, without photobleaching and apparent cell toxicity. U50,488H-induced KOPR internalization occurred as early as 4 min and plateaued at about 30 min. A unique pattern of internalized KOPR in processes of primary neurons was induced by U50,488H. Discussion tdT is an alternative to, or even a better tool than, GFPs for fusing to GPCR for trafficking studies, because tdT has higher brightness and thus better resolution and less photobleaching problems due to reduced laser power used. It also has advantages associated with its longer-wavelength emission including spectral separation from autofluorescence and GFPs, reduced cell toxicity the laser may impose, and greater tissue penetration. These advantages of tdT over GPFs may be critical for live cell imaging studies of GPCRs in vitro and for studying GPCRs in vivo because of their low abundance. PMID:23856011
Photoinduced relaxation dynamics of nitrogen-capped silicon nanoclusters: a TD-DFT study

NASA Astrophysics Data System (ADS)

Liu, Xiang-Yang; Xie, Xiao-Ying; Fang, Wei-Hai; Cui, Ganglong

2018-04-01

Herein we have developed and implemented a TD-DFT-based surface-hopping dynamics simulation method with a recently proposed numerical algorithm capable of efficiently computing nonadiabatic couplings, a semiclassical spectrum simulation method, and an excited-state character analysis method based on one-electron transition density matrix. With the use of these developed methods, we have studied the spectroscopic properties, excited-state characters, and photoinduced relaxation dynamics of three silicon nanoclusters capped with different chromophores (Cl@SiQD, Car@SiQD, Azo@SiQD). Spectroscopically, the main absorption peak is visibly red-shifted from Cl@SiQD via Car@SiQD to Azo@SiQD. In contrast to Cl@SiQD and Car@SiQD, there are two peaks observed in Azo@SiQD. Mechanistically, the excited-state relaxation to the lowest S1 excited singlet state is ultrafast in Cl@SiQD, which is less than 190 fs and without involving excited-state trapping. In comparison, there are clear excited-state trappings in Car@SiQD and Azo@SiQD. In the former, the S2 state is trapped more than 300 fs; in the latter, the S3 excited-state trapping is more than 615 fs. These results demonstrate that the interfacial interaction has significant influences on the spectroscopic properties and excited-state relaxation dynamics. The knowledge gained in this work could be helpful for the design of silicon nanoclusters with better photoluminescence performance.
Tight-binding approximations to time-dependent density functional theory — A fast approach for the calculation of electronically excited states

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

Rüger, Robert, E-mail: rueger@scm.com; Department of Theoretical Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam; Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Linnéstr. 2, 04103 Leipzig

2016-05-14

We propose a new method of calculating electronically excited states that combines a density functional theory based ground state calculation with a linear response treatment that employs approximations used in the time-dependent density functional based tight binding (TD-DFTB) approach. The new method termed time-dependent density functional theory TD-DFT+TB does not rely on the DFTB parametrization and is therefore applicable to systems involving all combinations of elements. We show that the new method yields UV/Vis absorption spectra that are in excellent agreement with computationally much more expensive TD-DFT calculations. Errors in vertical excitation energies are reduced by a factor of twomore » compared to TD-DFTB.« less
The energy structure and decay channels of the 4p6-shell excited states in Sr

NASA Astrophysics Data System (ADS)

Kupliauskienė, A.; Kerevičius, G.; Borovik, V.; Shafranyosh, I.; Borovik, A.

2017-11-01

The ejected-electron spectra arising from the decay of the 4p{}5{{nln}}{\\prime }{l}{\\prime }{n}{\\prime\\prime }{l}{\\prime\\prime } autoionizing states in Sr atoms have been studied precisely at the incident-electron energies close to excitation and ionization thresholds of the 4{{{p}}}6 subshell. The excitation behaviors for 58 lines observed between 12 and 21 eV ejected-electron kinetic energy have been investigated. Also, the ab initio calculations of excitation energies, autoionization probabilities and electron-impact excitation cross sections of the states 4p{}5{{nln}}{\\prime }{l}{\\prime }{n}{\\prime\\prime }{l}{\\prime\\prime } (nl = 4d, 5s, 5p; {n}{\\prime }{l}{\\prime } = 4d, 5s, 5p; {n}{\\prime\\prime }{l}{\\prime\\prime } = 5s, 6s, 7s, 8s, 9s, 5p, 6p, 5d, 6d, 7d, 8d, 4f, 5g) have been performed by employing the large-scale configuration-interaction method in the basis of the solutions of Dirac-Fock-Slater equations. The obtained experimental and theoretical data have been used for the accurate identification of the 60 lines in ejected-electron spectra and the 68 lines observed earlier in photoabsorption spectra. The excitation and decay processes for 105 classified states in the 4p55s{}2{nl}, 4p54d{}2{nl} and 4p55s{{nln}}{\\prime }{l}{\\prime } configurations have been considered in detail. In particular, most of the states lying below the ionization threshold of the 4p6 subshell at 26.92 eV possess up to four decay channels with formation of Sr+ in 5s{}1/2, 4d{}3/{2,5/2} and 5p{}1/{2,3/2} states. Two-step autoionization and two-electron Auger transitions with formation of Sr2+ in the 4p6 {}1{{{S}}}0 ground state are the main decay paths for high-lying autoionizing states. The excitation threshold of the 4{{{p}}}6 subshell in Sr has been established at 20.98 ± 0.05 eV.
Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

PubMed

Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

2016-04-21

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.
Experimental and TD-DFT study of optical absorption of six explosive molecules: RDX, HMX, PETN, TNT, TATP, and HMTD.

PubMed

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

2013-07-25

Time dependent density function theory (TD-DFT) has been utilized to calculate the excitation energies and oscillator strengths of six common explosives: RDX (1,3,5-trinitroperhydro-1,3,5-triazine), β-HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), TATP (triacetone triperoxide), HMTD (hexamethylene triperoxide diamine), TNT (2,4,6-trinitrotoluene), and PETN (pentaerythritol tetranitrate). The results were compared to experimental UV-vis absorption spectra collected in acetonitrile. Four computational methods were tested including: B3LYP, CAM-B3LYP, ωB97XD, and PBE0. PBE0 outperforms the other methods tested. Basis set effects on the electronic energies and oscillator strengths were evaluated with 6-31G(d), 6-31+G(d), 6-31+G(d,p), and 6-311+G(d,p). The minimal basis set required was 6-31+G(d); however, additional calculations were performed with 6-311+G(d,p). For each molecule studied, the natural transition orbitals (NTOs) were reported for the most prominent singlet excitations. The TD-DFT results have been combined with the IPv calculated by CBS-QB3 to construct energy level diagrams for the six compounds. The results suggest optimization approaches for fluorescence based detection methods for these explosives by guiding materials selections for optimal band alignment between fluorescent probe and explosive analyte. Also, the role of the TNT Meisenheimer complex formation and the resulting electronic structure thereof on of the quenching mechanism of II-VI semiconductors is discussed.

Hydrogen bond strengthening between o-nitroaniline and formaldehyde in electronic excited states: A theoretical study

NASA Astrophysics Data System (ADS)

Yang, Juan; Li, An Yong

2018-06-01

To study the hydrogen bonds upon photoexcited, the time dependent density function method (TD DFT) was performed to investigate the excited state hydrogen bond properties of between o-nitroaniline (ONA) and formaldehyde (CH2O). The optimized structures of the complex and the monomers both in the ground state and the electronically excited states are calculated using DFT and TD DFT method respectively. Quantum chemical calculations of the electronic and vibrational absorption spectra are also carried out by TD DFT method at the different level. The complex ONA⋯CH2O forms the intramolecular hydrogen bond and intermolecular hydrogen bonds. Since the strength of hydrogen bonds can be measured by studying the vibrational absorption spectra of the characteristic groups on the hydrogen bonding acceptor and donor, it evidently confirms that the hydrogen bonds is strengthened in the S1/S2/T1 excited states upon photoexcitation. As a result, the hydrogen bonds cause that the CH stretch frequency of the proton donor CH2O has a blue shift, and the electron excitations leads to a frequency red shift of Ndbnd O and Nsbnd H stretch modes in the o-nitroaniline(ONA) and a small frequency blue shift of CH stretch mode in the formaldehyde(CH2O) in the S1 and S2 excited states. The excited states S1, S2 and T1 are locally excited states where only the ONA moiety is excited, but the CH2O moiety remains in its ground state.
Preoptimised VB: a fast method for the ground and excited states of ionic clusters I. Localised preoptimisation for (ArCO) +, (ArN 2) + and N 4+

NASA Astrophysics Data System (ADS)

Langenberg, J. H.; Bucur, I. B.; Archirel, P.

1997-09-01

We show that in the simple case of van der Waals ionic clusters, the optimisation of orbitals within VB can be easily simulated with the help of pseudopotentials. The procedure yields the ground and the first excited states of the cluster simultaneously. This makes the calculation of potential energy surfaces for tri- and tetraatomic clusters possible, with very acceptable computation times. We give potential curves for (ArCO) +, (ArN 2) + and N 4+. An application to the simulation of the SCF method is shown for Na +H 2O.
Development and evaluation of the TD97 measles virus vaccine

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

Suzuki, K.; Morita, M.; Katoh, M.

1990-11-01

The TD97 strain vaccine virus was prepared from the Tanabe strain measles virus by low-temperature passages in primary cell cultures and ultraviolet (UV) mutagenesis. The TD97 strain exhibited the following characteristics: highly temperature sensitive, neither multiplying nor forming any plaques at 40 degrees C in Vero cells; genetically stable, maintaining high temperature sensitivity after ten successive passages in CE cells at 30 degrees C or 35 degrees C; and M proteins of this virus about 1 KD slower in mobility in SDS-PAGE than that of the Tanabe strain. The TD97 strain was further confirmed to be attenuated by an inoculationmore » test into primate brain. In field trials, 752 healthy children were inoculated with a live virus vaccine prepared with this strain, and the following results were obtained: the seroconversion rate was 97% (517/533), and the average HI antibody titer was 2(5.2). An antibody-increasing effect was also observed in children who were initially seropositive. In children who seroconverted, the rates of fever were 15.7% (55/351) for 37.5 degrees C or higher and 4.0% (14/351) for 39 degrees C or higher. The rash rate was 7.7% (27/351), and the incidence of local reaction was 5.4% (19/351). The TD97 strain is thus considered to be suitable in use for an attenuated measles vaccine.« less
Magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs 2CuBr 4

DOE PAGES

Zvyagin, S. A.; Ozerov, M.; Kamenskyi, D.; ...

2015-11-27

We present on high- field electron spin resonance (ESR) studies of magnetic excitations in the spin- 1/2 triangular-lattice antiferromagnet Cs 2CuBr 4. Frequency- field diagrams of ESR excitations are measured for different orientations of magnetic fields up to 25 T. We show that the substantial zero- field energy gap, Δ ≈ 9.5 K, observed in the low-temperature excitation spectrum of Cs 2CuBr 4 [Zvyagin et al:, Phys. Rev. Lett. 112, 077206 (2014)], is present well above T N. Noticeably, the transition into the long-range magnetically ordered phase does not significantly affect the size of the gap, suggesting that even belowmore » T N the high-energy spin dynamics in Cs 2CuBr 4 is determined by short-range-order spin correlations. The experimental data are compared with results of model spin-wave-theory calculations for spin-1/2 triangle-lattice antiferromagnet.« less
Role of excited N2 in the production of nitric oxide

NASA Astrophysics Data System (ADS)

Campbell, L.; Cartwright, D. C.; Brunger, M. J.

2007-08-01

Excited N2 plays a role in a number of atmospheric processes, including auroral and dayglow emissions, chemical reactions, recombination of free electrons, and the production of nitric oxide. Electron impact excitation of N2 is followed by radiative decay through a series of excited states, contributing to auroral and dayglow emissions. These processes are intertwined with various chemical reactions and collisional quenching involving the excited and ground state vibrational levels. Statistical equilibrium and time step atmospheric models are used to predict N2 excited state densities and emissions (as a test against previous models and measurements) and to investigate the role of excited nitrogen in the production of nitric oxide. These calculations predict that inclusion of the reaction N2[A3Σu +] + O, to generate NO, produces an increase by a factor of up to three in the calculated NO density at some altitudes.
Cyclic creep and fatigue of TD-NiCr (thoria-dispersion-strengthened nickel-chromium), TD-Ni, and NiCr sheet at 1200 C

NASA Technical Reports Server (NTRS)

Hirschberg, M. H.; Spera, D. A.; Klima, S. J.

1972-01-01

The resistance of thin TD-NiCr sheet to cyclic deformation was compared with that of TD-Ni and a conventional nickel-chromium alloy. Strains were determined by a calibration technique which combines room-temperature strain gage and deflection measurements with high-temperature deflection measurements. Analyses of the cyclic tests using measured tensile and creep-rupture data indicated that the TD-NiCr and NiCr alloy specimens failed by a cyclic creep mechanism. The TD-Ni specimens, on the other hand, failed by a fatigue mechanism.
Characterization of Thermophilic Halotolerant Aeribacillus pallidus TD1 from Tao Dam Hot Spring, Thailand

PubMed Central

Yasawong, Montri; Areekit, Supatra; Pakpitchareon, Arda; Santiwatanakul, Somchai; Chansiri, Kosum

2011-01-01

The bacterial strain TD1 was isolated from Tao Dam hot spring in Thailand. Strain TD1 was Gram positive, rod-shaped, aerobic, motile, and endospore forming. The cell was 2.0–40 μm in length and about 0.4 μm in diameter. The optimum growth occurred at 55–60 °C and at pH 7–8. Strain TD1 was able to grow on medium containing up to 10% NaCl. The DNA G+C content was 38.9 mol%. The cellular fatty acid content was mainly C16:0, which comprised 25.04% of the total amount of cellular fatty acid. 16S rDNA showed 99% identity to Aeribacillus pallidus DSM 3670T. Bayesian tree analysis strongly supported the idea that strain TD1 is affiliated with genus Aeribacillus, as Aeribacillus pallidus strain TD1. Although the 16S rDNA of A. pallidus strain TD1 is similar to that of A. pallidus DSM 3670T, some physiological properties and the cellular fatty acid profiles differ significantly. A. pallidus strain TD1 can produce extracellular pectate lyase, which has not been reported elsewhere for other bacterial strains in the genus Aeribacillus. A. pallidus strain TD1 may be a good candidate as a pectate lyase producer, which may have useful industrial applications. PMID:21954359
Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

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

Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less
Hybrid excitations due to crystal field, spin-orbit coupling, and spin waves in LiFePO 4

DOE PAGES

Yiu, Yuen; Le, Manh Duc; Toft-Peterson, Rasmus; ...

2017-03-09

Here, we report on the spin waves and crystal field excitations in single crystal LiFePO 4 by inelastic neutron scattering over a wide range of temperatures, below and above the antiferromagnetic transition of this system. In particular, we find extra excitations below T N = 50 K that are nearly dispersionless and are most intense around magnetic zone centers. Furthermore, we show that these excitations correspond to transitions between thermally occupied excited states of Fe 2 + due to splitting of the S = 2 levels that arise from the crystal field and spin-orbit interactions. These excitations are further amplifiedmore » by the highly distorted nature of the oxygen octahedron surrounding the iron atoms. Above T N , magnetic fluctuations are observed up to at least 720 K, with an additional inelastic excitation around 4 meV, which we attribute to single-ion effects, as its intensity weakens slightly at 720 K compared to 100 K, which is consistent with the calculated cross sections using a single-ion model. This theoretical analysis, using the MF-RPA model, provides both detailed spectra of the Fe d shell and estimates of the average ordered magnetic moment and T N . By applying the MF-RPA model to a number of existing spin-wave results from other Li M PO 4 ( M = Mn , Co, and Ni), we are able to obtain reasonable predictions for the moment sizes and transition temperatures.« less
Evaluating excited state atomic polarizabilities of chromophores.

PubMed

Heid, Esther; Hunt, Patricia A; Schröder, Christian

2018-03-28

Ground and excited state dipoles and polarizabilities of the chromophores N-methyl-6-oxyquinolinium betaine (MQ) and coumarin 153 (C153) in solution have been evaluated using time-dependent density functional theory (TD-DFT). A method for determining the atomic polarizabilities has been developed; the molecular dipole has been decomposed into atomic charge transfer and polarizability terms, and variation in the presence of an electric field has been used to evaluate atomic polarizabilities. On excitation, MQ undergoes very site-specific changes in polarizability while C153 shows significantly less variation. We also conclude that MQ cannot be adequately described by standard atomic polarizabilities based on atomic number and hybridization state. Changes in the molecular polarizability of MQ (on excitation) are not representative of the local site-specific changes in atomic polarizability, thus the overall molecular polarizability ratio does not provide a good approximation for local atom-specific polarizability changes on excitation. Accurate excited state force fields are needed for computer simulation of solvation dynamics. The chromophores considered in this study are often used as molecular probes. The methods and data reported here can be used for the construction of polarizable ground and excited state force fields. Atomic and molecular polarizabilities (ground and excited states) have been evaluated over a range of functionals and basis sets. Different mechanisms for including solvation effects have been examined; using a polarizable continuum model, explicit solvation and via sampling of clusters extracted from a MD simulation. A range of different solvents have also been considered.
Laser excitation of the n =3 level of positronium for antihydrogen production

NASA Astrophysics Data System (ADS)

Aghion, S.; Amsler, C.; Ariga, A.; Ariga, T.; Bonomi, G.; Bräunig, P.; Bremer, J.; Brusa, R. S.; Cabaret, L.; Caccia, M.; Caravita, R.; Castelli, F.; Cerchiari, G.; Chlouba, K.; Cialdi, S.; Comparat, D.; Consolati, G.; Demetrio, A.; Di Noto, L.; Doser, M.; Dudarev, A.; Ereditato, A.; Evans, C.; Ferragut, R.; Fesel, J.; Fontana, A.; Forslund, O. K.; Gerber, S.; Giammarchi, M.; Gligorova, A.; Gninenko, S.; Guatieri, F.; Haider, S.; Holmestad, H.; Huse, T.; Jernelv, I. L.; Jordan, E.; Kellerbauer, A.; Kimura, M.; Koettig, T.; Krasnicky, D.; Lagomarsino, V.; Lansonneur, P.; Lebrun, P.; Lehner, S.; Liberadzka, J.; Malbrunot, C.; Mariazzi, S.; Marx, L.; Matveev, V.; Mazzotta, Z.; Nebbia, G.; Nedelec, P.; Oberthaler, M.; Pacifico, N.; Pagano, D.; Penasa, L.; Petracek, V.; Pistillo, C.; Prelz, F.; Prevedelli, M.; Ravelli, L.; Resch, L.; Rienäcker, B.; Røhne, O. M.; Rotondi, A.; Sacerdoti, M.; Sandaker, H.; Santoro, R.; Scampoli, P.; Smestad, L.; Sorrentino, F.; Spacek, M.; Storey, J.; Strojek, I. M.; Testera, G.; Tietje, I.; Vamosi, S.; Widmann, E.; Yzombard, P.; Zmeskal, J.; Zurlo, N.; AEgIS Collaboration

2016-07-01

We demonstrate the laser excitation of the n =3 state of positronium (Ps) in vacuum. A combination of a specially designed pulsed slow positron beam and a high-efficiency converter target was used to produce Ps. Its annihilation was recorded by single-shot positronium annihilation lifetime spectroscopy. Pulsed laser excitation of the n =3 level at a wavelength λ ≈205 nm was monitored via Ps photoionization induced by a second intense laser pulse at λ =1064 nm. About 15% of the overall positronium emitted into vacuum was excited to n =3 and photoionized. Saturation of both the n =3 excitation and the following photoionization was observed and explained by a simple rate equation model. The positronium's transverse temperature was extracted by measuring the width of the Doppler-broadened absorption line. Moreover, excitation to Rydberg states n =15 and 16 using n =3 as the intermediate level was observed, giving an independent confirmation of excitation to the 3 3P state.
Emission mechanisms in Al-rich AlGaN/AlN quantum wells assessed by excitation power dependent photoluminescence spectroscopy

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

Iwata, Yoshiya; Banal, Ryan G.; Ichikawa, Shuhei

2015-02-21

The optical properties of Al-rich AlGaN/AlN quantum wells are assessed by excitation-power-dependent time-integrated (TI) and time-resolved (TR) photoluminescence (PL) measurements. Two excitation sources, an optical parametric oscillator and the 4th harmonics of a Ti:sapphire laser, realize a wide range of excited carrier densities between 10{sup 12} and 10{sup 21 }cm{sup −3}. The emission mechanisms change from an exciton to an electron-hole plasma as the excitation power increases. Accordingly, the PL decay time is drastically reduced, and the integrated PL intensities increase in the following order: linearly, super-linearly, linearly again, and sub-linearly. The observed results are well accounted for by rate equationsmore » that consider the saturation effect of non-radiative recombination processes. Using both TIPL and TRPL measurements allows the density of non-radiative recombination centers, the internal quantum efficiency, and the radiative recombination coefficient to be reliably extracted.« less
Excited states of neutral donor bound excitons in GaN

NASA Astrophysics Data System (ADS)

Callsen, G.; Kure, T.; Wagner, M. R.; Butté, R.; Grandjean, N.

2018-06-01

We investigate the excited states of a neutral donor bound exciton (D0X) in bulk GaN by means of high-resolution, polychromatic photoluminescence excitation (PLE) spectroscopy. The optically most prominent donor in our sample is silicon accompanied by only a minor contribution of oxygen—the key for an unambiguous assignment of excited states. Consequently, we can observe a multitude of Si0X-related excitation channels with linewidths down to 200 μeV. Two groups of excitation channels are identified, belonging either to rotational-vibrational or electronic excited states of the hole in the Si0X complex. Such identification is achieved by modeling the excited states based on the equations of motion for a Kratzer potential, taking into account the particularly large anisotropy of effective hole masses in GaN. Furthermore, several ground- and excited states of the exciton-polaritons and the dominant bound exciton are observed in the photoluminescence (PL) and PLE spectra, facilitating an estimate of the associated complex binding energies. Our data clearly show that great care must be taken if only PL spectra of D0X centers in GaN are analyzed. Every PL feature we observe at higher emission energies with regard to the Si0X ground state corresponds to an excited state. Hence, any unambiguous peak identification renders PLE spectra highly valuable, as important spectral features are obscured in common PL spectra. Here, GaN represents a particular case among the wide-bandgap, wurtzite semiconductors, as comparably low localization energies for common D0X centers are usually paired with large emission linewidths and the prominent optical signature of exciton-polaritons, making the sole analysis of PL spectra a challenging task.
Spectroscopic Study and Astronomical Detection of Vibrationally Excited n-PROPYL Cyanide

NASA Astrophysics Data System (ADS)

Müller, Holger S. P.; Wehres, Nadine; Wilkins, Olivia H.; Lewen, Frank; Schlemmer, Stephan; Walters, Adam; Vicente, Rémi; Liu, Delong; Garrod, Robin T.; Belloche, Arnaud; Menten, Karl M.

2016-06-01

We have obtained ALMA data of Sagittarius (Sgr for short) B2(N) between 84.0 and 114.4 GHz in its Early Science Cycles 0 and 1. We have focused our analyses on the northern, secondary hot molecular core Sgr B2(N2) because of the smaller line widths. The survey led to the first detection of a branched alkyl compound, iso-propyl cyanide, i-C_3H_7CN, in space besides the ˜2.5 times more abundant straight chain isomer n-propyl cyanide, a molecule which we had detected in our IRAM 30 m survey. We suspected to be able to detect n-propyl cyanide in vibrationally excited states in our ALMA data. We have recorded laboratory rotational spectra of this molecule in three large frequency regions and identified several excited vibrational states. The analyses of these spectra have focused on the 36 to 70 GHz and 89 to 127 GHz regions and on the four lowest excited vibrational states of both the lower lying gauche- and the slightly higher lying anti-conformer for which rotational constants had been published. We will present results of our laboratory spectroscopic investigations and will report on the detection of these states toward Sgr B2(N2). A. Belloche et al., Science 345 (2014) 1584. A. Belloche et al., A&A 499 (2009) 215. E. Hirota, J. Chem. Phys. 37 (1962) 2918.
Travellers' diarrhoea: Impact of TD definition and control group design on study results.

PubMed

Lääveri, Tinja; Pakkanen, Sari H; Kirveskari, Juha; Kantele, Anu

2018-02-02

Travellers' diarrhoea (TD) is a common health problem among visitors to the (sub)tropics. Much research deals with aetiology, prevention, and post-infection sequalae, yet the data may not allow comparisons due to incompatible definitions of TD and No TD control groups. The impact of defining TD and No TD control groups was explored by revisiting our recent data. We set up two TD groups: classical TD i.e. ≥3 loose or liquid stools/day and WHO TD (diarrhoea as defined by the WHO) i.e. any diarrhoea, and four No TD groups by TD definition and timing (no classical/WHO TD during travel, no ongoing classical/WHO TD). TD was recorded for 37% versus 65% of subjects when using classical versus WHO definitions, respectively; the proportions of the various pathogens proved similar. The strictest criterion for the No TD control group (no WHO TD during travel) yielded pathogens among 61% and the least strict (no ongoing classical TD) among 73% of the travellers; the differences were greatest for enteroaggregative Escherichia coli and Campylobacter. Definition of TD and control group design substantially impact on TD study results. The WHO definition yields more cases, but the pathogen selection is similar by both definitions. Design of the No TD control group was found critical: only those remaining asymptomatic throughout the journey should be included. Copyright © 2018 Elsevier Ltd. All rights reserved.
Identification of Excited States in the N=Z Nucleus 82Nb

NASA Astrophysics Data System (ADS)

Caceres, L. S.; Gorska, M.; Jungclaus, A.; Regan, P. H.; Garnsworthy, A. B.; Pietri, S.; Podolyak, Zs.; Rudolph, D.; Steer, S. J.; Grawe, H.; Balabanski, D. L.; Becker, F.; Bednarczyk, P.; Benzoni, G.; Blank, B.; Brandau, C.; Bruce, A. M.; Camera, F.; Catford, W. N.; Cullen, I. J.; Dombradi, Zs.; Doornenbal, P.; Estevez, E.; Geissel, H.; Gelletly, W.; Gerl, J.; Grebosz, J.; Heinz, A.; Hoischen, R.; Ilie, G.; Jolie, J.; Jones, G. A.; Kmiecik, M.; Kojouharov, I.; Kondev, F. G.; Kurtukian-Nieto, T.; Kurz, N.; Lalkowski, S.; Liu, L.; Maj, A.; Myalski, S.; Montes, F.; Pfuetzner, M.; Prokopowicz, W.; Saito, T.; Schaffner, H.; Schwertel, S.; Shizuma, T.; Simons, A. J.; Tashenov, S.; Walker, P. M.; Werner-Malento, E.; Wieland, O.; Wollersheim, H. J.

2007-04-01

Information on the first excited states in the N=Z=41 nucleus 82Nb sheds light on the competition of isospin T=0 and T=1 states in the A sim 80 region. The measurement was performed at the GSI laboratory using fragmentation of a 107Ag primary beam at 750 MeV/u on a 4 g/cm2 9Be target. The fragments were separated and identified unambiguously in the FRagment Separator. Three excited states were observed and the half-life estimate for the isomeric state was extracted. A tentative spin assignment based on the isobaric analogue states systematics in the Tz=1 nucleus 82Zr, and transition probabilities indicate T=1 character of the first two excited states, and T=0 for the isomeric state.
Highly selective "turn-on" fluorescent and colorimetric sensing of fluoride ion using 2-(2-hydroxyphenyl)-2,3-dihydroquinolin-4(1H)-one based on excited-state proton transfer.

PubMed

Kanagaraj, Kuppusamy; Pitchumani, Kasi

2014-01-01

A simple, highly selective and sensitive colorimetric system for the detection of fluoride ion in an aqueous medium has been developed using 2-(2-hydroxyphenyl)-2,3-dihydroquinolin-4(1H)-one. This system allows selective "turn-on" fluorescence detection of fluoride ion, which is found to be dependent upon guest basicity. An excited-state proton transfer is proposed to be the signaling mechanism, which is rationalized by DFT and TD-DFT calculations. The present sensor can also be applied to detect fluoride levels in real water samples. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Absence of Change in Total Daily Energy Expenditure (EE(sub TD)) in Young and Mature Rats During 14 Days of Hypergravity

NASA Technical Reports Server (NTRS)

Wade, C. E.; Moran, M. M.; Stein, T. P.; Hoban-Higgins, T. M.; Fuller, P.; Fuller, C. A.; Dalton, Bonnie P. (Technical Monitor)

1999-01-01

Effect of age on the response of EE(sub TD) to an increase in gravity was assessed in young (Y; 1.5 month old) and mature (M; 8 month old) Sprague-Dawley rats. Rats were implanted with transmitters to monitor activity, and metabolism was determined by the double labeled water technique. Daily food intake was measured. For each age, rats (n=8 per treatment) were exposed to centrifugation at 2G, or remained at 1G. There was a difference in EE(sub TD) between age groups, 182 plus or minus 11 and 143 plus or minus 5 kcal/kg/day in Y and M, respectively. This difference was attributed in part to a lower activity level in M animals, 48% of Y rats. After day 6 there was no effect on EE(sub TD) of exposure to 2G, or on food intake per 100g BW. Prior studies show a 20% increase in resting EE with hypergravity. In our study the level of activity was reduced to 41% of 1G in both age groups during 2G. For Y at 1G resting EE accounted for 78% of the EE(sub TD) and activity 22%, while at 2G resting EE was 96% of EE(sub TD) and activity 4%. M rats had similar changes. Independent of age, with exposure to hypergravity EE(sub TD) is maintained by behavioral changes.
Excitations in the quantum liquid 4He: A review

NASA Astrophysics Data System (ADS)

Glyde, H. R.

2018-01-01

Progress made in measuring and interpreting the elementary excitations of superfluid and normal liquid {\\hspace{0pt}}^4He in the past 25 years is reviewed. The goal is to bring up to date the data, calculations and our understanding of the excitations since the books and reviews of the early 1990s. Only bulk liquid {\\hspace{0pt}}^4He is considered. Reference to liquid {\\hspace{0pt}}^3He , mixtures, reduced dimensions (films and confined helium) is made where useful to enhance interpretation. The focus is on the excitations as measured by inelastic neutron scattering methods. The review covers the dynamical response of liquid {\\hspace{0pt}}^4He from the collective excitations at low energy and long wavelength (i.e. phonon-roton modes) to the single particle excitations at high energy from which the atomic momentum distribution and Bose-Einstein condensate fraction are determined. A goal is to show the interplay of these excitations with other spectacular properties such as superfluidity and the test of fundamental calculations of quantum liquids that is possible. The role of Bose-Einstein condensation in determining the nature of the \
Steric hindrance inhibits excited-state relaxation and lowers the extent of intramolecular charge transfer in two-photon absorbing dyes.

PubMed

Stewart, David J; Dalton, Matthew J; Long, Stephanie L; Kannan, Ramamurthi; Yu, Zhenning; Cooper, Thomas M; Haley, Joy E; Tan, Loon-Seng

2016-02-21

The two-photon absorbing dye AF240 [1, (7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)diphenylamine] is modified by adding bulky alkyl groups to the diphenylamino moiety. Three new compounds are synthesized which have ethyl groups in both ortho positions of each phenyl ring (2), t-butyl groups in one ortho position of each phenyl ring (3), and t-butyl groups in the para position of each phenyl ring (4). The dyes are examined in several aprotic solvents with varying polarity to observe the effects of the sterically hindering bulky groups on the ground and excited-state photophysical properties. While the ground state shows minimal solvent dependence, there is significant dependence on the fluorescence quantum yield and lifetime, as well as the excited-state energy levels. This effect is caused by the formation of an intramolecular charge-transfer (ICT) state, which is observed in the solvents more polar than n-hexane and supported by TD-DFT calculations. Electronic effects of ortho or para alkyl substitution should be similar, yet drastic differences are observed. A red shift in the fluorescence maximum is observed in 4 relative to 1, yet a blue shift occurs in 2 and 3 because the substituents at the sterically sensitive ortho-positions inhibit excited-state geometric relaxation and result in less ICT character than 1. Coupled with theoretical calculations, the data support a planar ICT (PICT) excited state where the diphenylamino nitrogen in an sp(2)-like geometry is integral with the plane containing the fluorene and benzothiazole moieties. Ultrafast transient absorption experiments show that ICT occurs rapidly (<150 fs) followed by geometric and solvent relaxation in ∼ 1-4 ps to form the PICT or solvent-stabilized ICT (SSICT) state. This relaxation is not observed in non-polar n-hexane because the solvent dependent ICT state energy lies higher than the locally-excited (LE) state. Finally, formation of a triplet state (T1) is only efficiently observed in n

Accurate simulation of geometry, singlet-singlet and triplet-singlet excitation of cyclometalated iridium(III) complex.

PubMed

Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Zhang, Hong-Xing; Cui, Tian

2014-03-01

In the current contribution, we present a critical study of the theoretical protocol used for the determination of the electronic spectra properties of luminescent cyclometalated iridium(III) complex, [Ir(III)(ppy)₂H₂dcbpy]⁺ (where, ppy = 2-phenylpyridine, H₂dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid), considered as a representative example of the various problems related to the prediction of electronic spectra of transition metal complex. The choice of the exchange-correlation functional is crucial for the validity of the conclusions that would be drawn from the numerical results. The influence of the exchange-correlation on geometry parameter and absorption/emission band, the role of solvent effects on time-dependent density function theory (TD-DFT) calculations, as well as the importance of the chosen proper procedure to optimize triplet excited geometry, have been thus examined in detail. From the obtained results, some general conclusions and guidelines are presented: i) PBE0 functional is the most accurate in prediction of ground state geometry; ii) the well-established B3LYP, B3P86, PBE0, and X3LYP have similar accuracy in calculation of absorption spectrum; and iii) the hybrid approach TD-DFT//CIS gives out excellent agreement in the evaluation of triplet excitation energy.
Long-range interactions of hydrogen atoms in excited states. III. n S -1 S interactions for n ≥3

NASA Astrophysics Data System (ADS)

Adhikari, C. M.; Debierre, V.; Jentschura, U. D.

2017-09-01

The long-range interaction of excited neutral atoms has a number of interesting and surprising properties such as the prevalence of long-range oscillatory tails and the emergence of numerically large van der Waals C6 coefficients. Furthermore, the energetically quasidegenerate n P states require special attention and lead to mathematical subtleties. Here we analyze the interaction of excited hydrogen atoms in n S states (3 ≤n ≤12 ) with ground-state hydrogen atoms and find that the C6 coefficients roughly grow with the fourth power of the principal quantum number and can reach values in excess of 240 000 (in atomic units) for states with n =12 . The nonretarded van der Waals result is relevant to the distance range R ≪a0/α , where a0 is the Bohr radius and α is the fine-structure constant. The Casimir-Polder range encompasses the interatomic distance range a0/α ≪R ≪ℏ c /L , where L is the Lamb shift energy. In this range, the contribution of quasidegenerate excited n P states remains nonretarded and competes with the 1 /R2 and 1 /R4 tails of the pole terms, which are generated by lower-lying m P states with 2 ≤m ≤n -1 , due to virtual resonant emission. The dominant pole terms are also analyzed in the Lamb shift range R ≫ℏ c /L . The familiar 1 /R7 asymptotics from the usual Casimir-Polder theory is found to be completely irrelevant for the analysis of excited-state interactions. The calculations are carried out to high precision using computer algebra in order to handle a large number of terms in intermediate steps of the calculation for highly excited states.
TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

NASA Astrophysics Data System (ADS)

Kozlowski, Pawel; Liu, Hui; Kornobis, Karina; Lodowski, Piotr; Jaworska, Maria

2013-12-01

Coenzyme B12 (AdoCbl) is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT) has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl) was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM). Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C) triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl). Furthermore, potential energy surfaces (PESs) obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer) and a σ bonding-ligand charge transfer (SBLCT) states.
Coulomb Excitation of the N = 50 nucleus 80Zn

NASA Astrophysics Data System (ADS)

van de Walle, J.; Aksouh, F.; Ames, F.; Behrens, T.; Bildstein, V.; Blazhev, A.; Cederkäll, J.; Clément, E.; Cocolios, T. E.; Davinson, T.; Delahaye, P.; Eberth, J.; Ekström, A.; Fedorov, D. V.; Fedosseev, V. N.; Fraile, L. M.; Franchoo, S.; Gernhauser, R.; Georgiev, G.; Habs, D.; Heyde, K.; Huber, G.; Huyse, M.; Ibrahim, F.; Ivanov, O.; Iwanicki, J.; Jolie, J.; Kester, O.; Köster, U.; Kröll, T.; Krücken, R.; Lauer, M.; Lisetskiy, A. F.; Lutter, R.; Marsh, B. A.; Mayet, P.; Niedermaier, O.; Nilsson, T.; Pantea, M.; Perru, O.; Raabe, R.; Reiter, P.; Sawicka, M.; Scheit, H.; Schrieder, G.; Schwalm, D.; Seliverstov, M. D.; Sieber, T.; Sletten, G.; Smirnova, N.; Stanoiu, M.; Stefanescu, I.; Thomas, J.-C.; Valiente-Dobón, J. J.; van Duppen, P.; Verney, D.; Voulot, D.; Warr, N.; Weisshaar, D.; Wenander, F.; Wolf, B. H.; Zielińska, M.

2008-05-01

Neutron rich Zinc isotopes, including the N = 50 nucleus 80Zn, were produced and post-accelerated at the Radioactive Ion Beam (RIB) facility REX-ISOLDE (CERN). Low-energy Coulomb excitation was induced on these isotopes after post-acceleration, yielding B(E2) strengths to the first excited 2+ states. For the first time, an excited state in 80Zn was observed and the 21+ state in 78Zn was established. The measured B(E2,21+-->01+) values are compared to two sets of large scale shell model calculations. Both calculations reproduce the observed B(E2) systematics for the full Zinc isotopic chain. The results for N = 50 isotones indicate a good N = 50 shell closure and a strong Z = 28 proton core polarization. The new results serve as benchmarks to establish theoretical models, predicting the nuclear properties of the doubly magic nucleus 78Ni.
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.
Gain and saturation energy measurements in low pressure longitudinally excited N 2-lasers

NASA Astrophysics Data System (ADS)

Ghoreyshi, S.; Rahimian, K.; Hariri, Akbar

2004-08-01

A flat-plate Blumlein circuit has been used for operating a low pressure longitudinally excited oscillator-amplifier N 2-laser at 14 kV input voltage (LE-LE type). For investigating the effect of the excitation length on the laser performances, various amplifiers made of glass tubes of different lengths ranging from 15.5 to 35 cm with 4 mm inner bore diameters have been used. The measurements have been carried out for the laser parameters: small signal gain, and saturation energy density; and the laser beam divergence. Details of our measurements are presented. The results of our measurements have also been compared with the reported values of laser parameters in TE-TEA and LE N 2-laser configurations.
Safety and immunogenicity of a single intramuscular dose of a tetanus-diphtheria toxoid (Td) vaccine (BR-TD-1001) in healthy Korean adult subjects.

PubMed

Hong, Taegon; Chung, Yong-Ju; Kim, Tae-Yeon; Kim, Ik-Hwan; Choe, Yong-Kyung; Lee, Jongtae; Jeon, Sangil; Han, Seunghoon; Yim, Dong-Seok

2015-01-01

BR-TD-1001 was developed as a booster for the immunity maintenance of diphtheria and tetanus. The aim of this study was to evaluate the safety and immunogenicity of BR-TD-1001 (test vaccine) in comparison with placebo and an active comparator in healthy Korean adults. A randomized, double-blind, placebo-controlled, active comparator, phase I clinical trial was conducted. Fifty subjects were randomly assigned to one of 3 treatment groups in a ratio of 2:2:1, and were administered a single intramuscular dose of test vaccine, active comparator, or placebo, respectively. All subjects were monitored for 4 weeks after injection. The antibody titers of the patients 2 and 4 weeks after vaccination were compared with the baseline. The frequencies of all adverse events including adverse drug reactions in the test group were not statistically different from those of the other treatment groups (P = 0.4974, 0.3061). No serious adverse event occurred, and no subject was withdrawn from the study for safety. The seroprotection rates against both tetanus and diphtheria at 4 weeks after vaccination were over 0.95. For anti-tetanus antibody, the geometric mean titer in the test group was significantly higher than those of the other groups (P = 0.0364, 0.0033). The geometric mean titer of anti-diphtheria antibody in the test group was significantly higher than the value of the placebo (P = 0.0347) while it was not for the value of the active comparator (P = 0.8484). In conclusion, BR-TD-1001 was safe, well-tolerated, and showed sufficient immunogenicity as a booster for diphtheria and tetanus.
Production of vibrationally excited N 2 by electron impact

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Cartwright, D. C.; Teubner, P. J. O.

2004-08-01

Energy transfer from electrons to neutral gases and ions is one of the dominant electron cooling processes in the ionosphere, and the role of vibrationally excited N 2 in this is particularly significant. We report here the results from a new calculation of electron energy transfer rates ( Q) for vibrational excitation of N 2, as a function of the electron temperature Te. The present study was motivated by the development of a new cross-section compilation for vibrational excitation processes in N 2 which supercedes those used in the earlier calculations of the electron energy transfer rates. We show that the energy dependence and magnitude of these cross sections, particularly in the region of the well-known 2Π g resonance in N 2, significantly affect the calculated values of Q. A detailed comparison between the current and previous calculated electron energy transfer rates is made and coefficients are provided so that these rates for transitions from level 0 to levels 1-10 can be calculated for electron temperatures less than 6000 K.
Quantum Scattering Study of Ro-Vibrational Excitations in N+N(sub 2) Collisions under Re-entry Conditions

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Stallcop, James R.; Dateo, Christopher E.; Schwenke, David W.; Huo, Winifred M.

2004-01-01

A three-dimensional time-dependent quantum dynamics approach using a recently developed ab initio potential energy surface is applied to study ro-vibrational excitation in N+N2 exchange scattering for collision energies in the range 2.1- 3.2 eV. State-to-state integral exchange cross sections are examined to determine the distribution of excited rotational states of N(sub 2). The results demonstrate that highly-excited rotational states are produced by exchange scattering and furthermore, that the maximum value of (Delta)j increases rapidly with increasing collision energies. Integral exchange cross sections and exchange rate constants for excitation to the lower (upsilon = 0-3) vibrational energy levels are presented as a function of the collision energy. Excited-vibrational-state distributions for temperatures at 2,000 K and 10,000 K are included.
Fluorescent excitation of Fe 2, Mn 2, Ti 2, N 1 lines by V 4, N 5, O 6: Emission lines in the spectra of symbiotic stars and Seyfert galaxies

NASA Technical Reports Server (NTRS)

Gilra, D. P.

1984-01-01

Analysis of the published IUE and ground based high resolution spectra of symbiotic stars, particularly RR Tel, shows that the dominant excitation mechanism of Fe II, Mn II, Ti II, and N I lines is the selective fluorescent excitation of some levels by the strong C IV, N V, and O VI emission lines. The same mechanism should work for the excitation of Fe II lines in the spectra of Seyfert galaxies and Q60's whose emission spectra are quite similar to those of symbiotic stars. The similarities and differences between the fluroescent excitation mechanism reported herein and the Bowen's mechanism is analyzed.
Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C{sub 2}H{sub 4}N{sub 4}O{sub 4})

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

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

Decomposition of the energetic material FOX-7 (1,1-diamino-2,2-dinitroethylene, C{sub 2}H{sub 4}N{sub 4}O{sub 4}) is investigated both theoretically and experimentally. The NO molecule is observed as an initial decomposition product subsequent to electronic excitation. The observed NO product is rotationally cold (<35 K) and vibrationally hot (2800 K). The initial decomposition mechanism is explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 2} FOX-7 can radiationlessly relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{submore » 1}/S{sub 0}){sub CI} conical intersections and undergo a nitro-nitrite isomerization to generate NO product on the S{sub 0} state. The theoretically predicted mechanism is consistent with the experimental results. As FOX-7 decomposes on the ground electronic state, thus, the vibrational energy of the NO product from FOX-7 is high. The observed rotational energy distribution for NO is consistent with the final transition state structure on the S{sub 0} state. Ground state FOX-7 decomposition agrees with previous work: the nitro-nitrite isomerization has the lowest average energy barrier, the C–NH{sub 2} bond cleavage is unlikely under the given excitation conditions, and HONO formation on the ground state surface is energy accessible but not the main process.« less
Exact PsTd invariant and PsTd symmetric breaking solutions, symmetry reductions and Bäcklund transformations for an AB-KdV system

NASA Astrophysics Data System (ADS)

Jia, Man; Lou, Sen Yue

2018-05-01

In natural and social science, many events happened at different space-times may be closely correlated. Two events, A (Alice) and B (Bob) are defined as correlated if one event is determined by another, say, B = f ˆ A for suitable f ˆ operators. A nonlocal AB-KdV system with shifted-parity (Ps, parity with a shift), delayed time reversal (Td, time reversal with a delay) symmetry where B =Ps ˆ Td ˆ A is constructed directly from the normal KdV equation to describe two-area physical event. The exact solutions of the AB-KdV system, including PsTd invariant and PsTd symmetric breaking solutions are shown by different methods. The PsTd invariant solution show that the event happened at A will happen also at B. These solutions, such as single soliton solutions, infinitely many singular soliton solutions, soliton-cnoidal wave interaction solutions, and symmetry reduction solutions etc., show the AB-KdV system possesses rich structures. Also, a special Bäcklund transformation related to residual symmetry is presented via the localization of the residual symmetry to find interaction solutions between the solitons and other types of the AB-KdV system.
Uplink scheduling and adjacent-channel coupling loss analysis for TD-LTE deployment.

PubMed

Yeo, Woon-Young; Moon, Sung Ho; Kim, Jae-Hoon

2014-01-01

TD-LTE, one of the two duplexing modes in LTE, operates in unpaired spectrum and has the advantages of TDD-based technologies. It is expected that TD-LTE will be more rapidly deployed in near future and most of WiMax operators will upgrade their networks to TD-LTE gradually. Before completely upgrading to TD-LTE, WiMax may coexist with TD-LTE in an adjacent frequency band. In addition, multiple TD-LTE operators may deploy their networks in adjacent bands. When more than one TDD network operates in adjacent frequency bands, severe interference may happen due to adjacent channel interference (ACI) and unsynchronized operations. In this paper, coexistence issues between TD-LTE and other systems are analyzed and coexistence requirements are provided. This paper has three research objectives. First, frame synchronization between TD-LTE and WiMax is discussed by investigating possible combinations of TD-LTE and WiMax configurations. Second, an uplink scheduling algorithm is proposed to utilize a leakage pattern of ACI in synchronized operations. Third, minimum requirements for coexistence in unsynchronized operations are analyzed by introducing a concept of adjacent-channel coupling loss. From the analysis and simulation results, we can see that coexistence of TD-LTE with other TDD systems is feasible if the two networks are synchronized. For the unsynchronized case, some special cell-site engineering techniques may be required to reduce the ACI.
Design and qualification of the SEU/TD Radiation Monitor chip

NASA Technical Reports Server (NTRS)

Buehler, Martin G.; Blaes, Brent R.; Soli, George A.; Zamani, Nasser; Hicks, Kenneth A.

1992-01-01

This report describes the design, fabrication, and testing of the Single-Event Upset/Total Dose (SEU/TD) Radiation Monitor chip. The Radiation Monitor is scheduled to fly on the Mid-Course Space Experiment Satellite (MSX). The Radiation Monitor chip consists of a custom-designed 4-bit SRAM for heavy ion detection and three MOSFET's for monitoring total dose. In addition the Radiation Monitor chip was tested along with three diagnostic chips: the processor monitor and the reliability and fault chips. These chips revealed the quality of the CMOS fabrication process. The SEU/TD Radiation Monitor chip had an initial functional yield of 94.6 percent. Forty-three (43) SEU SRAM's and 14 Total Dose MOSFET's passed the hermeticity and final electrical tests and were delivered to LL.
Uplink Scheduling and Adjacent-Channel Coupling Loss Analysis for TD-LTE Deployment

PubMed Central

Yeo, Woon-Young; Moon, Sung Ho

2014-01-01

TD-LTE, one of the two duplexing modes in LTE, operates in unpaired spectrum and has the advantages of TDD-based technologies. It is expected that TD-LTE will be more rapidly deployed in near future and most of WiMax operators will upgrade their networks to TD-LTE gradually. Before completely upgrading to TD-LTE, WiMax may coexist with TD-LTE in an adjacent frequency band. In addition, multiple TD-LTE operators may deploy their networks in adjacent bands. When more than one TDD network operates in adjacent frequency bands, severe interference may happen due to adjacent channel interference (ACI) and unsynchronized operations. In this paper, coexistence issues between TD-LTE and other systems are analyzed and coexistence requirements are provided. This paper has three research objectives. First, frame synchronization between TD-LTE and WiMax is discussed by investigating possible combinations of TD-LTE and WiMax configurations. Second, an uplink scheduling algorithm is proposed to utilize a leakage pattern of ACI in synchronized operations. Third, minimum requirements for coexistence in unsynchronized operations are analyzed by introducing a concept of adjacent-channel coupling loss. From the analysis and simulation results, we can see that coexistence of TD-LTE with other TDD systems is feasible if the two networks are synchronized. For the unsynchronized case, some special cell-site engineering techniques may be required to reduce the ACI. PMID:24707214
In vitro activities of the new semisynthetic glycopeptide telavancin (TD-6424), vancomycin, daptomycin, linezolid, and four comparator agents against anaerobic gram-positive species and Corynebacterium spp.

PubMed

Goldstein, Ellie J C; Citron, Diane M; Merriam, C Vreni; Warren, Yumi A; Tyrrell, Kerin L; Fernandez, Helen T

2004-06-01

Telavancin is a new semisynthetic glycopeptide anti-infective with multiple mechanisms of action, including inhibition of bacterial membrane phospholipid synthesis and inhibition of bacterial cell wall synthesis. We determined the in vitro activities of telavancin, vancomycin, daptomycin, linezolid, quinupristin-dalfopristin, imipenem, piperacillin-tazobactam, and ampicillin against 268 clinical isolates of anaerobic gram-positive organisms and 31 Corynebacterium strains using agar dilution methods according to National Committee for Clinical Laboratory Standards procedures. Plates with daptomycin were supplemented with Ca(2+) to 50 mg/liter. The MICs at which 90% of isolates tested were inhibited (MIC(90)s) for telavancin and vancomycin were as follows: Actinomyces spp. (n = 45), 0.25 and 1 microg/ml, respectively; Clostridium difficile (n = 14), 0.25 and 1 microg/ml, respectively; Clostridium ramosum (n = 16), 1 and 4 microg/ml, respectively; Clostridium innocuum (n = 15), 4 and 16 microg/ml, respectively; Clostridium clostridioforme (n = 15), 8 and 1 microg/ml, respectively; Eubacterium group (n = 33), 0.25 and 2 microg/ml, respectively; Lactobacillus spp. (n = 26), 0.5 and 4 microg/ml, respectively; Propionibacterium spp. (n = 34), 0.125 and 0.5 microg/ml, respectively; Peptostreptococcus spp. (n = 52), 0.125 and 0.5 microg/ml, respectively; and Corynebacterium spp. (n = 31), 0.03 and 0.5 microg/ml, respectively. The activity of TD-6424 was similar to that of quinupristin-dalfopristin for most strains except C. clostridioforme and Lactobacillus casei, where quinupristin-dalfopristin was three- to fivefold more active. Daptomycin had decreased activity (MIC > 4 microg/ml) against 14 strains of Actinomyces spp. and all C. ramosum, Eubacterium lentum, and Lactobacillus plantarum strains. Linezolid showed decreased activity (MIC > 4 microg/ml) against C. ramosum, two strains of C. difficile, and 15 strains of Lactobacillus spp. Imipenem and piperacillin
A simplified Tamm-Dancoff density functional approach for the electronic excitation spectra of very large molecules

NASA Astrophysics Data System (ADS)

Grimme, Stefan

2013-06-01

Two approximations in the Tamm-Dancoff density functional theory approach (TDA-DFT) to electronically excited states are proposed which allow routine computations for electronic ultraviolet (UV)- or circular dichroism (CD) spectra of molecules with 500-1000 atoms. Speed-ups compared to conventional time-dependent DFT (TD-DFT) treatments of about two to three orders of magnitude in the excited state part at only minor loss of accuracy are obtained. The method termed sTDA ("s" for simplified) employs atom-centered Löwdin-monopole based two-electron repulsion integrals with the asymptotically correct 1/R behavior and perturbative single excitation configuration selection. It is formulated generally for any standard global hybrid density functional with given Fock-exchange mixing parameter ax. The method performs well for two standard benchmark sets of vertical singlet-singlet excitations for values of ax in the range 0.2-0.6. The mean absolute deviations from reference data are only 0.2-0.3 eV and similar to those from standard TD-DFT. In three cases (two dyes and one polypeptide), good mutual agreement between the electronic spectra (up to 10-11 eV excitation energy) from the sTDA method and those from TD(A)-DFT is obtained. The computed UV- and CD-spectra of a few typical systems (e.g., C60, two transition metal complexes, [7]helicene, polyalanine, a supramolecular aggregate with 483 atoms and about 7000 basis functions) compare well with corresponding experimental data. The method is proposed together with medium-sized double- or triple-zeta type atomic-orbital basis sets as a quantum chemical tool to investigate the spectra of huge molecular systems at a reliable DFT level.
Dissociation and Internal Excitation of Molecular Nitrogen Due to N + N2 Collisions Using Direct Molecular Simulation

NASA Technical Reports Server (NTRS)

Grover, Maninder S.; Schwartzentruber, Thomas E.; Jaffe, Richard L.

2017-01-01

In this work we present a molecular level study of N2+N collisions, focusing on excitation of internal energy modes and non-equilibrium dissociation. The computation technique used here is the direct molecular simulation (DMS) method and the molecular interactions have been modeled using an ab-initio potential energy surface (PES) developed at NASA's Ames Research Center. We carried out vibrational excitation calculations between 5000K and 30000K and found that the characteristic vibrational excitation time for the N + N2 process was an order of magnitude lower than that predicted by the Millikan and White correlation. It is observed that during vibrational excitation the high energy tail of the vibrational energy distribution gets over populated first and the lower energy levels get populated as the system evolves. It is found that the non-equilibrium dissociation rate coefficients for the N + N2 process are larger than those for the N2 + N2 process. This is attributed to the non-equilibrium vibrational energy distributions for the N + N2 process being less depleted than that for the N2 +N2 process. For an isothermal simulation we find that the probability of dissociation goes as 1/T(sub tr) for molecules with internal energy (epsilon(sub int)) less than approximately 9.9eV, while for molecules with epsilon (sub int) greater than 9.9eV the dissociation probability was weakly dependent on translational temperature of the system. We compared non-equilibrium dissociation rate coefficients and characteristic vibrational excitation times obtained by using the ab-initio PES developed at NASA's Ames Research Center to those obtained by using an ab-initio PES developed at the University of Minnesota. Good agreement was found between the macroscopic properties and molecular level description of the system obtained by using the two PESs.
Integer ratios of S{sub n}/E{sub n} in {sup 40}Ca+n resonances suggesting two-oscillator excitations in the target nucleus

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

Ohkubo, Makio

2009-08-15

In s-wave neutron resonances of {sup 40}Ca at E{sub n}{<=}2.5 MeV, S{sub n}/E{sub n} for many levels is found to be of the form 17(n/m) where n, m are small integers. Statistical tests show small probabilities for the observed dispositions of many levels at E{sub n}=(j/k)(1/70)G (j, k; small integers). To meet the requirement of time periodicity of the compound nucleus at resonance, a breathing model is developed, where the excitation energies E{sub x} are written as a sum of inverse integers; E{sub x}=S{sub n}+E{sub n}=G{sigma}(1/k) (k: integer). In {sup 40}Ca+n, the separation energy S{sub n}=8362 keV is written asmore » S{sub n}=(17/70)G=(1/7+1/10)G, where G=34.4 MeV. G is almost equal to the Fermi energy of the nucleus. It is suggested that two oscillators of energy (1/7)G and (1/10)G are excited in {sup 40}Ca by neutron incidence, in which the recurrence energy (1/70)G is resonant with neutrons of energies at (j/k)(1/70)G, forming a simple compound nucleus.« less
Deformation and annealing response of TD-nickel chromium sheet

NASA Technical Reports Server (NTRS)

Kane, R. D.; Ebert, L. J.

1973-01-01

The deformation and annealing response of TD-nickel chromium (TD-NiCr) 0.1 inch thick sheet was examined using various cold-rolling and annealing treatments. Upon annealing (above 816 C (1500 F), the as-received material was converted from an initially ultra-fine grain size (average grain dimension 0.51 micron) to a large grain structure. Increases in grain size by a factor of 100 to 200 were observed for this transformation. However, in those material states where the large grain transformation was absent, a fine grain recrystallized structure formed upon annealing (above 732 C (1350 F)). The deformation and annealing response of TD-NiCr sheet was evaluated with respect to the processing related variables as mode and severity of deformation and annealing temperature. Results indicate that the large grain transformation, classical primary recrystallization occurs. Using selected materials produced during the deformation and annealing study, the elevated temperature tensile properties of TD-NiCr sheet were examined in the temperature range 593 C (1100 F) to 1093 C (2000 F). It was observed that the elevated temperature tensile properties of TD-NiCr sheet could be optimized by the stabilization of a large grain size in this material using the cold working and/or annealing treatments developed during the present investigation.

Effects of TD-5108 on Gastrointestinal Transit and Bowel Function in Health and Pharmacokinetics in Health and Constipation

PubMed Central

Manini, Mhd Louai; Camilleri, Michael; Goldberg, Michael; Sweetser, Seth; McKinzie, Sanna; Burton, Duane; Wong, Shekman; Kitt, Michael M.; Li, Yu-Ping; Zinsmeister, Alan R.

2010-01-01

Background TD-5108 is a potent, selective high intrinsic activity serotonin 5-HT4 receptor agonist. Aim To assess effects of TD-5108 on gastrointestinal transit and compare its pharmacokinetics (PK) in healthy volunteers (HV) and chronic constipation (CC) patients. Methods 60 HV were randomly assigned, double-blind to placebo, 5, 15, 30 or 50 mg TD-5108 (single and 6-day dosing). Primary endpoints were colonic transit (geometric center at 24 hours, GC24) and ascending colon emptying (ACE) T1/2 after first dose. Secondary endpoints included gastric emptying (GE) T1/2 and colonic filling at 6 h (CF6). Results Single dose TD-5108 significantly accelerated GC24, ACE T1/2, and CF6; 30 and 50°mg TD-5108 accelerated all 3 endpoints. With multiple doses, TD-5108 30 mg accelerated GC24, and overall accelerated GE T1/2 at 15–50 mg. PK studies showed dose proportionality in health, and no significant differences between health and chronic constipation with a 15 mg oral dose of TD-5108. Stimulation of bowel function after15 mg TD-5108 were similar in CC and controls. There were no serious adverse events; notable adverse were the predictable GI effects such as diarrhea or altered bowel movements. Conclusions TD-5108 significantly accelerated intestinal and colonic transit after single dosing and accelerated gastric emptying after multiple dosing. Further studies of its potential as a gastrointestinal and colonic prokinetic are warranted. PMID:19691492
Microtubule association of EML proteins and the EML4-ALK variant 3 oncoprotein require an N-terminal trimerization domain.

PubMed

Richards, Mark W; O'Regan, Laura; Roth, Daniel; Montgomery, Jessica M; Straube, Anne; Fry, Andrew M; Bayliss, Richard

2015-05-01

Proteins of the echinoderm microtubule (MT)-associated protein (EMAP)-like (EML) family contribute to formation of the mitotic spindle and interphase MT network. EML1-4 consist of Trp-Asp 40 (WD40) repeats and an N-terminal region containing a putative coiled-coil. Recurrent gene rearrangements in non-small cell lung cancer (NSCLC) fuse EML4 to anaplastic lymphoma kinase (ALK) causing expression of several oncogenic fusion variants. The fusions have constitutive ALK activity due to self-association through the EML4 coiled-coil. We have determined crystal structures of the coiled-coils from EML2 and EML4, which describe the structural basis of both EML self-association and oncogenic EML4-ALK activation. The structures reveal a trimeric oligomerization state directed by a conserved pattern of hydrophobic residues and salt bridges. We show that the trimerization domain (TD) of EML1 is necessary and sufficient for self-association. The TD is also essential for MT binding; however, this property requires an adjacent basic region. These observations prompted us to investigate MT association of EML4-ALK and EML1-ABL1 (Abelson 1) fusions in which variable portions of the EML component are present. Uniquely, EML4-ALK variant 3, which includes the TD and basic region of EML4 but none of the WD40 repeats, was localized to MTs, both when expressed recombinantly and when expressed in a patient-derived NSCLC cell line (H2228). This raises the question of whether the mislocalization of ALK activity to MTs might influence downstream signalling and malignant properties of cells. Furthermore, the structure of EML4 TD may enable the development of protein-protein interaction inhibitors targeting the trimerization interface, providing a possible avenue towards therapeutic intervention in EML4-ALK NSCLC.
Photocurrent characteristics of metal–AlGaN/GaN Schottky-on-heterojunction diodes induced by GaN interband excitation

NASA Astrophysics Data System (ADS)

Tang, Xi; Li, Baikui; Chen, Kevin J.; Wang, Jiannong

2018-05-01

The photocurrent characteristics of metal–AlGaN/GaN Schottky-on-heterojunction diodes were investigated. When the photon energy of incident light was larger than the bandgap of GaN but smaller than that of AlGaN, the alternating-current (ac) photocurrent measured using lock-in techniques increased with the chopper frequency. Analyzing the generation and flow processes of photocarriers revealed that the photocurrent induced by GaN interband excitation featured a transient behavior, and its direction reversed when the light excitation was removed. The abnormal dependence of the measured ac photocurrent magnitude on the chopper frequency was explained considering the detection principles of a lock-in amplifier.
Functional heterogeneity of memory B lymphocytes: in vivo analysis of TD-primed B cells responsive to secondary stimulation with TD and TI antigens.

PubMed

Rennick, D M; Morrow, P R; Benjamini, E

1983-08-01

The functional heterogeneity of memory B cells induced by a single determinant, consisting of a decapeptide representing amino acid residues 103-112 of tobacco mosaic virus protein (TMVP), was analyzed. Decapeptide specific antibodies were elicited in mice adoptively transferred with TMVP-immune spleen cells when challenged with TMVP, decapeptide conjugated to succinylated human gamma-globulin (SHGG), or decapeptide conjugated to Brucella abortus (BA). Whereas secondary stimulation by either TMVP or decapeptide-SHGG was dependent on appropriately primed T cells, stimulation by decapeptide-BA was independent of conventional T cell help. Furthermore, memory B cells responsive to TMVP (TD), decapeptide-SHGG (TD), or decapeptide-BA (TI. 1 prototype) were shown to consist of overlapping populations because adoptive recipients of TMVP-primed cells challenged simultaneously with TD and TI decapeptide antigens did not result in a higher antibody response than that elicited by one of the TD antigens injected alone. However, decapeptide-BA consistently induced a smaller antidecapeptide response than either TMVP or decapeptide-SHGG. This suggested that only a fraction of the memory B cell population which was activated by the original priming antigen (thymus-dependent) was also responsive to secondary in vivo stimulation by the priming hapten conjugated to Brucella abortus. Detailed analyses of the antibodies induced in the recipients of TMVP-immune spleen cells after secondary challenge with either TMVP, decapeptide-SHGG, or decapeptide-BA failed to distinguish between the responsive memory B cells; the antidecapeptide antibodies induced by all three immunogens shared the same fine specificities and immunoglobulin isotype composition. These data are viewed as further evidence that subsets of TD-primed B cells, which may display differential sensitivity to cross-stimulation with TD and TI forms of the antigen, represent distinct stages of memory B cell maturation within a
Development of forming and joining technology for TD-NiCr sheet

NASA Technical Reports Server (NTRS)

Torgerson, R. T.

1973-01-01

Forming joining techniques and properties data were developed for thin-gage TD-NiCr sheet in the recrystallized and unrecrystallized conditions. Theoretical and actual forming limit data are presented for several gages of each type of material for five forming processes: brake forming, corrugation forming, joggling, dimpling and beading. Recrystallized sheet can be best formed at room temperature, but unrecrystallized sheet requires forming at elevated temperature. Formability is satisfactory with most processes for the longitudinal orientation but poor for the transverse orientation. Dimpling techniques require further development for both material conditions. Data on joining techniques and joint properties are presented for four joining processes: resistance seam welding (solid-state), resistance spot welding (solid-state), resistance spot welding (fusion) and brazing. Resistance seam welded (solid-state) joints with 5t overlap were stronger than parent material for both material conditions when tested in tensile-shear and stress-rupture. Brazing studies resulted in development of NASA 18 braze alloy (Ni-16Cr-15Mo-8Al-4Si) with several properties superior to baseline TD-6 braze alloy, including lower brazing temperture, reduced reaction with Td-Ni-Cr, and higher stress-rupture properties.
RNA-Binding Protein L1TD1 Interacts with LIN28 via RNA and is Required for Human Embryonic Stem Cell Self-Renewal and Cancer Cell Proliferation

PubMed Central

Närvä, Elisa; Rahkonen, Nelly; Emani, Maheswara Reddy; Lund, Riikka; Pursiheimo, Huha-Pekka; Nästi, Juuso; Autio, Reija; Rasool, Omid; Denessiouk, Konstantin; Lähdesmäki, Harri; Rao, Anjana; Lahesmaa, Ritta

2012-01-01

Human embryonic stem cells (hESC) have a unique capacity to self-renew and differentiate into all the cell types found in human body. Although the transcriptional regulators of pluripotency are well studied, the role of cytoplasmic regulators is still poorly characterized. Here, we report a new stem cell-specific RNA-binding protein L1TD1 (ECAT11, FLJ10884) required for hESC self-renewal and cancer cell proliferation. Depletion of L1TD1 results in immediate downregulation of OCT4 and NANOG. Furthermore, we demonstrate that OCT4, SOX2, and NANOG all bind to the promoter of L1TD1. Moreover, L1TD1 is highly expressed in seminomas, and depletion of L1TD1 in these cancer cells influences self-renewal and proliferation. We show that L1TD1 colocalizes and interacts with LIN28 via RNA and directly with RNA helicase A (RHA). LIN28 has been reported to regulate translation of OCT4 in complex with RHA. Thus, we hypothesize that L1TD1 is part of the L1TD1-RHA-LIN28 complex that could influence levels of OCT4. Our results strongly suggest that L1TD1 has an important role in the regulation of stemness. PMID:22162396
F-16 Task Analysis Criterion-Referenced Objective and Objectives Hierarchy Report. Volume 4

DTIC Science & Technology

1981-03-01

Initiation cues: Engine flameout Systems presenting cues: Aircraft fuel, engine STANDARD: Authority: TACR 60-2 Performance precision: TD in first 1/3 of...task: None Initiation cues: On short final Systems preventing cues: N/A STANDARD: Authority: 60-2 Performance precision: +/- .5 AOA; TD zone 150-1000...precision: +/- .05 AOA; TD Zone 150-1000 Computational accuracy: N/A ... . . ... . ... e e m I TASK NO.: 1.9.4 BEHAVIOR: Perform short field landing
State-of-technology for joining TD-NiCr sheet.

NASA Technical Reports Server (NTRS)

Holko, K. H.; Moore, T. J.; Gyorgak, C. A.

1972-01-01

At the current state-of-technology there are many joining processes that can be used to make sound welds in TD-NiCr sheet. Some of these that are described in this report are electron beam welding (EBW), gas-tungsten arc welding (GTAW), diffusion welding (DFW), resistance spot welding (RSW), resistance seam welding (RSEW), and brazing. Roll welding (RW) and explosion welding (EXW) have not been developed to the point where they can be used to make sound welds in TD-NiCr. Joining work that has previously been done on TD-NiCr by various organizations, both privately supported and under Air Force and NASA contracts, is described in this summary. Current work is also described that is being done at General Dynamics/Convair (under NASA contract) and at NASA/Lewis to develop and evaluate DFW, RSW, RSEW, and brazing. Preliminary comparisons of joining processes are made for typical applications. A brief description of the manufacture of TD-NiCr sheet by a recently standardized process (under NASA contract) also is given.
Excited state intramolecular proton transfer reaction of 4'-N,N-diethylamino-3-hydroxyflavone and solvation dynamics in room temperature ionic liquids studied by optical Kerr gate fluorescence measurement.

PubMed

Kimura, Yoshifumi; Fukuda, Masanori; Suda, Kayo; Terazima, Masahide

2010-09-16

Fluorescence dynamics of 4'-N,N-diethylamino-3-hydroxyflavone (DEAHF) and its methoxy derivative (DEAMF) in various room temperature ionic liquids (RTILs) have been studied mainly by an optical Kerr gate method. DEAMF showed a single band fluorescence whose peak shifted with time by the solvation dynamics. The averaged solvation time determined by the fluorescence peak shift was proportional to the viscosity of the solvent except for tetradecyltrihexylphosphonium bis(trifluoromethanesulfonyl)amide. The solvation times were consistent with reported values determined with different probe molecules. DEAHF showed dual fluorescence due to the normal and tautomer forms produced by the excited state intramolecular proton transfer (ESIPT), and the relative intensities were dependent on the time and the solvent cation or anion species. By using the information of the fluorescence spectrum of DEAMF, the fluorescence spectrum of DEAHF at each delay time after the photoexcitation was decomposed into the normal and the tautomer fluorescence components, respectively. The normal component showed a very fast decay simulated by a biexponential function (2-3 and 20-30 ps) with an additional slower decay component. The tautomer component showed a rise with the time constants corresponding to the faster decay of the normal form with an additional instantaneous rise. The faster dynamics of the normal and tautomer population changes were assigned to the ESIPT process, while the slower decay of the fluorescence was attributed to the population decay from the excited state through the radiative and nonradiative processes. The average ESIPT time was much faster than the averaged solvation time of RTILs. Basically, the ESIPT kinetics in RTILs is similar to those in conventional liquid solvents like acetonitrile (Chou et al. J. Phys. Chem. A 2005, 109, 3777). The faster ESIPT is interpreted in terms of the activation barrierless process from the Franck-Condon state before the solvation of
Emission switching of 4,6-diphenylpyrimidones: solvent and solid state effects.

PubMed

Adjaye-Mensah, Edward; Gonzalez, Walter G; Bussé, David R; Captain, Burjor; Miksovska, Jaroslava; Wilson, James N

2012-08-30

The photophysics of 1-ethyl-4,6-bis(4-methoxyphenyl)-2(1H)-pyrimidone (1) and 1-ethyl-4,6-bis(4-(dimethylamino)phenyl)-2(1H)-pyrimidone (2) were investigated to determine the mechanisms of emission switching in response to protonation. UV-vis and steady state emission spectroscopy of the protonated and unprotonated forms across a range of solvents reveal the polarity dependence of the vertical excitation energies. Emission lifetimes and quantum yields show the solvent dependency of the excited states. Emission enhancements were observed in polyethylene glycol solutions and in the solid state (both thin film and single crystal), demonstrating the role of intramolecular rotation in thermal relaxation of the excited states. TD-DFT calculations provide insights into the excited state geometries and the role of intramolecular charge transfer. The collected data show that emission of diphenylpyrimidones can be modulated by four factors, including the identity of the electron-donating auxochrome, protonation state, solvent polarity, and viscosity.
DFTBaby: A software package for non-adiabatic molecular dynamics simulations based on long-range corrected tight-binding TD-DFT(B)

NASA Astrophysics Data System (ADS)

Humeniuk, Alexander; Mitrić, Roland

2017-12-01

A software package, called DFTBaby, is published, which provides the electronic structure needed for running non-adiabatic molecular dynamics simulations at the level of tight-binding DFT. A long-range correction is incorporated to avoid spurious charge transfer states. Excited state energies, their analytic gradients and scalar non-adiabatic couplings are computed using tight-binding TD-DFT. These quantities are fed into a molecular dynamics code, which integrates Newton's equations of motion for the nuclei together with the electronic Schrödinger equation. Non-adiabatic effects are included by surface hopping. As an example, the program is applied to the optimization of excited states and non-adiabatic dynamics of polyfluorene. The python and Fortran source code is available at http://www.dftbaby.chemie.uni-wuerzburg.de.
Deformation and annealing response of TD-nickel chromium

NASA Technical Reports Server (NTRS)

Kane, R. D.; Ebert, L. J.

1975-01-01

The recrystallization and grain growth processes occurring in TD-NiCr were examined with respect to deformation severity, annealing time, and temperature. Results indicated that two different annealing responses of TD-NiCr are possible, depending on the initial state and processing history prior to annealing. As-received sheet showed a dramatic increase in grain size with decreasing annealing temperature, whereas sheet prior-annealed at 1316 C for 1 hr exhibited very little variation with subsequent annealing temperature.
Exploratory study of friction welds in Udimet 700 and TD-Nickel bar

NASA Technical Reports Server (NTRS)

Moore, T. J.

1971-01-01

Friction welded butt joints were made in both Udimet 700 and TD-Nickel bar. Also, dissimilar metal friction welds were made between these materials. Friction welding of Udimet 700 shows great promise because the welds were found to be as strong as the parent metal in stress rupture and tensile tests at 760 and 980 C. The weld line was not detectable metallographically in the heat treated condition. Friction welding for TD-Nickel, however, holds little if any promise. TD-Nickel friction weldments could support only 9 percent as much stress as the base metal for a 10-hour stress-rupture life at 1090 C. Dissimilar Udimet 700/TD-Nickel friction welds could sustain only 15 percent as much stress as the TD-Nickel parent metal for a 10-hour rupture life at 930 C.
Intravital Fluorescence Excitation in Whole-Animal Optical Imaging.

PubMed

Nooshabadi, Fatemeh; Yang, Hee-Jeong; Bixler, Joel N; Kong, Ying; Cirillo, Jeffrey D; Maitland, Kristen C

2016-01-01

Whole-animal fluorescence imaging with recombinant or fluorescently-tagged pathogens or cells enables real-time analysis of disease progression and treatment response in live animals. Tissue absorption limits penetration of fluorescence excitation light, particularly in the visible wavelength range, resulting in reduced sensitivity to deep targets. Here, we demonstrate the use of an optical fiber bundle to deliver light into the mouse lung to excite fluorescent bacteria, circumventing tissue absorption of excitation light in whole-animal imaging. We present the use of this technology to improve detection of recombinant reporter strains of tdTomato-expressing Mycobacterium bovis BCG (Bacillus Calmette Guerin) bacteria in the mouse lung. A microendoscope was integrated into a whole-animal fluorescence imager to enable intravital excitation in the mouse lung with whole-animal detection. Using this technique, the threshold of detection was measured as 103 colony forming units (CFU) during pulmonary infection. In comparison, the threshold of detection for whole-animal fluorescence imaging using standard epi-illumination was greater than 106 CFU.
TD-60 links RalA GTPase function to the CPC in mitosis

PubMed Central

Papini, Diana; Langemeyer, Lars; Abad, Maria A.; Kerr, Alastair; Samejima, Itaru; Eyers, Patrick A.; Jeyaprakash, A. Arockia; Higgins, Jonathan M. G.; Barr, Francis A.; Earnshaw, William C.

2015-01-01

TD-60 (also known as RCC2) is a highly conserved protein that structurally resembles the Ran guanine exchange factor (GEF) RCC1, but has not previously been shown to have GEF activity. TD-60 has a typical chromosomal passenger complex (CPC) distribution in mitotic cells, but associates with integrin complexes and is involved in cell motility during interphase. Here we show that TD-60 exhibits GEF activity, in vitro and in cells, for the small GTPase RalA. TD-60 or RalA depletion causes spindle abnormalities in prometaphase associated with abnormal centromeric accumulation of CPC components. TD-60 and RalA apparently work together to contribute to the regulation of kinetochore–microtubule interactions in early mitosis. Importantly, several mitotic phenotypes caused by TD-60 depletion are reverted by the expression of a GTP-locked mutant, RalA (Q72L). The demonstration that a small GTPase participates in the regulation of the CPC reveals a level of mitotic regulation not suspected in previous studies. PMID:26158537
Intensities of the Martian N2 electron-impact excited dayglow emissions

NASA Astrophysics Data System (ADS)

Fox, Jane L.; Hać, Nicholas E. F.

2013-06-01

The first N2 emissions in the Martian dayglow were detected by the SPICAM UV spectrograph on board the Mars Express spacecraft. Intensities of the (0,5) and (0,6) Vegard-Kaplan bands were found to be about one third of those predicted more than 35 years ago. The Vegard-Kaplan band system arises from the transition from the lowest N2 triplet state (A3Σu+;v') to the electronic ground state (X1Σg+;v″). It is excited in the Martian dayglow by direct electron-impact excitation of the ground N2(X) state to the A state and by excitation to higher triplet states that populate the A state by cascading. Using revised data, we compute here updated intensities of several of the bands in the N2 triplet systems and those involving the a1Πg state, the upper state of the Lyman-Birge-Hopfield bands. We find that the predicted limb intensities for the (0,5) and (0,6) Vegard-Kaplan bands are consistent with the measured values.
BK/TD models for analyzing in vitro impedance data on cytotoxicity.

PubMed

Teng, S; Barcellini-Couget, S; Beaudouin, R; Brochot, C; Desousa, G; Rahmani, R; Pery, A R R

2015-06-01

The ban of animal testing has enhanced the development of new in vitro technologies for cosmetics safety assessment. Impedance metrics is one such technology which enables monitoring of cell viability in real time. However, analyzing real time data requires moving from static to dynamic toxicity assessment. In the present study, we built mechanistic biokinetic/toxicodynamic (BK/TD) models to analyze the time course of cell viability in cytotoxicity assay using impedance. These models account for the fate of the tested compounds during the assay. BK/TD models were applied to analyze HepaRG cell viability, after single (48 h) and repeated (4 weeks) exposures to three hepatotoxic compounds (coumarin, isoeugenol and benzophenone-2). The BK/TD models properly fit the data used for their calibration that was obtained for single or repeated exposure. Only for one out of the three compounds, the models calibrated with a single exposure were able to predict repeated exposure data. We therefore recommend the use of long-term exposure in vitro data in order to adequately account for chronic hepatotoxic effects. The models we propose here are capable of being coupled with human biokinetic models in order to relate dose exposure and human hepatotoxicity. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.
AV-block and conduction slowing prevail over TdP arrhythmias in the methoxamine-sensitized pro-arrhythmic rabbit model.

PubMed

Varkevisser, Rosanne; Vos, Marc A; Beekman, Jet D; Tieland, Ralph G; Van Der Heyden, Marcel A

2015-01-01

The methoxamine-sensitized rabbit model is widely used to screen drugs for proarrhythmic properties, especially repolarization-dependent TdP arrhythmias. With the change of anesthesia and/or sensitizing agent, conduction disturbances have been reported as well. Therefore, we compared currently available in-house anesthetics in order to preserve arrhythmia sensitivity and preclude conduction disturbances. Rabbits were randomly assigned to 3 groups: (1) 35 mg/kg ketamine + 5 mg/kg xylazine; (2) 0.5 mL/kg hypnorm + 3 mg/kg midazolam; (3) 35 mg/kg ketamine + 20 mg/kg propofol. Anesthesia was maintained by 1.5% isoflurane. Concomitant infusion of methoxamine (17 μg/kg/min for 40 minutes) and dofetilide (10 μg/kg/min for 30 minutes) was used to induce arrhythmias. Sole methoxamine infusion exclusively decreased HR in groups 1 and 3. Dofetilide lengthened repolarization, followed in time by PQ/QRS prolongation, second-degree AV block, and subsequently TdP arrhythmias. TdP was seen in 80%, 0%, and 33% of the rabbits in groups 1, 2, and 3, respectively. Decreasing the dose of dofetilide to 5 μg/kg/min in ketamine/xylazine anesthetized rabbits resulted in a drop in TdP incidence (25%) while conduction disturbances persisted. Flunarizine (n = 6) suppressed all TdP arrhythmias while conduction disturbances remained present. TdP incidence in the methoxamine-sensitized rabbit could be dramatically influenced by anesthesia, drug dose, and flunarizine, while conduction slowing remained present. Thus, conduction slowing seems to be the integral outcome in this model. © 2014 Wiley Periodicals, Inc.
Theoretical analyses of the effects on the linear and quadratic nonlinear optical properties of N-arylation of pyridinium groups in stilbazolium dyes.

PubMed

Coe, Benjamin J; Beljonne, David; Vogel, Henryk; Garín, Javier; Orduna, Jesús

2005-11-10

N-Arylation of the pyridinium electron acceptor unit in stilbazolium chromophores has been found by previous experimental hyper-Rayleigh scattering and electronic Stark effect (electroabsorption) spectroscopic studies to lead to substantial increases in the static first hyperpolarizability beta(0). We show here that INDO/SCI calculations on the isolated cations trans-4'-(dimethylamino)-N-R-4-stilbazolium (R = methyl 1, phenyl 2, 2,4-dinitrophenyl 3, or 2-pyrimidyl 4) predict only slight red-shifts in the energy of the intramolecular charge-transfer (ICT) transition and accompanying relatively small changes in beta(0) on moving along the series. The inclusion of acetonitrile solvent using a polarizable continuum model affords a somewhat better agreement with the experimental data, especially the red-shifting of the ICT transition and the increase in beta(0) on going from 1 to 4. Time-dependent density functional theory (TD-DFT), finite field, and coupled perturbed Hartree-Fock calculations reproduce even more closely the empirical data and trends; the latter two approaches lead to the highest quadratic nonlinear optical (NLO) response of the studied chromophores for 3, for which the predicted beta(0) is ca. 50-100% larger than that of the analogous N-methylated cation 1. Although the TD-DFT and INDO/SCI approaches give quite different results for ground- and excited-state dipole moments, the overall conclusions of these two methods regarding the ICT absorption and NLO responses are similar.
Rotational excitations of N2O in small helium clusters and the role of Bose permutation symmetry

NASA Astrophysics Data System (ADS)

Paesani, F.; Whaley, K. B.

2004-09-01

We present a detailed study of the energetics, structures, and Bose properties of small clusters of 4He containing a single nitrous oxide (N2O) molecule, from N=1 4He up to sizes corresponding to completion of the first solvation shell around N2O (N=16 4He). Ground state properties are calculated using the importance-sampled rigid-body diffusion Monte Carlo method, rotational excited state calculations are made with the projection operator imaginary time spectral evolution method, and Bose permutation exchange and associated superfluid properties are calculated with the finite temperature path integral method. For N⩽5 the helium atoms are seen to form an equatorial ring around the molecular axis, at N=6 helium density starts to occupy the second (local) minimum of the N2O-He interaction at the oxygen side of the molecule, and N=9 is the critical size at which there is onset of helium solvation all along the molecular axis. For N⩾8 six 4He atoms are distributed in a symmetric, quasirigid ring around N2O. Path integral calculations show essentially complete superfluid response to rotation about the molecular axis for N⩾5, and a rise of the perpendicular superfluid response from zero to appreciable values for N⩾8. Rotational excited states are computed for three values of the total angular momentum, J=1-3, and the energy levels fitted to obtain effective spectroscopic constants that show excellent agreement with the experimentally observed N dependence of the effective rotational constant Beff. The non-monotonic behavior of the rotational constant is seen to be due to the onset of long 4He permutation exchanges and associated perpendicular superfluid response of the clusters for N⩾8. We provide a detailed analysis of the role of the helium solvation structure and superfluid properties in determining the effective rotational constants.

Intravital Fluorescence Excitation in Whole-Animal Optical Imaging

PubMed Central

Bixler, Joel N.; Kong, Ying; Cirillo, Jeffrey D.; Maitland, Kristen C.

2016-01-01

Whole-animal fluorescence imaging with recombinant or fluorescently-tagged pathogens or cells enables real-time analysis of disease progression and treatment response in live animals. Tissue absorption limits penetration of fluorescence excitation light, particularly in the visible wavelength range, resulting in reduced sensitivity to deep targets. Here, we demonstrate the use of an optical fiber bundle to deliver light into the mouse lung to excite fluorescent bacteria, circumventing tissue absorption of excitation light in whole-animal imaging. We present the use of this technology to improve detection of recombinant reporter strains of tdTomato-expressing Mycobacterium bovis BCG (Bacillus Calmette Guerin) bacteria in the mouse lung. A microendoscope was integrated into a whole-animal fluorescence imager to enable intravital excitation in the mouse lung with whole-animal detection. Using this technique, the threshold of detection was measured as 103 colony forming units (CFU) during pulmonary infection. In comparison, the threshold of detection for whole-animal fluorescence imaging using standard epi-illumination was greater than 106 CFU. PMID:26901051
Single particle excitations in RbAg/sub 4/I/sub 5/

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

Shapiro, S.M.; Salamon, M.B.

1979-01-01

In an inelastic neutron experiment on RbAg/sub 4/I/sub 5/ a broad quasielastic peak was observed throughout Q-space. As the temperature was lowered, the quasielastic peak became a broad propagating excitation with dirac constant ..omega.. approx. 2.2 meV. This excitation was measured along several symmetry directions and it exhibited little dispersion. This confirms that the original idea of a single particle excitation corresponding to the Ag/sup +/ ions moving within a potential well created by the rest of the lattice. The temperature dependence of this excitation is consistent with recent calculations of neutron scattering in superionic conductors.
Semiconductor color-center structure and excitation spectra: Equation-of-motion coupled-cluster description of vacancy and transition-metal defect photoluminescence

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

PubMed

Zhang, Duo; Zhang, Hui; Zhang, Xiaohong; Sham, Tsun-Kong; Hu, Yongfeng; Sun, Xuhui

2016-03-07

The electronic structure and optical properties of di[4-(4-diphenylaminophenyl)phenyl]sulfone (denoted as DAPSF), a highly efficient fluorophor, have been investigated using X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) spectroscopy at excitation energies across the C, N, O K-edges and the sulfur K-edge. The results indicate that the blue luminescence is mainly related to the sulfur functional group.
Photo-Hall-effect study of excitation and recombination in Fe-doped GaN

NASA Astrophysics Data System (ADS)

Look, David C.; Leach, Jacob H.; Metzger, Robert

2017-02-01

The photo-Hall-effect was applied to the study of electron dynamics in semi-insulating Fe-doped GaN. High-powered light-emitting diodes of wavelengths λ = 940, 536, 449, 402, and 365 nm were used to excite steady-state free-electron volume concentrations Δn = 105-108 cm-3, depending on λ and intensity I0. Electron lifetime τ was determined from the energy E dependence of the excited sheet electron concentration Δns through the relationship Δns = I0τA(E), where the absorbance A(E) is a known function of sample thickness d and absorption coefficient α, and the energy dependence of α is taken from a theory of deep-center photoionization. The major sample impurities were Fe, Si, and C, with [Fe] ≫ [Si] and [C]. Fitted lifetimes τ ranged from 15 to 170 ps, depending on [Fe]. It was found that Δns ∝ I0 for [Si] > [C] and ∝ I01/2 for [Si] < [C]; the latter dependence arises possibly from self-compensation of neutral C impurities by N-vacancy donors. For [Si] > [C], some of the neutral Fe3+ is converted to Fe2+ with ground state Fe2+(5E) and excited state Fe2+(5T2); a fit of n vs. temperature T over the range of 290-325 K in the dark establishes E5E with respect to the conduction band: ECB - E5E = 0.564 eV - β5ET, where β5E = 3.6 × 10-4 eV/K. At room temperature, 294 K, ECB - E5E = 0.46 eV and ECB - E5T2 = 0.07 eV.
Elevated temperature deformation of TD-nickel base alloys

NASA Technical Reports Server (NTRS)

Petrovic, J. J.; Kane, R. D.; Ebert, L. J.

1972-01-01

Sensitivity of the elevated temperature deformation of TD-nickel to grain size and shape was examined in both tension and creep. Elevated temperature strength increased with increasing grain diameter and increasing L/D ratio. Measured activation enthalpies in tension and creep were not the same. In tension, the internal stress was not proportional to the shear modulus. Creep activation enthalpies increased with increasing L/D ratio and increasing grain diameter, to high values compared with that of the self diffusion enthalpy. It has been postulated that two concurrent processes contribute to the elevated temperature deformation of polycrystalline TD-nickel: (1) diffusion controlled grain boundary sliding, and (2) dislocation motion.
Quenching of I(2P1/2) by NO2, N2O4, and N2O.

PubMed

Kabir, Md Humayun; Azyazov, Valeriy N; Heaven, Michael C

2007-10-11

Quenching of excited iodine atoms (I(5p5, 2P1/2)) by nitrogen oxides are processes of relevance to discharge-driven oxygen iodine lasers. Rate constants at ambient and elevated temperatures (293-380 K) for quenching of I(2P1/2) atoms by NO2, N2O4, and N2O have been measured using time-resolved I(2P1/2) --> I(2P3/2) 1315 nm emission. The excited atoms were generated by pulsed laser photodissociation of CF3I at 248 nm. The rate constants for I(2P1/2) quenching by NO2 and N2O were found to be independent of temperature over the range examined with average values of (2.9 +/- 0.3) x 10(-15) and (1.4 +/- 0.1) x 10(-15) cm3 s(-1), respectively. The rate constant for quenching of I(2P1/2) by N2O4 was found to be (3.5 +/- 0.5) x 10(-13) cm3 s(-1) at ambient temperature.
Development of a microwave photoconductance measurement technique for the study of carrier dynamics in highly-excited 4H-SiC

NASA Astrophysics Data System (ADS)

Subačius, L.; Jarašiūnas, K.; Ščajev, P.; Kato, M.

2015-12-01

The microwave conductance decay (MCD) technique combining an initially matched transmission line setup and picosecond optical excitation was developed and applied for the monitoring of transmitted and reflected microwave power transients in a 4H-SiC epilayer in a wide excitation range, from 2 × 1014 to 1018 cm-3. The excitation-dependent decrease in measurement sensitivity in the power-law relations of the transients was observed at excess carrier densities above 1016 cm-3 due to the line mismatches and decrease in the internal microwave field in the illuminated sample. The calibration procedure of MCD data on excess carrier density was applied for the correction of the MCD transients and resulted in nearly identical MCD kinetics in the reflection and transmission. In a 35 μm-thick n-type 4H-SiC epilayer, the tendencies of the gradual decrease of the initial decay time with an excitation increase and the excitation-enhanced carrier recombination rate in MCD tails were analyzed numerically. These tendencies were attributed to the excitation dependent surface recombination rate and the enhanced trap-related bulk recombination, correspondingly.
75 FR 49023 - Proposed Collection; Comment Request for Form TD F 90-22.1

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-12

... TD F 90-22.1 AGENCY: Internal Revenue Service (IRS), Treasury. ACTION: Notice and request for... Form TD F 90-22.1, Report of Foreign Bank and Financial Accounts. DATES: Written comments should be.... OMB Number: 1545-2038. Form Number: TD F 90-22.1. Abstract: This information is collected because of...
Earliest humans in Europe: The age of TD6 Gran Dolina, Atapuerca, Spain

USGS Publications Warehouse

Falgueres, Christophe; Bahain, J.-J.; Yokoyama, Y.; Arsuaga, J.L.; Bermudez de Castro, Jose Maria; Carbonell, E.; Bischoff, J.L.; Dolo, J.-M.

1999-01-01

Hominid remains found in 1994 from the stratified Gran Dolina karst-filling at the Atapuerca site in NE Spain were dated to somewhat greater than 780 ka based on palaeomagnetic measurements, making these the oldest known hominids in Europe (sensu stricto). We report new ESR and U-series results on teeth from four levels of the Gran Dolina deposit which confirm the palaeomagnetic evidence, and indicate that TD6 (from which the human remains have been recovered) dates to the end of the Early Pleistocene. The results for the other levels are consistent with estimates based mainly on microfaunal evidence, and suggest that TD8, TD10 and TD11 date to the Middle Pleistocene. (C) 1999 Academic Press.
VUV dissociative excitation cross sections of H2O, NH3, and CH4 by electron impact. [Vacuum Ultra-Violet

NASA Technical Reports Server (NTRS)

Morgan, H. D.; Mentall, J. E.

1974-01-01

Absolute excitation functions for excited fragments resulting from electron bombardment of H2O, NH3, and CH4 by low-energy electrons (0 to 300 eV) have been measured in the vacuum ultraviolet (1100 to 1950 A). The predominant emission for each molecule was the H Lyman-alpha line, while the O I, N I, C I, and C II emissions were at least an order of magnitude weaker. Absolute cross sections at 100 eV are given along with the appearance potential of the various processes and the possible dissociative-excitation channels through which such processes proceed.
Multi-quasiparticle excitations in 145Tb

NASA Astrophysics Data System (ADS)

Zheng, Y.; Zhou, X. H.; Zhang, Y. H.; Hayakawa, T.; Oshima, M.; Toh, Y.; Shizuma, T.; Katakura, J.; Hatsukawa, Y.; Matsuda, M.; Kusakari, H.; Sugawara, M.; Furuno, K.; Komatsubara, T.

2004-04-01

High-spin states in 145Tb have been investigated by means of in-beam ggr-ray spectroscopy techniques with the 118Sn(32S, 1p4n) reaction. Excitation functions, X-ggr-t and ggr-ggr-t coincidences and ggr-ray anisotropies were measured. A level scheme of 145Tb was established up to Exap 7 MeV. The level structure shows characteristics of a spherical nucleus. Based on the systematics of level structure in the odd-A N = 80 isotones, the level structure below 2 MeV excitation is interpreted by coupling an h11/2 proton to the excitations in the even-even 144Gd core. Above 2 MeV excitation, most of the yrast levels are interpreted with multi-quasiparticle shell-model configurations.
The low-energy, charge-transfer excited states of 4-amino-4-prime-nitrodiphenyl sulfide

NASA Technical Reports Server (NTRS)

O'Connor, Donald B.; Scott, Gary W.; Tran, Kim; Coulter, Daniel R.; Miskowski, Vincent M.; Stiegman, Albert E.; Wnek, Gary E.

1992-01-01

Absorption and emission spectra of 4-amino-4-prime-nitrodiphenyl sulfide in polar and nonpolar solvents were used to characterize and assign the low-energy excited states of the molecule. Fluorescence-excitation anisotropy spectra and fluorescence quantum yields were also used to characterize the photophysics of these states. The lowest-energy fluorescent singlet state was determined to be an intramolecular charge transfer (ICT) state involving transfer of a full electron charge from the amino to the nitro group yielding a dipole moment of about 50 D. A low-energy, intense absorption band is assigned as a transition to a different ICT state involving a partial electron charge transfer from sulfur to the nitro group.
Development of nanostructured EuAl2O4 phosphors with strong long-UV excitation.

PubMed

Hirata, Gustavo A; Bosze, Eric J; McKittrick, Joanna

2008-12-01

Fueled by the need to develop novel materials for applications in solid state white-emitting lamps we have improved a new low-cost, clean and efficient technique to produce high luminescence phosphors with strong excitation in the long-UV range (350-400 nm) which makes them useful for applications in GaN-based solid state lamps. In this work, pressurized combustion synthesis has been successfully used to develop EuAl2O4 (europium aluminate), a new green photoluminescent material with monoclinic structure. The combustion synthesis reaction conditions can be adjusted to produce either the AlEuO3 orthorhombic phase at low pressures (0.1 MPa), or the new monoclinic EuAl2O4 phase, which is apparently more thermodynamically favorable at higher combustion reaction pressures (1.4 MPa). The luminescent material is a high surface area powder (approximately 50 m2/g) composed mainly of nanostructured needles and plates with 5-10 nm in diameter and 100-150 nm in length. A broad emission peak centered at 530 nm with a decay time of 1.5 approximately 2 ms is obtained at the maximum excitation wavelength lambda(exc) = 370 nm.
LIF excitation spectra for S 0 → S 1 transition of deuterated anthranilic acid COOD, ND 2 in supersonic-jet expansion

NASA Astrophysics Data System (ADS)

Kolek, Przemysław; Leśniewski, Sebastian; Andrzejak, Marcin; Góra, Maciej; Cias, Pawel; Weģrzynowicz, Adam; Najbar, Jan

2010-12-01

Laser induced fluorescence (LIF) excitation spectrum for the S 0 → S 1 transition of anthranilic acid molecules deuterated in the substituent groups (COOD, ND 2) was investigated. Analysis of the LIF spectrum allowed for the assignment of the six most prominent fundamental in-plane modes of frequencies up to ca. 850 cm. The experimental results show good correlation with the frequency changes upon deuteration computed with CIS (CI-Singles) and TD-DFT for the S 1 state. Deuteration induced red-shifts of the identified fundamental bands are used for examination of the alternative assignments proposed in earlier studies. Potential energy distributions (PED) and overlaps of the in-plane normal modes with frequencies below 850 cm indicate that the correspondence of the respective vibrations of the deuterated and non-deuterated molecule is very good. A blue-shift of the 00 transition due to the isotopic substitution, is equal to 47 cm. This relatively large value is caused primarily by a significant decrease of the N-H stretching frequency associated with the increase of strength of the intramolecular hydrogen bond upon the electronic excitation. The deuteration shift of the 00 band was interpreted in terms of the differences of the zero point energy (ZPE) between the S 0 and S 1 electronic states, computed with DFT and TD-DFT methods, respectively.
Intentionally Designed Three-Phase Time Diary (TD) as a Multi-Pronged Practice

ERIC Educational Resources Information Center

Chen, Hsin-Yu; Yarnal, Careen

2017-01-01

Adopting qualitative approaches, this study highlights the value of integrating cognitive understanding with students' daily experiences through a time diary (TD) project. Using an innovative three-phase design, the TD effectively heightened self-awareness, promoted self-reflection, inspired the desire to change, and facilitated knowledge…
75 FR 47893 - Proposed Collection; Comment Request for REG-111583-07, (T.D. 9405) (Final)

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-09

...-111583-07, (T.D. 9405) (Final) AGENCY: Internal Revenue Service (IRS), Treasury. ACTION: Notice and... comments concerning temporary and final regulations (REG-111583-07) (T.D. 9405), Employment Tax Adjustments... Adjustments. OMB Number: 1545-2097. Form Number: REG-111583-07 (T.D. 9405) (final). Abstract: This document...
Theoretical study of geometry relaxation following core excitation: H2O, NH3, and CH4

NASA Astrophysics Data System (ADS)

Takahashi, Osamu; Kunitake, Naoto; Takaki, Saya

2015-10-01

Single core-hole (SCH) and double core-hole excited state molecular dynamics (MD) calculations for neutral and cationic H2O, NH3, and CH4 have been performed to examine geometry relaxation after core excitation. We observed faster X-H (X = C, N, O) bond elongation for the core-ionized state produced from the valence cationic molecule and the double-core-ionized state produced from the ground and valence cationic molecules than for the first resonant SCH state. Using the results of SCH MD simulations of the ground and valence cationic molecules, Auger decay spectra calculations were performed. We found that fast bond scission leads to peak broadening of the spectra.
Electron impact excitation of the n = 2 to n = 3 transition in atomic hydrogen near threshold

NASA Astrophysics Data System (ADS)

Hata, J.; Morgan, L. A.; McDowell, M. R. C.

1980-06-01

Close-coupling calculations of electron impact excitation of the n = 2 to n = 3 transition of atomic hydrogen at energies below the n = 4 threshold are presented. The algebraic variational close-coupling code of Morgan (1980) with an eighteen-state basis was used to obtain cross sections at eight impact energies from 2.04 to 2.45 eV, and calculations in a six-state close-coupling model were compared with the six-state calculations of Burke et al. (1967). The six-state values are found to be in satisfactory agreement with the exception of the singlet contribution to the 2s-3s transition. Near the n = 3 threshold the cross section obtained in the full calculation is found to be almost a factor of 2 lower than that predicted by Johnson (1972), thus explaining in part the discrepancy between Johnson's results and experiments on hydrogen plasmas. Estimates of rate coefficients based on the cross sections and assuming a Maxwellian velocity distribution, however, are shown to remain in disagreement with experiment.
Review of FD-TD numerical modeling of electromagnetic wave scattering and radar cross section

NASA Technical Reports Server (NTRS)

Taflove, Allen; Umashankar, Korada R.

1989-01-01

Applications of the finite-difference time-domain (FD-TD) method for numerical modeling of electromagnetic wave interactions with structures are reviewed, concentrating on scattering and radar cross section (RCS). A number of two- and three-dimensional examples of FD-TD modeling of scattering and penetration are provided. The objects modeled range in nature from simple geometric shapes to extremely complex aerospace and biological systems. Rigorous analytical or experimental validatons are provided for the canonical shapes, and it is shown that FD-TD predictive data for near fields and RCS are in excellent agreement with the benchmark data. It is concluded that with continuing advances in FD-TD modeling theory for target features relevant to the RCS problems and in vector and concurrent supercomputer technology, it is likely that FD-TD numerical modeling will occupy an important place in RCS technology in the 1990s and beyond.

An improved diffusion welding technique for TD-NiCr

NASA Technical Reports Server (NTRS)

Holko, K. H.

1973-01-01

An improved diffusion welding technique has been developed for TD-NiCr sheet. In the most preferred form, the improved technique consists of diffusion welding 320-grit sanded plus chemically polished surfaces of unrecrystallized TD-NiCr at 760 C under 140 MN/m2 pressure for 1hr followed by postheating at 1180 C for 2hr. Compared to previous work, this improved technique has the advantages of shorter welding time, lower welding temperature, lower welding pressure, and a simpler and more reproducible surface preparation procedure. Weldments were made that had parent-metal creep-rupture shear strength at 1100 C.
Damping of hard excitations in strongly coupled $$ \\mathcal{N} $$ = 4 plasma

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

Fuini, John F.; Uhlemann, Christoph F.; Yaffe, Laurence G.

2016-12-13

The damping of high momentum excitations in strongly coupled maximally supersymmetric Yang-Mills plasma is studied. Previous calculations of the asymptotic behavior of the quasinormal mode spectrum are extended and clarified. We con rm that subleading corrections to the lightlike dispersion relation ω(q) = |q| have a universal |q| -1/3 form. Sufficiently narrow, weak planar shocks may be viewed as coherent superpositions of short wavelength quasinormal modes. The attenuation and evolution in profile of narrow planar shocks are examined as an application of our results.
Tetrahedral 4 α and 12C+α cluster structures in 16O

NASA Astrophysics Data System (ADS)

Kanada-En'yo, Yoshiko

2017-09-01

I have investigated structures of the ground and excited states of 16O with the method of variation after spin-parity projection in the antisymmetrized molecular dynamics model combined with the generator coordinate method of 12C+α cluster. The calculation reasonably reproduces the experimental energy spectra; E 2 , E 3 , E 4 , and I S 1 transitions; and α -decay properties. The formation of 4 α clusters has been confirmed from nucleon degrees of freedom in the AMD model without assuming the existence of any clusters. They form "tetrahedral" 4 α - and 12C+α cluster structures. The 12C+α structure constructs the Kπ=0+ band consisting of the 02+, 21+, and 41+ states and the Kπ=0- band of the 12-, 32-, and 51- states. The 01+, 31-, and 42+ states are assigned to the ground band constructed from the tetrahedral 4 α structure. The 01+ and 31- are approximately interpreted as Td band members with the ideal tetrahedral configuration. The ground-state 4 α correlation plays an important role in the enhancement of the E 3 transition strength to the 31-. The 42+ state is not the ideal Td member but constructed from a distorted tetrahedral 4 α structure. Moreover, significant state mixing of the tetrahedral 4 α and 12C+α cluster structures occurs between 41+ and 42+ states, indicating that the Td configuration of 4 α is rather fragile at Jπ=4+ .
Spin-adapted open-shell random phase approximation and time-dependent density functional theory. I. Theory.

PubMed

Li, Zhendong; Liu, Wenjian

2010-08-14

The spin-adaptation of single-reference quantum chemical methods for excited states of open-shell systems has been nontrivial. The primary reason is that the configuration space, generated by a truncated rank of excitations from only one component of a reference multiplet, is spin-incomplete. Those "missing" configurations are of higher ranks and can, in principle, be recaptured by a particular class of excitation operators. However, the resulting formalisms are then quite involved and there are situations [e.g., time-dependent density functional theory (TD-DFT) under the adiabatic approximation] that prevent one from doing so. To solve this issue, we propose here a tensor-coupling scheme that invokes all the components of a reference multiplet (i.e., a tensor reference) rather than increases the excitation ranks. A minimal spin-adapted n-tuply excited configuration space can readily be constructed by tensor products between the n-tuple tensor excitation operators and the chosen tensor reference. Further combined with the tensor equation-of-motion formalism, very compact expressions for excitation energies can be obtained. As a first application of this general idea, a spin-adapted open-shell random phase approximation is first developed. The so-called "translation rule" is then adopted to formulate a spin-adapted, restricted open-shell Kohn-Sham (ROKS)-based TD-DFT (ROKS-TD-DFT). Here, a particular symmetry structure has to be imposed on the exchange-correlation kernel. While the standard ROKS-TD-DFT can access only excited states due to singlet-coupled single excitations, i.e., only some of the singly excited states of the same spin (S(i)) as the reference, the new scheme can capture all the excited states of spin S(i)-1, S(i), or S(i)+1 due to both singlet- and triplet-coupled single excitations. The actual implementation and computation are very much like the (spin-contaminated) unrestricted Kohn-Sham-based TD-DFT. It is also shown that spin-contaminated spin
A study on the electronic spectra of some 2-azidobenzothiazoles, TD-DFT treatment.

PubMed

Abu-Eittah, Rafie H; El-Taher, Sabry; Hassan, Walid; Noamaan, Mahmoud

2015-12-05

The electronic absorption spectra of some 2-azidobenzothiazoles were measured in different solvents. The effects of solvent and substitution on the spectra were investigated. Substitution by a bromine atom and by a nitro group have significant effects on both band maxima and band intensity. Correlation between the spectra of the studied compounds and the corresponding hydrocarbons proved to be weak, whereas the correlation between the observed spectra and those calculated is adequate. Theoretical treatment of the ultraviolet spectra of the studied compounds was carried out by using the TD-DFT procedures, at the B3LYP level and the 6-311+G(∗∗) basis sets, the results compared well with the experimental values. The computed molecular orbitals of the ground state indicate that some orbitals are "localized-π" or "localized σ" molecular orbitals while the others are delocalized orbitals. The calculated functions of the excited states lead to an accurate assignment of the bands observed in the spectra. Copyright © 2015. Published by Elsevier B.V.
Constitutive expression of tdTomato protein as a cytotoxicity and proliferation marker for space radiation biology

NASA Astrophysics Data System (ADS)

Chishti, Arif A.; Hellweg, Christine E.; Berger, Thomas; Baumstark-Khan, Christa; Feles, Sebastian; Kätzel, Thorben; Reitz, Günther

2015-01-01

The radiation risk assessment for long-term space missions requires knowledge on the biological effectiveness of different space radiation components, e.g. heavy ions, on the interaction of radiation and other space environmental factors such as microgravity, and on the physical and biological dose distribution in the human body. Space experiments and ground-based experiments at heavy ion accelerators require fast and reliable test systems with an easy readout for different endpoints. In order to determine the effect of different radiation qualities on cellular proliferation and the biological depth dose distribution after heavy ion exposure, a stable human cell line expressing a novel fluorescent protein was established and characterized. tdTomato, a red fluorescent protein of the new generation with fast maturation and high fluorescence intensity, was selected as reporter of cell proliferation. Human embryonic kidney (HEK/293) cells were stably transfected with a plasmid encoding tdTomato under the control of the constitutively active cytomegalovirus (CMV) promoter (ptdTomato-N1). The stably transfected cell line was named HEK-ptdTomato-N1 8. This cytotoxicity biosensor was tested by ionizing radiation (X-rays and accelerated heavy ions) exposure. As biological endpoints, the proliferation kinetics and the cell density reached 100 h after irradiation reflected by constitutive expression of the tdTomato were investigated. Both were reduced dose-dependently after radiation exposure. Finally, the cell line was used for biological weighting of heavy ions of different linear energy transfer (LET) as space-relevant radiation quality. The relative biological effectiveness of accelerated heavy ions in reducing cellular proliferation peaked at an LET of 91 keV/μm. The results of this study demonstrate that the HEK-ptdTomato-N1 reporter cell line can be used as a fast and reliable biosensor system for detection of cytotoxic damage caused by ionizing radiation.
DFT and PCM-TD-DFT investigation of the electronic structures and spectra of 5-(3-phenyl-2-propenylidene)-2-thioxo-4-thiazolidinone derivatives

NASA Astrophysics Data System (ADS)

El-Taher, Sabry; Metwaly, Mohamed

2017-04-01

UV-Visible absorption spectra of 5-(3-phenyl-2-propenylidene)-2-thioxo-4-thiazolidinones (5pR-PPTT, R = H, CH3, CH3O, and N(CH3)2) were measured in different solvents and investigated using the theoretical PCM-TD-DFT scheme. A benchmark evaluation against experimental results on the accuracy of different DFT functionals has been performed. The best agreement with X-ray data is achieved by using the long-range corrected LC-wPBE functional, while the PBE0 functional provided the most accurate λmax for the studied compounds. The thionic forms of the ZE isomers of the studied compounds are found to be the most stable tautomers. The assignation debate of the second absorption band of rhodanine [2-thioxo-4-thiazolidinone (Rd)] has been solved by confirming on its π-π∗ nature. It was found that the expansion of the π-conjugation system at position 5 of Rd ring leads to significant bathochromic shift. The CT lengths (Δr) and dipole moment change (ΔμCT) indices showed that the charge transfer character of the electronic transitions is directly proportional to the electron-releasing strength of substituted phenyl ring. It was concluded that the red shifting of the maximum absorption is mainly regulated by the solvent polarizability and much less by solvent polarity.
Responses of transgenic Arabidopsis plants and recombinant yeast cells expressing a novel durum wheat manganese superoxide dismutase TdMnSOD to various abiotic stresses.

PubMed

Kaouthar, Feki; Ameny, Farhat-Khemakhem; Yosra, Kamoun; Walid, Saibi; Ali, Gargouri; Faiçal, Brini

2016-07-01

In plant cells, the manganese superoxide dismutase (Mn-SOD) plays an elusive role in the response to oxidative stress. In this study, we describe the isolation and functional characterization of a novel Mn-SOD from durum wheat (Triticum turgidum L. subsp. Durum), named TdMnSOD. Molecular phylogeny analysis showed that the durum TdMnSOD exhibited high amino acids sequence identity with other Mn-SOD plants. The three-dimensional structure showed that TdMnSOD forms a homotetramer and each subunit is composed of a predominantly α-helical N-terminal domain and a mixed α/β C-terminal domain. TdMnSOD gene expression analysis showed that this gene was induced by various abiotic stresses in durum wheat. The expression of TdMnSOD enhances tolerance of the transformed yeast cells to salt, osmotic, cold and H2O2-induced oxidative stresses. Moreover, the analysis of TdMnSOD transgenic Arabidopsis plants subjected to different environmental stresses revealed low H2O2 and high proline levels as compared to the wild-type plants. Compared with the non-transformed plants, an increase in the total SOD and two other antioxidant enzyme activities including catalase (CAT) and peroxidases (POD) was observed in the three transgenic lines subjected to abiotic stress. Taken together, these data provide evidence for the involvement of durum wheat TdMnSOD in tolerance to multiple abiotic stresses in crop plants. Copyright © 2016 Elsevier GmbH. All rights reserved.
Dynamics of electron solvation in I(-)(CH3OH)n clusters (4 ≤ n ≤ 11).

PubMed

Young, Ryan M; Yandell, Margaret A; Neumark, Daniel M

2011-03-28

The dynamics of electron solvation following excitation of the charge-transfer-to-solvent precursor state in iodide-doped methanol clusters, I(-)(CH(3)OH)(n = 4-11), are studied with time-resolved photoelectron imaging. This excitation produces a I···(CH(3)OH)(n)(-) cluster that is unstable with respect to electron autodetachment and whose autodetachment lifetime increases monotonically from ~800 fs to 85 ps as n increases from 4 to 11. The vertical detachment energy (VDE) and width of the excited state feature in the photoelectron spectrum show complex time dependence during the lifetime of this state. The VDE decreases over the first 100-400 fs, then rises exponentially to a maximum with a ~1 ps time constant, and finally decreases by as much as 180 meV with timescales of 3-20 ps. The early dynamics are associated with electron transfer from the iodide to the methanol cluster, while the longer-time changes in VDE are attributed to solvent reordering, possibly in conjunction with ejection of neutral iodine from the cluster. Changes in the observed width of the spectrum largely follow those of the VDEs; the dynamics of both are attributed to the major rearrangement of the solvent cluster during relaxation. The relaxation dynamics are interpreted as a reorientation of at least one methanol molecule and the disruption and formation of the solvent network in order to accommodate the excess charge.
Relaxation times measurement in single and multiply excited xenon clusters

NASA Astrophysics Data System (ADS)

Serdobintsev, P. Yu.; Melnikov, A. S.; Pastor, A. A.; Timofeev, N. A.; Khodorkovskiy, M. A.

2018-05-01

Direct measurement of the rates of nonradiative relaxation processes in electronically excited xenon clusters was carried out. The clusters were created in a pulsed supersonic beam and two-photon excited by femtosecond laser pulses with a wavelength of 263 nm. The measurements were performed using the pump-probe method and electron spectroscopy. It is shown that relaxation of light clusters XeN (N < 15) predominantly occurs by desorption of excited xenon atoms with a characteristic time constant of 3 ps. Heavier electronically excited clusters (N > 10) vibrationally relax to the lowest electronically excited state at a rate of about 0.075 eV/ps. Multiply excited clusters are deactivated via energy exchange between excited centers with the ionization of one of them. The production of electrons in this process occurs with a delay of ˜4 ps from the pump pulse, and the process is completed in 10 ps.
Multi-quasiparticle excitations in145Tb

NASA Astrophysics Data System (ADS)

Zheng, Yong; Zhou, Xiaohong; Zhang, Yuhu; Liu, Minliang; Guo, Yingxiang; Lei, Xiangguo; Hayakawa, T.; Oshima, M.; Toh, T.; Shizuma, T.; Katakura, J.; Hatsukawa, Y.; Matsuda, M.; Kusakari, H.; Sugawara, M.

2004-09-01

High-spin states in145Tb have been populated using the118Sn (32S, 1p4n) reaction at beam energy of 165 MeV. The level scheme of145Tb has been established up to Ex≈7.4 MeV. The level scheme shows characteristics of a spherical or slightly oblate nucleus. Based on the systematic trends of the level structure in the neighboring N=80 isotones, the level structure in145Tb below 2 MeV excitation is well eplained by coupling an h 11/2 valence proton to the even-even144Gd core. Above 2 MeV excitation, most of the yrast levels are interpreted with multi-quasiparticle shell-model configurations.
Growth kinetics for temperature-controlled atomic layer deposition of GaN using trimethylgallium and remote-plasma-excited NH3

NASA Astrophysics Data System (ADS)

Pansila, P.; Kanomata, K.; Miura, M.; Ahmmad, B.; Kubota, S.; Hirose, F.

2015-12-01

Fundamental surface reactions in the atomic layer deposition of GaN with trimethylgallium (TMG) and plasma-excited NH3 are investigated by multiple-internal-reflection infrared absorption spectroscopy (MIR-IRAS) at surface temperatures varying from room temperature (RT) to 400 °C. It is found that TMG is saturated at RT on GaN surfaces when the TMG exposure exceeds 8 × 104 Langmuir (L), where 1 L corresponds to 1.33 × 10-4 Pa s (or 1.0 × 10-6 Torr s), and its saturation density reaches the maximum value at RT. Nitridation with the plasma-excited NH3 on the TMG-saturated GaN surface is investigated by X-ray photoelectron spectroscopy (XPS). The nitridation becomes effective at surface temperatures in excess of 100 °C. The reaction models of TMG adsorption and nitridation on the GaN surface are proposed in this paper. Based on the surface analysis, a temperature-controlled ALD process consisting of RT-TMG adsorption and nitridation at 115 °C is examined, where the growth per cycle of 0.045 nm/cycle is confirmed. XPS analysis indicates that all N atoms are bonded as GaN. Atomic force microscopy indicates an average roughness of 0.23 nm. We discuss the reaction mechanism of GaN ALD in the low-temperature region at around 115 °C with TMG and plasma-excited NH3.
Toll-like receptor 4 enhancement of non-NMDA synaptic currents increases dentate excitability after brain injury.

PubMed

Li, Ying; Korgaonkar, Akshata A; Swietek, Bogumila; Wang, Jianfeng; Elgammal, Fatima S; Elkabes, Stella; Santhakumar, Vijayalakshmi

2015-02-01

Concussive brain injury results in neuronal degeneration, microglial activation and enhanced excitability in the hippocampal dentate gyrus, increasing the risk for epilepsy and memory dysfunction. Endogenous molecules released during injury can activate innate immune responses including toll-like receptor 4 (TLR4). Recent studies indicate that immune mediators can modulate neuronal excitability. Since non-specific agents that reduce TLR4 signaling can limit post-traumatic neuropathology, we examined whether TLR4 signaling contributes to early changes in dentate excitability after brain injury. Concussive brain injury caused a transient increase in hippocampal TLR4 expression within 4h, which peaked at 24h. Post-injury increase in TLR4 expression in the dentate gyrus was primarily neuronal and persisted for one week. Acute, in vitro treatment with TLR4 ligands caused bidirectional modulation of dentate excitability in control and brain-injured rats, with a reversal in the direction of modulation after brain injury. TLR4 antagonists decreased, and agonist increased, afferent-evoked dentate excitability one week after brain injury. NMDA receptor antagonist did not occlude the ability of LPS-RS, a TLR4 antagonist, to decrease post-traumatic dentate excitability. LPS-RS failed to modulate granule cell NMDA EPSCs but decreased perforant path-evoked non-NMDA EPSC peak amplitude and charge transfer in both granule cells and mossy cells. Our findings indicate an active role for TLR4 signaling in early post-traumatic dentate hyperexcitability. The novel TLR4 modulation of non-NMDA glutamatergic currents, identified herein, could represent a general mechanism by which immune activation influences neuronal excitability in neurological disorders that recruit sterile inflammatory responses. Copyright © 2014 Elsevier Inc. All rights reserved.
Enhanced upconversion emission in colloidal (NaYF4:Er(3+))/NaYF4 core/shell nanoparticles excited at 1523 nm.

PubMed

Shao, Wei; Chen, Guanying; Damasco, Jossana; Wang, Xianliang; Kachynski, Aliaksandr; Ohulchanskyy, Tymish Y; Yang, Chunhui; Ågren, Hans; Prasad, Paras N

2014-03-15

In this work, we report on efficient visible and near-IR upconversion emissions in colloidal hexagonal-phase core/shell NaYF4:Er(3+)/NaYF4 nanoparticles (∼38 nm) under IR laser excitation at 1523 nm. Varying amounts of Er(3+) dopants were introduced into the core NaYF4:Er(3+) nanoparticles, revealing an optimized Er(3+) concentration of 10% for the highest luminescent efficiency. An inert epitaxial shell layer of NaYF4 grown onto the core of the NaYF4:Er(3+) 10% nanoparticle increased its upconversion emission intensity fivefold due to suppression of surface-related quenching mechanisms, yielding the absolute upconversion efficiency to be as high as ∼3.9±0.3% under an excitation density of 18 W/cm(2). The dependence of the intensity of upconversion emission peaks on laser excitation density in the core/shell nanoparticle displayed "saturation effects" at low excitation density in the range of 1.5-18 W/cm(2), which again demonstrates high upconversion efficiency.
Dynamics and couplings of N-H stretching excitations of guanosine-cytidine base pairs in solution.

PubMed

Yang, Ming; Szyc, Łukasz; Röttger, Katharina; Fidder, Henk; Nibbering, Erik T J; Elsaesser, Thomas; Temps, Friedrich

2011-05-12

N-H stretching vibrations of hydrogen-bonded guanosine-cytidine (G·C) base pairs in chloroform solution are studied with linear and ultrafast nonlinear infrared (IR) spectroscopy. Assignment of the IR-active bands in the linear spectrum is made possible by combining structural information on the hydrogen bonds in G·C base pairs with literature results of density functional theory calculations, and empirical relations connecting frequency shifts and intensity of the IR-active vibrations. A local mode representation of N-H stretching vibrations is adopted, consisting of ν(G)(NH(2))(f) and ν(C)(NH(2))(f) modes for free NH groups of G and C, and of ν(G)(NH(2))(b), ν(G)(NH), and ν(C)(NH(2))(b) modes associated with N-H stretching motions of hydrogen-bonded NH groups. The couplings and relaxation dynamics of the N-H stretching excitations are studied with femtosecond mid-infrared two-dimensional (2D) and pump-probe spectroscopy. The N-H stretching vibrations of the free NH groups of G and C have an average population lifetime of 2.4 ps. Besides a vibrational population lifetime shortening to subpicosecond values observed for the hydrogen-bonded N-H stretching vibrations, the 2D spectra reveal vibrational excitation transfer from the ν(G)(NH(2))(b) mode to the ν(G)(NH) and/or ν(C)(NH(2))(b) modes. The underlying intermode vibrational couplings are on the order of 10 cm(-1).
A Novel Approach to Dual Excitation Ratiometric Optical Mapping of Cardiac Action Potentials with Di-4-ANEPPS using Pulsed LED Excitation

PubMed Central

Bachtel, Andrew D.; Gray, Richard A.; Stohlman, Jayna M.; Bourgeois, Elliot B.; Pollard, Andrew E.

2011-01-01

We developed a new method for ratiometric optical mapping of transmembrane potential (Vm) in cardiac preparations stained with di-4-ANEPPS. Vm-dependent shifts of excitation and emission spectra establish two excitation bands (<481 and >481 nm) that produce fluorescence changes of opposite polarity within a single emission band (575–620 nm). The ratio of these positive and negative fluorescence signals (excitation ratiometry) increases Vm sensitivity and removes artifacts common to both signals. We pulsed blue (450±10 nm) and cyan (505±15 nm) light emitting diodes (LEDs) at 375 Hz in alternating phase synchronized to a camera (750 frames-per-second). Fluorescence was bandpass filtered (585±20 nm). This produced signals with upright (blue) and inverted (cyan) action potentials (APs) interleaved in sequential frames. In 4 whole swine hearts with motion chemically arrested, fractional fluorescence for blue, cyan, and ratio signals was 1.2±0.3%, 1.2±0.3%, and 2.4±0.6%, respectively. Signal-to-noise ratios were 4.3±1.4, 4.0±1.2, and 5.8±1.9, respectively. After washing out the electromechanical uncoupling agent, we characterized motion artifact by cross-correlating blue, cyan, and ratio signals with a signal with normal AP morphology. Ratiometry improved cross-correlation coefficients from 0.50±0.48 to 0.81±0.25, but did not cancel all motion artifacts. These findings demonstrate the feasibility of pulsed LED excitation ratiometry in myocardium. PMID:21536528
Electronic excitations in long polyenes revisited

NASA Astrophysics Data System (ADS)

Schmidt, Maximilian; Tavan, Paul

2012-03-01

We apply the valence shell model OM2 [W. Weber and W. Thiel, Theor. Chem. Acc. 103, 495, (2000), 10.1007/s002149900083] combined with multireference configuration interaction (MRCI) to compute the vertical excitation energies and transition dipole moments of the low-energy singlet excitations in the polyenes with 4 ⩽ N ⩽ 22π-electrons. We find that the OM2/MRCI descriptions closely resemble those of Pariser-Parr-Pople (PPP) π-electron models [P. Tavan and K. Schulten, Phys. Rev. B 36, 4337, (1987)], if equivalent MRCI procedures and regularly alternating model geometries are used. OM2/MRCI optimized geometries are shown to entail improved descriptions particularly for smaller polyenes (N ⩽ 12), for which sizeable deviations from the regular model geometries are found. With configuration interaction active spaces covering also the σ- in addition to the π-electrons, OM2/MRCI excitation energies turn out to become smaller by at most 0.35 eV for the ionic and 0.15 eV for the covalent excitations. The particle-hole (ph) symmetry, which in Pariser-Parr-Pople models arises from the zero-differential overlap approximation, is demonstrated to be only weakly broken in OM2 such that the oscillator strengths of the covalent 1B_u^- states, which artificially vanish in ph-symmetric models, are predicted to be very small. According to OM2/MRCI and experimental data the 1B_u^- state is the third excited singlet state for N < 12 and becomes the second for N ⩾ 14. By comparisons with results of other theoretical approaches and experimental evidence we argue that deficiencies of the particular MRCI method employed by us, which show up in a poor size consistency of the covalent excitations for N > 12, are caused by its restriction to at most doubly excited references.
Metallographic examination of TD-nickel base alloys. [thermal and chemical etching technique evaluation

NASA Technical Reports Server (NTRS)

Kane, R. D.; Petrovic, J. J.; Ebert, L. J.

1975-01-01

Techniques are evaluated for chemical, electrochemical, and thermal etching of thoria dispersed (TD) nickel alloys. An electrochemical etch is described which yielded good results only for large grain sizes of TD-nickel. Two types of thermal etches are assessed for TD-nickel: an oxidation etch and vacuum annealing of a polished specimen to produce an etch. It is shown that the first etch was somewhat dependent on sample orientation with respect to the processing direction, the second technique was not sensitive to specimen orientation or grain size, and neither method appear to alter the innate grain structure when the materials were fully annealed prior to etching. An electrochemical etch is described which was used to observe the microstructures in TD-NiCr, and a thermal-oxidation etch is shown to produce better detail of grain boundaries and to have excellent etching behavior over the entire range of grain sizes of the sample.
Mark 4A DSN receiver-exciter and transmitter subsystems

NASA Technical Reports Server (NTRS)

Wick, M. R.

1986-01-01

The present configuration of the Mark 4A DSN Receiver-Exciter and Transmitter Subsystems is described. Functional requirements and key characteristics are given to show the differences in the capabilities required by the Networks Consolidation task for combined High Earth Orbiter and Deep Space Network tracking support.
Vector Sum Excited Linear Prediction (VSELP) speech coding at 4.8 kbps

NASA Technical Reports Server (NTRS)

Gerson, Ira A.; Jasiuk, Mark A.

1990-01-01

Code Excited Linear Prediction (CELP) speech coders exhibit good performance at data rates as low as 4800 bps. The major drawback to CELP type coders is their larger computational requirements. The Vector Sum Excited Linear Prediction (VSELP) speech coder utilizes a codebook with a structure which allows for a very efficient search procedure. Other advantages of the VSELP codebook structure is discussed and a detailed description of a 4.8 kbps VSELP coder is given. This coder is an improved version of the VSELP algorithm, which finished first in the NSA's evaluation of the 4.8 kbps speech coders. The coder uses a subsample resolution single tap long term predictor, a single VSELP excitation codebook, a novel gain quantizer which is robust to channel errors, and a new adaptive pre/postfilter arrangement.

Comparison of modified driver circuit and capacitor-transfer circuit in longitudinally excited N2 laser.

PubMed

Uno, Kazuyuki; Akitsu, Tetsuya; Nakamura, Kenshi; Jitsuno, Takahisa

2013-04-01

We developed a modified driver circuit composed of a capacitance and a spark gap, called a direct-drive circuit, for a longitudinally excited gas laser. The direct-drive circuit uses a large discharge impedance caused by a long discharge length of the longitudinal excitation scheme and eliminates the buffer capacitance used in the traditional capacitor-transfer circuit. We compared the direct-drive circuit and the capacitor-transfer circuit in a longitudinally excited N2 laser (wavelength: 337 nm). Producing high output energy with the capacitor-transfer circuit requires a large storage capacitance and a discharge tube with optimum dimensions (an inner diameter of 4 mm and a length of 10 cm in this work); in contrast, the direct-drive circuit requires a high breakdown voltage, achieved with a small storage capacitance and a large discharge tube. Additionally, for the same input energy of 792 mJ, the maximum output energy of the capacitor-transfer circuit was 174.2 μJ, and that of the direct-drive circuit was 344.7 μJ.
Probing defect states in polycrystalline GaN grown on Si(111) by sub-bandgap laser-excited scanning tunneling spectroscopy

NASA Astrophysics Data System (ADS)

Hsiao, F.-M.; Schnedler, M.; Portz, V.; Huang, Y.-C.; Huang, B.-C.; Shih, M.-C.; Chang, C.-W.; Tu, L.-W.; Eisele, H.; Dunin-Borkowski, R. E.; Ebert, Ph.; Chiu, Y.-P.

2017-01-01

We demonstrate the potential of sub-bandgap laser-excited cross-sectional scanning tunneling microscopy and spectroscopy to investigate the presence of defect states in semiconductors. The characterization method is illustrated on GaN layers grown on Si(111) substrates without intentional buffer layers. According to high-resolution transmission electron microscopy and cathodoluminescence spectroscopy, the GaN layers consist of nanoscale wurtzite and zincblende crystallites with varying crystal orientations and hence contain high defect state densities. In order to discriminate between band-to-band excitation and defect state excitations, we use sub-bandgap laser excitation. We probe a clear increase in the tunnel current at positive sample voltages during sub-bandgap laser illumination for the GaN layer with high defect density, but no effect is found for high quality GaN epitaxial layers. This demonstrates the excitation of free charge carriers at defect states. Thus, sub-bandgap laser-excited scanning tunneling spectroscopy is a powerful complimentary characterization tool for defect states.
Role of Excited Nitrogen In The Ionosphere

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Cartwright, D. C.; Bolorizadeh, M. A.

2006-12-01

Sunlight photoionises atoms and molecules in the Earth's upper atmosphere, producing ions and photoelectrons. The photoelectrons then produce further ionisation by electron impact. These processes produce the ionosphere, which contains various positive ions, such as NO+, N+, and O+, and an equal density of free electrons. O+(4S) ions are long-lived and so the electron density is determined mainly by the density of O+(4S). This density is dependent on ambipolar diffusion and on loss processes, which are principally reactions with O2 and N2. The reaction with N2 is known to be strongly dependent on the vibrational state of N2 but the rate constants are not well determined for the ionosphere. Vibrational excitation of N2 is produced by direct excitation by thermal electrons and photoelectrons and by cascade from the excited states of N2 that are produced by photoelectron impact. It can also be produced by a chemical reaction and by vibrational-translational transitions. The vibrational excitation is lost by deexcitation by electron impact, by step-wise quenching in collisions with O atoms, and in the reaction with O+(4S). The distribution of vibrational levels is rearranged by vibrational-vibrational transitions, and by molecular diffusion vertically in the atmosphere. A computational model that includes these processes and predicts the electron density as a function of height in the ionosphere is described. This model is a combination of a "statistical equilibrium" calculation, which is used to predict the populations of the excited states of N2, and a time-step calculation of the atmospheric reactions and processes. The latter includes a calculation of photoionisation down through the atmosphere as a function of time of day and solar activity, and calculations at 0.1 s intervals of the changing densities of positive ions, electrons and N2 in the different vibrational levels. The validity of the model is tested by comparison of the predicted electron densities with
Spectrophotometric, voltammetric and cytotoxicity studies of 2-hydroxy-5-methoxyacetophenone thiosemicarbazone and its N(4)-substituted derivatives: A combined experimental-computational study

NASA Astrophysics Data System (ADS)

Akgemci, Emine Guler; Saf, Ahmet Ozgur; Tasdemir, Halil Ugur; Türkkan, Ercan; Bingol, Haluk; Turan, Suna Ozbas; Akkiprik, Mustafa

2015-02-01

In this study, 2-hydroxy-5-methoxyacetophenone thiosemicarbazone (HMAT) and its novel N(4) substituted derivatives were synthesized and characterized by different techniques. The optical band gap of the compounds and the energy of HOMO were experimentally examined by UV-vis spectra and cyclic voltammetry measurements, respectively. Furthermore, the conformational spaces of the compounds were scanned with molecular mechanics method. The geometry optimization, HOMO and LUMO energies, the energy gap of the HOMO-LUMO, dipole moment of the compounds were theoretically calculated by the density functional theory B3LYP/6-311++G(d,p) level. The minimal electronic excitation energy and maximum wavelength calculations of the compounds were also performed by TD-DFT//B3LYP/6-311++G(d,p) level of theory. Theoretically calculated values were compared with the related experimental values. The combined results exhibit that all compounds have good electron-donor properties which affect anti-proliferative activity. The cytotoxic effects of the compounds were also evaluated against HeLa (cervical carcinoma), MCF-7 (breast carcinoma) and PC-3 (prostatic carcinoma) cell lines using the standard MTT assay. All tested compounds showed antiproliferative effect having IC50 values in different range. In comparison with that of HMAT, it was obtained that while ethyl group on 4(N)-substituted position decreased in potent anti-proliferative effect, the phenyl group on the position increased in anti-proliferative effect for the tested cancer cell line. Considering the molecular energy parameters, the cytotoxicity activities of the compounds were discussed.
Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) Study.

PubMed

Kang, Guo-Jun; Song, Chao; Ren, Xue-Feng

2016-11-25

The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH₃-YD2 and TPhe-YD) were systematically investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO₂ cluster were fully investigated. From the analyses of natural bond orbital (NBO), extended charge decomposition analysis (ECDA), and electron density variations (Δρ) between the excited state and ground state, it was found that the introduction of N(CH₃)₂ and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT) character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH₃)₂ and 1,1,2-triphenylethene groups. NCH₃-YD2 with N(CH₃)₂ groups in the donor part is an effective way to improve the interactions between the dyes and TiO₂ surface, light having efficiency (LHE), and free energy change (ΔG inject ), which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs).
Coulomb excitation of radioactive 20, 21Na

NASA Astrophysics Data System (ADS)

Schumaker, M. A.; Cline, D.; Hackman, G.; Pearson, C.; Svensson, C. E.; Wu, C. Y.; Andreyev, A.; Austin, R. A. E.; Ball, G. C.; Bandyopadhyay, D.; Becker, J. A.; Boston, A. J.; Boston, H. C.; Buchmann, L.; Churchman, R.; Cifarelli, F.; Cooper, R. J.; Cross, D. S.; Dashdorj, D.; Demand, G. A.; Dimmock, M. R.; Drake, T. E.; Finlay, P.; Gallant, A. T.; Garrett, P. E.; Green, K. L.; Grint, A. N.; Grinyer, G. F.; Harkness, L. J.; Hayes, A. B.; Kanungo, R.; Lisetskiy, A. F.; Leach, K. G.; Lee, G.; Maharaj, R.; Martin, J.-P.; Moisan, F.; Morton, A. C.; Mythili, S.; Nelson, L.; Newman, O.; Nolan, P. J.; Orce, J. N.; Padilla-Rodal, E.; Phillips, A. A.; Porter-Peden, M.; Ressler, J. J.; Roy, R.; Ruiz, C.; Sarazin, F.; Scraggs, D. P.; Waddington, J. C.; Wan, J. M.; Whitbeck, A.; Williams, S. J.; Wong, J.

2009-12-01

The low-energy structures of the radioactive nuclei 20, 21Na have been examined using Coulomb excitation at the TRIUMF-ISAC radioactive ion beam facility. Beams of ˜ 5×106 ions/s were accelerated to 1.7MeV/A and Coulomb excited in a 0.5mg/cm^2 natTi target. Two TIGRESS HPGe clover detectors perpendicular to the beam axis were used for γ -ray detection, while scattered nuclei were observed by the Si detector BAMBINO. For 21Na , Coulomb excitation from the 3/2+ ground state to the first excited 5/2+ state was observed, while for 20Na , Coulomb excitation was observed from the 2+ ground state to the first excited 3+ and 4+ states. For both beams, B ( λ L) values were determined using the 2+ rightarrow 0+ de-excitation in 48Ti as a reference. The resulting B( E2) ↓ value for 21Na is 137±9 e^2fm^4, while the resulting B( λ L) ↓ values for 20Na are 55±6 e^2fm^4 for the 3+ rightarrow 2+ , 35.7±5.7 e^2 fm^4 for the 4+ rightarrow 2+ , and 0.154±0.030 μ_ N^2 for the 4+ rightarrow 3+ transitions. This analysis significantly improves the measurement of the 21Na B( E2) value, and provides the first experimental determination of B( λ L) values for the proton dripline nucleus 20Na .-1
SSCC TD: A Serial and Simultaneous Configural-Cue Compound Stimuli Representation for Temporal Difference Learning

PubMed Central

Mondragón, Esther; Gray, Jonathan; Alonso, Eduardo; Bonardi, Charlotte; Jennings, Dómhnall J.

2014-01-01

This paper presents a novel representational framework for the Temporal Difference (TD) model of learning, which allows the computation of configural stimuli – cumulative compounds of stimuli that generate perceptual emergents known as configural cues. This Simultaneous and Serial Configural-cue Compound Stimuli Temporal Difference model (SSCC TD) can model both simultaneous and serial stimulus compounds, as well as compounds including the experimental context. This modification significantly broadens the range of phenomena which the TD paradigm can explain, and allows it to predict phenomena which traditional TD solutions cannot, particularly effects that depend on compound stimuli functioning as a whole, such as pattern learning and serial structural discriminations, and context-related effects. PMID:25054799
Inertial Navigation System for India's Reusable Launch Vehicle-Technology Demonstrator (RLV-TD HEX) Mission

NASA Astrophysics Data System (ADS)

Umadevi, P.; Navas, A.; Karuturi, Kesavabrahmaji; Shukkoor, A. Abdul; Kumar, J. Krishna; Sreekumar, Sreejith; Basim, A. Mohammed

2017-12-01

This work presents the configuration of Inertial Navigation System (INS) used in India's Reusable Launch Vehicle-Technology Demonstrator (RLV-TD) Program. In view of the specific features and requirements of the RLV-TD, specific improvements and modifications were required in the INS. A new system was designed, realised and qualified meeting the mission requirements of RLV-TD, at the same time taking advantage of the flight heritage attained in INS through various Launch vehicle Missions of the country. The new system has additional redundancy in acceleration channel, in-built inclinometer based bias update scheme for acceleration channels and sign conventions as employed in an aircraft. Data acquisition in micro cycle periodicity (10 ms) was incorporated which was required to provide rate and attitude information at higher sampling rate for ascent phase control. Provision was incorporated for acquisition of rate and acceleration data with high resolution for aerodynamic characterisation and parameter estimation. GPS aided navigation scheme was incorporated to meet the stringent accuracy requirements of the mission. Navigation system configuration for RLV-TD, specific features incorporated to meet the mission requirements, various tests carried out and performance during RLV-TD flight are highlighted.
An investigation of the magnetic field of Transient Disturbances (TD) at the Earth's orbit, and a determination of solar sources of TD from their characteristics at R = 1 AU

NASA Technical Reports Server (NTRS)

Fainshtein, V. .G.; Kaigorodov, A. P.

1995-01-01

We have investigated and intercompared the typical features of the magnetic field of two types of solar wind transient disturbances with shock waves: the shock wave is accompanied by a magnetic cloud (MC), and the shock wave is followed by a region with bidirectional solar wind electron heat flux (BEHF), with no MC present. In this case, a separate study was made of the field features in two typical TD structures: in the region of impact-compressed solar wind between the shock wave and MC or BEHF, as well as in MC and BEHF. The study has provided new results on the influence of the ambient SW upon the TD magnetic field and the relationship between fields in various TD structures. A new test for the existence of interplanetary magnetic field draping around MC and BEHF is proposed and verified. It is concluded that the magnetic field configuration around MC is more adequately consistent with the concept of magnetic line draping than is the case around BEHF Two methods are proposed to infer the location of solar sources of TD from their characteristics at R = 1 AU.
Excited-State Dynamics of the Thiopurine Prodrug 6-Thioguanine: Can N9-Glycosylation Affect Its Phototoxic Activity?

PubMed

Ashwood, Brennan; Jockusch, Steffen; Crespo-Hernández, Carlos E

2017-02-28

6-Thioguanine, an immunosuppressant and anticancer prodrug, has been shown to induce DNA damage and cell death following exposure to UVA radiation. Its metabolite, 6-thioguanosine, plays a major role in the prodrug's overall photoreactivity. However, 6-thioguanine itself has proven to be cytotoxic following UVA irradiation, warranting further investigation into its excited-state dynamics. In this contribution, the excited-state dynamics and photochemical properties of 6-thioguanine are studied in aqueous solution following UVA excitation at 345 nm in order to provide mechanistic insight regarding its photochemical reactivity and to scrutinize whether N9-glycosylation modulates its phototoxicity in solution. The experimental results are complemented with time-dependent density functional calculations that include solvent dielectric effects by means of a reaction-field solvation model. UVA excitation results in the initial population of the S₂(ππ*) state, which is followed by ultrafast internal conversion to the S₁(nπ*) state and then intersystem crossing to the triplet manifold within 560 ± 60 fs. A small fraction (ca. 25%) of the population that reaches the S₁(nπ*) state repopulates the ground state. The T₁(ππ*) state decays to the ground state in 1.4 ± 0.2 μs under N₂-purged conditions, using a 0.2 mM concentration of 6-thioguanine, or it can sensitize singlet oxygen in 0.21 ± 0.02 and 0.23 ± 0.02 yields in air- and O₂-saturated solution, respectively. This demonstrates the efficacy of 6-thioguanine to act as a Type II photosensitizer. N9-glycosylation increases the rate of intersystem crossing from the singlet to triplet manifold, as well as from the T₁(ππ*) state to the ground state, which lead to a ca. 40% decrease in the singlet oxygen yield under air-saturated conditions. Enhanced vibronic coupling between the singlet and triplet manifolds due to a higher density of vibrational states is proposed to be responsible for the observed
A novel approach to dual excitation ratiometric optical mapping of cardiac action potentials with di-4-ANEPPS using pulsed LED excitation.

PubMed

Bachtel, Andrew D; Gray, Richard A; Stohlman, Jayna M; Bourgeois, Elliot B; Pollard, Andrew E; Rogers, Jack M

2011-07-01

We developed a new method for ratiometric optical mapping of transmembrane potential (V(m)) in cardiac preparations stained with di-4-ANEPPS. V(m)-dependent shifts of excitation and emission spectra establish two excitation bands (<481 and >481 nm) that produce fluorescence changes of opposite polarity within a single emission band (575-620 nm). The ratio of these positive and negative fluorescence signals (excitation ratiometry) increases V(m) sensitivity and removes artifacts common to both signals. We pulsed blue (450 ± 10 nm) and cyan (505 ± 15 nm) light emitting diodes (LEDs) at 375 Hz in alternating phase synchronized to a camera (750 frames-per-second). Fluorescence was bandpass filtered (585 ± 20 nm). This produced signals with upright (blue) and inverted (cyan) action potentials (APs) interleaved in sequential frames. In four whole swine hearts with motion chemically arrested, fractional fluorescence for blue, cyan, and ratio signals was 1.2 ± 0.3%, 1.2 ± 0.3%, and 2.4 ± 0.6%, respectively. Signal-to-noise ratios were 4.3 ± 1.4, 4.0 ± 1.2, and 5.8 ± 1.9, respectively. After washing out the electromechanical uncoupling agent, we characterized motion artifact by cross-correlating blue, cyan, and ratio signals with a signal with normal AP morphology. Ratiometry improved cross-correlation coefficients from 0.50 ± 0.48 to 0.81 ± 0.25, but did not cancel all motion artifacts. These findings demonstrate the feasibility of pulsed LED excitation ratiometry in myocardium. © 2011 IEEE
Shedding light on the Early Pleistocene of TD6 (Gran Dolina, Atapuerca, Spain): The technological sequence and occupational inferences

PubMed Central

2018-01-01

This paper aims to update the information available on the lithic assemblage from the entire sequence of TD6 now that the most recent excavations have been completed, and to explore possible changes in both occupational patterns and technological strategies evidenced in the unit. This is the first study to analyse the entire TD6 sequence, including subunits TD6.3 and TD6.1, which have never been studied, along with the better-known TD6.2 Homo antecessor-bearing subunit. We also present an analysis of several lithic refits found in TD6, as well as certain technical features that may help characterise the hominin occupations. The archaeo-palaeontological record from TD6 consists of 9,452 faunal remains, 443 coprolites, 1,046 lithic pieces, 170 hominin remains and 91 Celtis seeds. The characteristics of this record seem to indicate two main stages of occupation. In the oldest subunit, TD6.3, the lithic assemblage points to the light and limited hominin occupation of the cave, which does, however, grow over the course of the level. In contrast, the lithic assemblages from TD6.2 and TD6.1 are rich and varied, which may reflect Gran Dolina cave’s establishment as a landmark in the region. Despite the occupational differences between the lowermost subunit and the rest of the deposit, technologically the TD6 lithic assemblage is extremely homogeneous throughout. In addition, the composition and spatial distribution of the 12 groups of lithic refits found in unit TD6, as well as the in situ nature of the assemblage demonstrate the high degree of preservation at the site. This may help clarify the nature of the Early Pleistocene hominin occupations of TD6, and raise reasonable doubt about the latest interpretations that support the ex situ character of the assemblage as a whole. PMID:29370188
Shedding light on the Early Pleistocene of TD6 (Gran Dolina, Atapuerca, Spain): The technological sequence and occupational inferences.

PubMed

Mosquera, Marina; Ollé, Andreu; Rodríguez-Álvarez, Xose Pedro; Carbonell, Eudald

2018-01-01

This paper aims to update the information available on the lithic assemblage from the entire sequence of TD6 now that the most recent excavations have been completed, and to explore possible changes in both occupational patterns and technological strategies evidenced in the unit. This is the first study to analyse the entire TD6 sequence, including subunits TD6.3 and TD6.1, which have never been studied, along with the better-known TD6.2 Homo antecessor-bearing subunit. We also present an analysis of several lithic refits found in TD6, as well as certain technical features that may help characterise the hominin occupations. The archaeo-palaeontological record from TD6 consists of 9,452 faunal remains, 443 coprolites, 1,046 lithic pieces, 170 hominin remains and 91 Celtis seeds. The characteristics of this record seem to indicate two main stages of occupation. In the oldest subunit, TD6.3, the lithic assemblage points to the light and limited hominin occupation of the cave, which does, however, grow over the course of the level. In contrast, the lithic assemblages from TD6.2 and TD6.1 are rich and varied, which may reflect Gran Dolina cave's establishment as a landmark in the region. Despite the occupational differences between the lowermost subunit and the rest of the deposit, technologically the TD6 lithic assemblage is extremely homogeneous throughout. In addition, the composition and spatial distribution of the 12 groups of lithic refits found in unit TD6, as well as the in situ nature of the assemblage demonstrate the high degree of preservation at the site. This may help clarify the nature of the Early Pleistocene hominin occupations of TD6, and raise reasonable doubt about the latest interpretations that support the ex situ character of the assemblage as a whole.
First measurement of the 2.4 MeV and 2.9 MeV 6He three-cluster resonant states via the 3H(4He, pα)2n four-body reaction

NASA Astrophysics Data System (ADS)

Mandaglio, Giuseppe; Povoroznyk, Orest; Gorpinich, Olga K.; Jachmenjov, Olexiy O.; Anastasi, Antonio; Curciarello, Francesca; de Leo, Veronica; Mokhnach, Hanna V.; Ponkratenko, Oleg; Roznyuk, Yuri; Fazio, Giovanni; Giardina, Giorgio

2014-06-01

Two new low-lying 6He levels at excitation energies of about 2.4 MeV and 2.9 MeV were observed in the experimental investigation of the p-α coincidence spectra obtained by the 3H(4He, pα)2n four-body reaction at E4He beam energy of 27.2 MeV. The relevant E* peak energy and Γ energy width spectroscopic parameters for such 6He* excited states decaying into the α+n+n channel were obtained by analyzing the bidimensional (Ep, Eα) energy spectra. The present new result of two low-lying 6He* excited states above the 4He+2n threshold energy of 0.974 MeV is important for the investigation of the nuclear structure of neutron-rich light nuclei and also as a basic test for theoretical models in the study of the three-cluster resonance feature of 6He.
Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

PubMed

Ayub, Rabia; Bakouri, Ouissam El; Jorner, Kjell; Solà, Miquel; Ottosson, Henrik

2017-06-16

Compounds that can be labeled as "aromatic chameleons" are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T 1 ) of the compounds. Decreases in T 1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T 1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird's rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T 1 energies go down as the total number of aromatic cycles within a molecule in the T 1 state increases.
Looking but Not Seeing: Atypical Visual Scanning and Recognition of Faces in 2 and 4-Year-Old Children with Autism Spectrum Disorder

ERIC Educational Resources Information Center

Chawarska, Katarzyna; Shic, Frederick

2009-01-01

This study used eye-tracking to examine visual scanning and recognition of faces by 2- and 4-year-old children with autism spectrum disorder (ASD) (N = 44) and typically developing (TD) controls (N = 30). TD toddlers at both age levels scanned and recognized faces similarly. Toddlers with ASD looked increasingly away from faces with age,…
Resonance-enhanced electron-impact excitation of Cu-like gold

NASA Astrophysics Data System (ADS)

Xia, L.; Zhang, C. Y.; Si, R.; Guo, X. L.; Chen, Z. B.; Yan, J.; Li, S.; Chen, C. Y.; Wang, K.

2017-09-01

Employing the independent-process and isolated-resonance approximations using distorted-waves (IPIRDW), we have performed a series of calculations of the resonance-enhanced electron-impact excitations (EIE) among 27 singly excited levels from the n ≤ 6 configurations of Cu-like gold (Au, Z = 79). Resonance excitation (RE) contributions from both the n = 4 → 4 - 7 and n = 3 → 4 core excitations have been considered. Our results demonstrate that RE contributions are significant and enhance the effective collision strengths (ϒ) of certain excitations by up to an order of magnitude at low temperature (106.1 K), and are still important at relatively high temperature (107.5 K). Results from test calculations of the resonance-enhanced EIE processes among 16 levels from the n ≤ 5 configurations using both the Dirac R-matrix (DRM) and IPIRDW approaches agree very well with each other. This means that the close-coupling effects are not important for this ion, and thus warrants the reliability of present resonance-enhanced EIE data among the 27 levels. The results from the collisional-radiative model (CRM) show that, at 3000 eV, near where Cu-like Au is most abundant, RE contributions have important effects (up to 25%) on the density diagnostic line intensity ratios, which are sensitive near 1020 cm-3. The present work is the first EIE research including RE contributions for Cu-like Au. Our EIE data are more accurate than previous results due to our consideration of RE contributions, and the data should be helpful for modeling and diagnosing a variety of plasmas.
Electronic and optical properties of GaN/AlN quantum dots on Si(111) subject to in-plane uniaxial stresses and variable excitation

NASA Astrophysics Data System (ADS)

Moshe, O.; Rich, D. H.; Birner, S.; Povolotskyi, M.; Damilano, B.; Massies, J.

2010-10-01

We have studied the excitation- and polarization-dependent optical properties of GaN/AlN self-assembled quantum dots (QDs) grown on Si(111) substrates. Ensembles of QDs were subject to various external stress configurations that resulted from the thermal expansion coefficient mismatch between the GaN/AlN layers and the Si(111) substrate and ranged from in-plane uniaxial stress, primarily along the ⟨112¯0⟩ directions, to in-plane biaxial stress, having magnitudes ranging from 20-30 kbar. Limited regions of uniaxial stress were obtained by exploiting naturally occurring microcracks that form during the postgrowth cooling. These microcracks act as stressors in order to create the highly localized regions of uniaxial stress. The local strain tensors for such QDs, which are subject to an interfacial stress perturbation, have been determined by modeling the dependence of the QD excitonic transition energy on the interfacial stress. Cathodoluminescence (CL) measurements of the excitonic transitions exhibit an in-plane linear polarization anisotropy in close proximity to microcracks. The polarization anisotropy is strongly dependent on the sample temperature and the electron beam excitation conditions used to excite the QD ensemble. Localized CL spectroscopy of the QDs exhibits emissions from both the ground and excited states, whose relative contributions depend on the level of excitation and temperature. Experimental results indicate that the polarization anisotropy vanishes at high temperatures (˜300 K) with an increasing excitation of the QDs, while the anisotropy decreases more slowly with excitation at low temperatures (˜60 K). A theoretical modeling of the effect of carrier filling on the polarization anisotropy and the excitonic transition energy was performed, as based on three-dimensional self-consistent solutions of the Schrödinger and Poisson equations using the 6×6 kṡp and effective mass methods for calculations of the e-h wave functions and
TD-LTE Wireless Private Network QoS Transmission Protection

NASA Astrophysics Data System (ADS)

Zhang, Jianming; Cheng, Chao; Wu, Zanhong

With the commencement of construction of the smart grid, the demand power business for reliability and security continues to improve, the reliability transmission of power TD-LTE Wireless Private Network are more and more attention. For TD-LTE power private network, it can provide different QoS services according to the user's business type, to protect the reliable transmission of business. This article describes in detail the AF module of PCC in the EPC network, specifically introduces set up AF module station and QoS mechanisms in the EPS load, fully considers the business characteristics of the special power network, establishing a suitable architecture for mapping QoS parameters, ensuring the implementation of each QoS business. Through using radio bearer management, we can achieve the reliable transmission of each business on physical channel.
Tunable emission and excited state absorption induced optical limiting in Tb2(MoO4)3: Sm3+/Eu3+ nanophosphors

NASA Astrophysics Data System (ADS)

Mani, Kamal P.; Sreekanth, Perumbilavil; Vimal, G.; Biju, P. R.; Unnikrishnan, N. V.; Ittyachen, M. A.; Philip, Reji; Joseph, Cyriac

2016-12-01

Photoluminescence properties and optical limiting behavior of pure and Sm3+/Eu3+ doped Tb2(MoO4)3 nanophosphors are investigated. The prepared nanophosphors exhibit excellent emission when excited by UV light. Color-tunable emissions in Tb2-xSmx(MoO4)3 and Tb2-xEux(MoO4)3 are realized by employing different excitation wavelengths or by controlling the doping concentration of Sm3+ and Eu3+. Luminescence quantum yield and CIE chromatic coordinates of the prepared phosphors were also presented. Optical limiting properties of the samples are investigated by open aperture Z-scan technique using 5 ns laser pulses at 532 nm. Numerical fitting of the measured Z-scan data to the relevant nonlinear transmission equations reveals that the nonlinear absorption is arising from strong excited state absorption, along with weak absorption saturation and it is found that the optical nonlinearity of Tb2(MoO4)3 increases with Sm3+/Eu3+doping. Parameters such as saturation fluence, excited state absorption cross section and ground state absorption cross section of the samples have been determined numerically, from which the figure of merit for nonlinear absorption is calculated. The excited state absorption cross-section of the samples is found to be one order of magnitude higher than that of the ground state absorption cross-section, indicating strong reverse saturable absorption. These results indicate that Sm3+/Eu3+ doped Tb2(MoO4)3 nanophosphors are efficient media for UV/n-UV pumped LEDs, and are also potential candidates for designing efficient optical limiting devices for the protection of human eyes and sensitive optical detectors from harmful laser radiation.

Excited state absorption spectra of dissolved and aggregated distyrylbenzene: A TD-DFT state and vibronic analysis

NASA Astrophysics Data System (ADS)

Oliveira, Eliezer Fernando; Shi, Junqing; Lavarda, Francisco Carlos; Lüer, Larry; Milián-Medina, Begoña; Gierschner, Johannes

2017-07-01

A time-dependent density functional theory study is performed to reveal the excited state absorption (ESA) features of distyrylbenzene (DSB), a prototype π-conjugated organic oligomer. Starting with a didactic insight to ESA based on simple molecular orbital and configuration considerations, the performance of various density functional theory functionals is tested to reveal the full vibronic ESA features of DSB at short and long probe delay times.
Absorption spectra of PTCDI: A combined UV-Vis and TD-DFT study

NASA Astrophysics Data System (ADS)

Oltean, Mircea; Calborean, Adrian; Mile, George; Vidrighin, Mihai; Iosin, Monica; Leopold, Loredana; Maniu, Dana; Leopold, Nicolae; Chiş, Vasile

2012-11-01

Absorption spectra of PTCDI (3,4,9,10-perylene-tetracarboxylic-diimide) have been investigated in chloroform, N,N'-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). While no signature of assembled PTCDI molecules is observed in chloroform solution, distinct bands assigned to their aggregation have been identified in DMF and DMSO solutions. PTCDI monomers show very similar absorption patterns in chloroform and DMSO solutions. Experimental data, including the vibronic structure of the absorption spectra were explained based on the Franck-Condon approximation and quantum chemical results obtained at PBE0-DCP/6-31+G(d,p) level of theory. Geometry optimization of the first excited state leads to a nice agreement between the calculated adiabatic transition energies and experimental data.
Nonradiative recombination centers in GaAs:N δ-doped superlattice revealed by two-wavelength-excited photoluminescence

NASA Astrophysics Data System (ADS)

Dulal Haque, Md.; Kamata, Norihiko; Fukuda, Takeshi; Honda, Zentaro; Yagi, Shuhei; Yaguchi, Hiroyuki; Okada, Yoshitaka

2018-04-01

We use two-wavelength-excited photoluminescence (PL) to investigate nonradiative recombination (NRR) centers in GaAs:N δ-doped superlattice (SL) structures grown by molecular beam epitaxy. The change in photoluminescence (PL) intensity due to the superposition of below-gap excitation at energies of 0.75, 0.80, 0.92, and 0.95 eV and above-gap excitation at energies of 1.69 or 1.45 eV into the GaAs conduction band and the E- band implies the presence of NRR centers inside the GaAs:N δ-doped SL and/or GaAs layers. The change in PL intensity as a function of the photon number density of below-gap excitation is examined for both bands, which enables us to determine the distribution of NRR centers inside the GaAs:N δ-doped SL and GaAs layers. We propose recombination models to explain the experimental results. Defect-related parameters that give a qualitative insight into the samples are investigated systematically by fitting the rate equations to the experimental data.
Diffusional creep and creep degradation in the dispersion-strengthened alloy TD-NiCr

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1972-01-01

Dispersoid-free regions were observed in TD-NiCr (Ni-20Cr-2ThO2) after slow strain rate testing in air from 1145 to 1590 K. Formation of the dispersoid-free regions appears to be the result of diffusional creep. The net effect of this creep is the degradation of TD-NiCr to a duplex microstructure. Degradation is further enhanced by the formation of voids and integranular oxidation in the thoria-free regions. These regions apparently provided sites for void formation and oxide growth since the strength and oxidation resistance of Ni-20Cr is much less than Ni-20Cr-2ThO2. This localized oxidation does not appear to reduce the static load bearing capacity of TD-NiCr since long stress rupture lives were observed even with heavily oxidized microstructures. But this oxidation does significantly reduce the ductility and impact resistance of the material. Dispersoid-free bands and voids were also observed for two other dispersion strengthened alloys, TD-NiCrAl and IN-853. Thus, it appears that diffusional creep is charactertistic of dispersion-strengthened alloys and can play a major role in the creep degradation of these materials.
Enhanced efficacy of TD53, a novel algicidal agent, against the harmful algae via the liposomal delivery system.

PubMed

Han, Hyo-Kyung; Kim, Yeon-Mi; Lim, Soo-Jeong; Hong, Soon-Seok; Jung, Seul-Gi; Cho, Hoon; Lee, Wonjae; Jin, Eonseon

2011-02-28

The present study aimed to design the liposomal delivery system for TD53, a novel algicial drug in order to improve the delivery properties of TD53 and evaluate its algicidal effects as well as selectivity against harmful and non-harmful algae. Liposomes of TD53 were prepared with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) by a lyophilization, resulting in relatively small size vesicles (234±38nm) and narrow size distribution (PI=0.130±0.027). The drug leakage from the liposome was negligible in the F/2 media (<2% during 96h incubation). Subsequently algicidal activity of liposomal TD53 against harmful and nonharmful algae was evaluated at various concentrations. The IC(50) values of TD53 in liposome against harmful algae such as Chattonella marina, Heterosigma akashiwo and Cocholodinium polykrikoides were 2.675, 2.029, and 0.480μM, respectively, and were reduced by approximately 50% compared to those obtained from non-liposomal TD53. In contrast, the algicidal effect of liposomal TD53 was insignificant against non-harmful algae including Navicula pelliculosa, Nannochloropsis oculata and Phaeodactylum EPV. Those results suggested that liposomal delivery systems might be effective to enhance the efficacy of TD53 while maintaining the selectivity to harmful algal species. Copyright Â© 2010 Elsevier B.V. All rights reserved.
Red Luminescent Eu(III) Coordination Bricks Excited on Blue LED Chip.

PubMed

Koizuka, Toru; Yanagisawa, Kei; Hirai, Yuichi; Kitagawa, Yuichi; Nakanishi, Takayuki; Fushimi, Koji; Hasegawa, Yasuchika

2018-06-18

Three types of red luminescent Eu(III) complexes with Schiff base and hfa ligands (hfa: hexafluoroacetylacetonate), mononuclear [Eu(hfa) 2 (OAc)(salen) 2 ] (OAc: acetate anion, salen: N,N'-bis(salicylidene)ethylenediamine), brick-type [Eu 2 (hfa) 4 (OAc) 2 (salbn) 2 ] (salbn: N,N'-bis(salicylidene)-1,4-butanediamine), and polynuclear [Eu(hfa) 2 (OAc)(salhen)] n (salhen: N,N'-bis(salicylidene)-1,6-hexanediamine) are reported for white light-emitting diode (LED) devices. Among these complexes, brick-type [Eu 2 (hfa) 4 (OAc) 2 (salbn) 2 ] excited by blue light (460 nm) exhibits the photosensitized quantum yield (Φ π-π* = 47%) and remarkably high efficiency of sensitization (η sens = 96%). The efficiency of sensitization is caused by the excited state based on ligand-ligand interaction between the Schiff base and hfa ligands in Eu(III) complexes. To fabricate LED devices, the red luminescent [Eu 2 (hfa) 4 (OAc) 2 (salbn) 2 ] was mounted on an InGaN blue LED chip.
Collisional excitation and radiative properties of N II - The strong intercombination (1D - 3P0) transition at 748 A

NASA Technical Reports Server (NTRS)

Tripp, T. M.; Shemansky, D. E.; James, G. K.; Ajello, J. M.

1991-01-01

Laboratory measurements of EUV emission from electron-excited N2 have been obtained at medium resolution, providing N II EUV emission cross section measurements and allowing the confirmation of recent calculations by Fawcett (1987) indicating the presence of a strong intercombination line in N II at 748.37 A. The most recently available data are used to predict the basic collisional and radiative properties of N II, the plasma diagnostic properties are briefly explored, and radiative cooling coefficients are given. Some basic properties of electron-excited N II and N2 are examined in the EUV in order to diagnose emission spectra of the earth and Titan. The N II emissions in the earth dayglow, particularly at 916 A, are much brighter than current estimates of source rates. The N II 1085 A line in the dayglow contains a significant component from dissociative photoionization excitation. The N II 1085 A, 916 A, and 670 A lines in the Titan dayglow spectrum appear to be compatible with direct electron excitation of N2.
Measurements of Excitation Functions and Line Polarizations for Electron Impact Excitation of the n = 2, 3 States of Atomic Hydrogen in the Energy Range 11 - 2000 eV

NASA Technical Reports Server (NTRS)

James, G. K.; Ajello, J. M.; Kanik, I.; Slevin, J.; Franklin, B.; Shemansky, D.

1993-01-01

The electron-atomic hydrogen scattering system is an important testing ground for theoretical models and has received a great deal of attention from experimentalists and theoreticians alike over the years. A complete description of the excitation process requires a knowledge of many different parameters, and experimental measurements of these parameters have been performed in various laboratories around the world. As far as total cross section data are concerned it has been noted that the discrepancy between the data of Long et al. and Williams for n = 2 excitations needs to be resolved in the interests of any further refinement of theory. We report new measurements of total cross sections and atomic line polarizations for both n=2 and n=3 excitations at energies from threshold to 2000 eV...
Magnetic excitations in the orbital disordered phase of MnV2O4

NASA Astrophysics Data System (ADS)

Matsuura, Keisuke; Sagayama, Hajime; Uehara, Amane; Nii, Yoichi; Kajimoto, Ryoichi; Kamazawa, Kazuya; Ikeuchi, Kazuhiko; Ji, Sungdae; Abe, Nobuyuki; Arima, Taka-hisa

2018-05-01

We have investigated the temperature dependence of magnetic dynamics in a spinel-type vanadium oxide MnV2O4 by inelastic neutron scattering. The scattering intensity of excitation around 20 meV disappears in the collinear intermediate-temperature cubic-ferrimagnetic phase, which reveals that this excitation should be peculiar to the orbital ordered phase. We have found a weakly dispersive mode emergent from a non-integer wavevector (1.4,1.4,0) at 56 K, which lies in the cubic-ferrimagnetic phase between non-coplanar ferrimagnetic and paramagnetic phases. This indicates that the probable presence of an incommensurate instability in the simple collinear structure.
Onset of the Efficiency Droop in GaInN Quantum Well Light-Emitting Diodes under Photoluminescence and Electroluminescence Excitation

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

Lin, Guan-Bo; Schubert, E. Fred; Cho, Jaehee

2015-08-19

The efficiency of Ga0.87In0.13N/GaN single and multiple quantum well (QW) light-emitting diodes is investigated under photoluminescence (PL) and electroluminescence (EL) excitation. By measuring the laser spot area (knife-edge method) and the absorbance of the GaInN QW (transmittance/reflectance measurements), the PL excitation density can be converted to an equivalent EL excitation density. The EL efficiency droop-onset occurs at an excitation density of 2.08 × 1026 cm–3 s–1 (J = 10 A/cm2), whereas no PL efficiency droop is found for excitation densities as high as 3.11 × 1027 cm–3 s–1 (J = 149 A/cm2). Considering Shockley–Read–Hall, radiative, and Auger recombination and includingmore » carrier leakage shows that the EL efficiency droop is consistent with a reduction of injection efficiency.« less
Spin-Orbital Excitations in Ca2 RuO4 Revealed by Resonant Inelastic X-Ray Scattering

NASA Astrophysics Data System (ADS)

Das, L.; Forte, F.; Fittipaldi, R.; Fatuzzo, C. G.; Granata, V.; Ivashko, O.; Horio, M.; Schindler, F.; Dantz, M.; Tseng, Yi; McNally, D. E.; Rønnow, H. M.; Wan, W.; Christensen, N. B.; Pelliciari, J.; Olalde-Velasco, P.; Kikugawa, N.; Neupert, T.; Vecchione, A.; Schmitt, T.; Cuoco, M.; Chang, J.

2018-01-01

The strongly correlated insulator Ca2 RuO4 is considered as a paradigmatic realization of both spin-orbital physics and a band-Mott insulating phase, characterized by orbitally selective coexistence of a band and a Mott gap. We present a high resolution oxygen K -edge resonant inelastic x-ray scattering study of the antiferromagnetic Mott insulating state of Ca2 RuO4 . A set of low-energy (about 80 and 400 meV) and high-energy (about 1.3 and 2.2 eV) excitations are reported, which show strong incident light polarization dependence. Our results strongly support a spin-orbit coupled band-Mott scenario and explore in detail the nature of its exotic excitations. Guided by theoretical modeling, we interpret the low-energy excitations as a result of composite spin-orbital excitations. Their nature unveils the intricate interplay of crystal-field splitting and spin-orbit coupling in the band-Mott scenario. The high-energy excitations correspond to intra-atomic singlet-triplet transitions at an energy scale set by Hund's coupling. Our findings give a unifying picture of the spin and orbital excitations in the band-Mott insulator Ca2 RuO4 .
Contrasting intermolecular and intramolecular exciplex formation of a 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad.

PubMed

Imoto, Mitsutaka; Ikeda, Hiroshi; Fujii, Takayuki; Taniguchi, Hisaji; Tamaki, Akihiro; Takeda, Motonori; Mizuno, Kazuhiko

2010-05-07

An intramolecular exciplex is formed upon excitation of the cyclohexane solution of the 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad, but little if any intramolecular CT complex exists in the ground state of this substance in solution. In contrast, in the crystalline state, the dyad forms an intermolecular mixed-stack CT complex in the ground state and an intermolecular exciplex when it is photoexcited.
On the truncation of the number of excited states in density functional theory sum-over-states calculations of indirect spin spin coupling constants

NASA Astrophysics Data System (ADS)

Zarycz, M. Natalia C.; Provasi, Patricio F.; Sauer, Stephan P. A.

2015-12-01

It is investigated, whether the number of excited (pseudo)states can be truncated in the sum-over-states expression for indirect spin-spin coupling constants (SSCCs), which is used in the Contributions from Localized Orbitals within the Polarization Propagator Approach and Inner Projections of the Polarization Propagator (IPPP-CLOPPA) approach to analyzing SSCCs in terms of localized orbitals. As a test set we have studied the nine simple compounds, CH4, NH3, H2O, SiH4, PH3, SH2, C2H2, C2H4, and C2H6. The excited (pseudo)states were obtained from time-dependent density functional theory (TD-DFT) calculations with the B3LYP exchange-correlation functional and the specialized core-property basis set, aug-cc-pVTZ-J. We investigated both how the calculated coupling constants depend on the number of (pseudo)states included in the summation and whether the summation can be truncated in a systematic way at a smaller number of states and extrapolated to the total number of (pseudo)states for the given one-electron basis set. We find that this is possible and that for some of the couplings it is sufficient to include only about 30% of the excited (pseudo)states.
An electron microscopy examination of primary recrystallization in TD-nickel.

NASA Technical Reports Server (NTRS)

Petrovic, J. J.; Ebert, L. J.

1972-01-01

Primary recrystallization in TD-nickel 1 in. bar has previously been regarded as the process by which the initial fine grain structure is converted to a coarse grain size (increases in grain size by 500 times) under suitable deformation and annealing conditions. This process is dependent on deformation mode. While it occurs readily after rolling transverse to the bar axis and annealing (800 C), it is completely inhibited by longitudinal rolling and swaging deformations, even for very high (1320 C) annealing temperatures. A transmission electron microscopy examination of deformation and annealing substructures indicates that primary recrystallization in TD-nickel 1 in. bar actually occurs on the sub-light optical level, to produce a grain structure similar in size to the initial fine grained state.
Coulomb Excitation of 78,80Se and the radioactive 84Se (N = 50) isotopes

NASA Astrophysics Data System (ADS)

Galindo-Uribarri, A.; Padilla-Rodal, E.; Garcia-Ruiz, R. F.; Allmond, J. M.; Batchelder, J. C.; Beene, J. R.; Lagergren, K. B.; Mueller, P. E.; Radford, D. C.; Stracener, D. W.; Urrego-Blanco, J. P.; Varner, R. L.; Yu, C.-H.

2011-10-01

Coulomb excitation is a purely electromagnetic excitation process of nuclear states due to the Coulomb field of two colliding nuclei. It is a very precise tool to measure excitation probabilities and provide insight on the collectivity of nuclear excitations and in particular on nuclear shapes. We have measured the B(E2) value of various nuclei in the mass A ~ 80 region using particle-gamma coincidences with the HyBall and Clarion arrays at HRIBF. The Coulomb excitation of various projectile-target combinations (ASe on 12C, 24Mg, 27Al and 50Ti) allow the use of consistency cross checks and the systematic study of isotopic and isotonic chains using both stable and radioactive nuclei under almost identical experimental conditions.We present new results for 78Se, 80Se and the radioactive nucleus 84Se (N = 50). Research sponsored by the Office of Nuclear Physics, U.S. Department of Energy and CONACyT Grant 103366.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Yanai, Takeshi; Fann, George I.; Beylkin, Gregory

Using the fully numerical method for time-dependent Hartree–Fock and density functional theory (TD-HF/DFT) with the Tamm–Dancoff (TD) approximation we use a multiresolution analysis (MRA) approach to present our findings. From a reformulation with effective use of the density matrix operator, we obtain a general form of the HF/DFT linear response equation in the first quantization formalism. It can be readily rewritten as an integral equation with the bound-state Helmholtz (BSH) kernel for the Green's function. The MRA implementation of the resultant equation permits excited state calculations without virtual orbitals. Moreover, the integral equation is efficiently and adaptively solved using amore » numerical multiresolution solver with multiwavelet bases. Our implementation of the TD-HF/DFT methods is applied for calculating the excitation energies of H 2, Be, N 2, H 2O, and C 2H 4 molecules. The numerical errors of the calculated excitation energies converge in proportion to the residuals of the equation in the molecular orbitals and response functions. The energies of the excited states at a variety of length scales ranging from short-range valence excitations to long-range Rydberg-type ones are consistently accurate. It is shown that the multiresolution calculations yield the correct exponential asymptotic tails for the response functions, whereas those computed with Gaussian basis functions are too diffuse or decay too rapidly. Finally, we introduce a simple asymptotic correction to the local spin-density approximation (LSDA) so that in the TDDFT calculations, the excited states are correctly bound.« less
VUV Study of Electron-Pyrimidine Dissociative Excitation

NASA Astrophysics Data System (ADS)

Hein, Jeff; Al-Khazraji, Hajar; Tiessen, Collin; Lukic, Dragan; Trocchi, Joshuah; McConkey, William

2013-05-01

A crossed electron-gas beam system coupled to a VUV spectrometer has been used to investigate the dissociation of pyrimidine (C4H4N2) into excited atomic fragments in the electron-impact energy range from threshold to 375 eV. Data have been made absolute using Lyman- α from H2 as a secondary standard. The main features in the spectrum are the H Lyman series lines. The emission cross section of Lyman- α is measured to be (2.44 +/- 0.25) 10-18 cm2 at 100 eV impact energy. The probability of extracting C or N atoms from the ring is shown to be very small. Possible dissociation channels and excitation mechanisms in the parent molecule will be discussed. The authors thank NSERC (Canada) for financial support.
Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

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

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.

The excited state dynamics of solvated [Fe(bpy)(CN) 4] 2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less
Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

DOE PAGES

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.; ...

2018-01-19

The excited state dynamics of solvated [Fe(bpy)(CN) 4] 2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less
Solid-state and fusion resistance spot welding of TD-NiCr sheet

NASA Technical Reports Server (NTRS)

Moore, T. J.

1973-01-01

By using specially processed TD-NiCr sheet in both 0.4-mm (0.015-in.) and 1.6-mm (0.062-in.) thicknesses and carefully selected welding procedures, solid state resistance spot welds were produced which, after postheating at 1200 C, were indistinguishable from the parent material. Stress-rupture shear tests of single-spot lap joints in 0.4-mm (0.015-in.) thick sheet showed that these welds were as strong as the parent material. Similar results were obtained in tensile-shear tests at room temperature and 1100 C and in fatigue tests. Conventional fusion spot welds in commercial sheet were unsatisfactory because of poor stress-rupture shear properties resulting from metallurgical damage to the parent material.

^235U(n,xnγ) Excitation Function Measurements Using Gamma-Ray Spectroscopy at GEANIE

NASA Astrophysics Data System (ADS)

Younes, W.; Becker, J. A.; Bernstein, L. A.; Archer, D. E.; Stoyer, M. A.; Hauschild, K.; Drake, D. M.; Johns, G. D.; Nelson, R. O.; Wilburn, S. W.

1998-04-01

The ^235U(n,xn) cross sections (where x<=2) have previously been measured at several incident neutron energies. In particular, the ^235U(n,2n) cross section has been measured(J. Frehaut et al.), Nucl. Sci. Eng. 74,29 (1980). reliably up to peak near E_n≈ 11 MeV, but not along the tail which is predicted by some(M.B. Chadwick, private communication.) codes to yield significant (e.g. >= 10% of peak) cross section out to E_n≈ 30 MeV. We have measured gamma-ray spectra resulting from ^235U(n,xn) as a function of neutron energy in the range 1 MeV <~ En <~ 200 MeV using the GEANIE spectrometer at the LANSCE/WNR ``white'' neutron source. We will present excitation functions for the de-excitation gamma rays in ^234,235U compared to predictions from the Hauser-Feshbach-preequilibrium code GNASH(M.B. Chadwick and P.G. Young, Los Alamos Report No. LA-UR-93-104, 1993.).
Spectral and quantum chemical studies on 1,3-bis(N(1)-4-amino-6-methoxypyrimidinebenzenesulfonamide-2,2,4,4-ethane-1,2-dithiol)-2,4-dichlorocyclodiphosph(V)azane and its erbium complex.

PubMed

Al-Mogren, Muneerah M; Alaghaz, Abdel-Nasser M A; El-Gogary, Tarek M

2014-01-24

Novel 1,3-bis(N(1)-4-amino-6-methoxypyrimidine-benzenesulfonamide-2,2,4,4-ethane-1,2-dithiol)-2,4-dichlorocyclodiphosph(V)azane (L), was prepared and their coordinating behavior towards the lanthanide ion Er(III) was studied. The structures of the isolated products are proposed based on elemental analyses, IR, UV-VIS., (1)H NMR, (13)C NMR, (31)P NMR, SEM, XRD, mass spectra, effective magnetic susceptibility measurements and thermogravimetric analysis (TGA). Computational studies have been carried out at the DFT-B3LYP/6-31G(d) level of theory on the structural and spectroscopic properties of L and its binuclear Er(III) complex. Different tautomers of the ligand were optimized at the ab initio DFT level. Keto-form structure is about 17.7 kcal/mol more stable than the enol form (taking zpe correction into account). Simulated IR frequencies were scaled and compared with that experimentally measured. TD-DFT method was used to compute the UV-VIS spectra which compared by the measured electronic spectra. Copyright © 2013 Elsevier B.V. All rights reserved.
Photoinduced ICT vs. excited rotamer intercoversion in two quadrupolar polyaromatic N-methylpyridinium cations.

PubMed

Cesaretti, A; Carlotti, B; Elisei, F; Fortuna, C G; Spalletti, A

2018-01-24

The excited state dynamics of two quadrupolar polyaromatic N-methylpyridinium cations have been fully investigated in order to acquire detailed information on their photo-induced behavior. The two molecules are symmetric push-pull compounds having a D-π-A + -π-D motif, with the same electron-acceptor central unit (A = N-methylpyridinium) and two distinctive electron-donor polyaromatic side groups (D), namely naphthyl and pyrenyl substituents. Both molecules undergo charge transfer during the absorption, as revealed by a significant solvatochromism exhibited with solvent polarity, but the fate of their excited state was found to be markedly different. The careful analysis of the data gathered from femtosecond-resolved fluorescence up-conversion and transient absorption experiments, supported by DFT quantum mechanical calculations and temperature-dependent stationary measurements, shows the leading role of intramolecular charge transfer, assisted by symmetry breaking, in the pyrenyl derivative and that of rotamer interconversion in the naphthtyl one. Both excited state processes are controlled by the viscosity rather than polarity of the solvent, and they occur during inertial solvation in low-viscous media and lengthening up to tens of picoseconds in highly viscous solvents.
Coulomb Excitation of n-rich nuclei along the N = 50 shell closure

NASA Astrophysics Data System (ADS)

Padilla-Rodal, E.; Galindo-Uribarri, A.; Batchelder, J. C.; Beene, J. R.; Bingham, C.; Brown, B. A.; Lagergren, K. B.; Mueller, P. E.; Radford, D. C.; Stracener, D. W.; Urrego-Blanco, J. P.; Varner, R. L.; Yu, C.-H.

2008-04-01

Recently, we have been investigating characteristics of nuclear states around the neutron-rich mass A=80 region [1]. Using the Radioactive Ion Beams (RIBs) produced at HRIBF, we have successfully measured the B(E2) values for ^78,80,82Ge , using Coulomb excitation in inverse kinematics. For the germanium isotopes, these data allow a study of the systematic trend between the subshell N= 40 and the N=50 shell. Using the same technique, we have measured the B(E2) value of various nuclei along the N=50 shell including the radioactive nucleus ^84Se. This value together with our previously measured ^82Ge, and the recent result on ^80Zn from ISOLDE [2] are providing basic experimental information needed for a better understanding of the neutron-rich nuclei around A˜80. We report the new results and compare with shell model calculations. [1] E. Padilla-Rodal et al., Phys. Rev. Lett. 94 (2005) 122501. [2] J. Van de Walle et al., Phys. Rev. Lett. 99 (2007) 142501.
Pulsed-laser excitation of acoustic modes in open high-Q photoacoustic resonators for trace gas monitoring: results for C2H4

NASA Astrophysics Data System (ADS)

Brand, Christian; Winkler, Andreas; Hess, Peter; Miklós, András; Bozóki, Zoltán; Sneider, János

1995-06-01

The pulsed excitation of acoustic resonances was studied with a continuously monitoring photoacoustic detector system. Acoustic waves were generated in C2H4/N 2 gas mixtures by light absorption of the pulses from a transversely excited atmospheric CO2 laser. The photoacoustic part consisted of high-Q cylindrical resonators (Q factor 820 for the first radial mode in N2) and two adjoining variable acoustic filter systems. The time-resolved signal was Fourier transformed to a frequency spectrum of high resolution. For the first radial mode a Lorentzian profile was fitted to the measured data. The outside noise suppression and the signal-to-noise ratio were investigated in a normal laboratory environment in the flow-through mode. The acoustic and electric filter system combined with the
MAOA, DBH and SLC6A4 variants in CHARGE: A case control study of autism spectrum disorders

PubMed Central

Tassone, Flora; Qi, Lihong; Zhang, Wenting; Hansen, Robin L; Pessah, Isaac N; Hertz-Picciotto, Irva

2011-01-01

Background Genetic factors are established to contribute to the development of autism. We examined three loci, serotonin transporter (SLC6A4), dopamine hydroxylase (DBH) and the variable number of tandem repeat promoter of the monoamine oxidase A (MAOA) for association with autism in participants from the CHARGE (CHildhood Autism Risks from Genetics and the Environment) Study, the first large-scale population-based case-control investigation of both environmental and genetic contributions to autism risk. Methods Among male children enrolled in the CHARGE study we tested associations between each of the three polymorphisms and autism (AU) (n=119), or a combined group of autism and other autism spectrum disorders (AU+ASD, which includes an additional n=53) as compared with typically developing controls (TD, n=137). Results The case-control association analysis showed neither SLC6A4 nor DBH to be statistically significantly associated with AU or ASD. However, the male children carrying 4 tandem repeats in the promoter region of the MAOA gene showed a 2-fold higher risk of AU (or AU+ASD) than those carrying allele 3, adjusted for confounders (OR = 2.02, 95% CI = 1.12, 3.65, p = 0.02 for AU vs. TD, and OR = 2.05, 95% CI = 1.19, 3.53, p = 0.01 for ASD vs. TD). In addition, mothers homozygous for the 4 tandem repeat allele showed at least a 3-fold higher risk of AU (or AU+ASD) than mothers homozygous for allele 3 (OR = 3.07, 95% CI = 1.19, 7.91, p = 0.02 for AU vs. TD, and OR = 3.26, 95% CI = 1.35, 7.89, p = 0.009 for AU+ASD vs. TD). Conclusions These results suggest a potential role of the functional MAOA promoter alleles in the male child, the mother, or both in autism spectrum disorders. PMID:21538940
Electron impact excitation of highly charged sodium-like ions

NASA Technical Reports Server (NTRS)

Blaha, M.; Davis, J.

1978-01-01

Optical transition probabilities and electron collision strengths for Ca X, Fe XVI, Zn XX, Kr XXVI and Mo XXXII are calculated for transitions between n equal to 3 and n equal to 4 levels. The calculations neglect relativistic effects on the radial functions. A semi-empirical approach provides wave functions of the excited states; a distorted wave function without exchange is employed to obtain the excitation cross sections. The density dependence of the relative intensities of certain emission lines in the sodium isoelectronic sequence is also discussed.
Electronic absorption, vibrational spectra, nonlinear optical properties, NBO analysis and thermodynamic properties of N-(4-nitro-2-phenoxyphenyl) methanesulfonamide molecule by ab initio HF and density functional methods.

PubMed

Rajamani, T; Muthu, S; Karabacak, M

2013-05-01

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-100 cm(-1) and 4000-400 cm(-1), respectively, for N-(4-nitro-2-phenoxyphenyl) methanesulfonamide molecule. Theoretical calculations were performed by ab initio RHF and density functional theory (DFT) method using 6-31G(d,p) and 6-311G(d,p) basis sets. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra. The frontier orbital energy gap and dipole moment illustrates the high reactivity of the title molecule. The first order hyperpolarizability (β0) and related properties (μ, α and Δα) of the molecule were also calculated. Stability of the molecule arising from hyperconjugative interactions and charge delocalization were analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) anti-bonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. UV-vis spectrum of the compound was recorded in the region 200-500 nm in ethanol and electronic properties such as excitation energies, oscillator strength and wavelength were calculated by TD-DFT/B3LYP, CIS and TD-HF methods using 6-31G(d,p) basis set. Molecular electrostatic potential (MEP) and HOMO-LUMO energy levels are also constructed. The thermodynamic properties of the title compound were calculated at different temperatures and the results reveals the heat capacity (C), and entropy (S) increases with rise in temperature. Copyright © 2013 Elsevier B.V. All rights reserved.
Photofragment Coincidence Imaging of Small I- (H2O)n Clusters Excited to the Charge-transfer-to-solvent State

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

Neumark, D. E. Szpunar, K. E. Kautzman, A. E. Faulhaber, and D. M.; Kautzman, K.E.; Faulhaber, A.E.

2005-11-09

The photodissociation dynamics of small I{sup -}(H{sub 2}O){sub n} (n = 2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel ({approx}90%) is a 2-body process forming neutral I + (H{sub 2}O){sub n} photofragments, and the minor channel is a 3-body process forming I + (H{sub 2}O){sub n-1} + H{sub 2}O fragments. Both process display translational energy (P(E{sub T})) distributions peaking at E{sub T} = 0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather thanmore » to the CTTS state display the same two channels with similar P(E{sub T}) distributions. The observation of similar P(E{sub T}) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited (I(H{sub 2}O){sub n}{sup -})* cluster, or, less probably, that the presence of the excess electron has little effect on the departing I atom.« less
The electronic spectra and the structures of the individual copper(II) chloride and bromide complexes in acetonitrile according to steady-state absorption spectroscopy and DFT/TD-DFT calculations

NASA Astrophysics Data System (ADS)

Olshin, Pavel K.; Myasnikova, Olesya S.; Kashina, Maria V.; Gorbunov, Artem O.; Bogachev, Nikita A.; Kompanets, Viktor O.; Chekalin, Sergey V.; Pulkin, Sergey A.; Kochemirovsky, Vladimir A.; Skripkin, Mikhail Yu.; Mereshchenko, Andrey S.

2018-03-01

The results of spectrophotometric study and quantum chemical calculations for copper(II) chloro- and bromocomplexes in acetonitrile are reported. Electronic spectra of the individual copper(II) halide complexes were obtained in a wide spectral range 200-2200 nm. Stability constants of the individual copper(II) halide complexes in acetonitrile were calculated: log β1 = 8.5, log β2 = 15.6, log β3 = 22.5, log β4 = 25.7 for [CuCln]2-n and log β1 = 17.0, log β2 = 24.6, log β3 = 28.1, log β4 = 30.4 for [CuBrn]2-n. Structures of the studied complexes were optimized and electronic spectra were simulated using DFT and TD-DFT methodologies, respectively. According to the calculations, the more is the number of halide ligands the less is coordination number of copper ion.
Installation Restoration Program. Phase 2. Confirmation/Quantification. Stage 1. Air Force Plant 4, Fort Worth, Texas. Volume 2. Appendix A-1.

DTIC Science & Technology

1987-12-01

N1 4. j -0 z0 Uc n 41 or tD D, C a z 4s -J’ - - -T. = 3 CL Ct UL Cfl a-4 CL c r- 0CL U 4 -40 0 CL - :r j3 :) c c 0 0.’ 0- 1- 0 j c D4 C 4) 4 M 48= u...Ii el ozi - - 1 2 1 * ~ ~ ~ ~ L I.) z T L F-, ~ ~ - - *~~~~~ ~~ 093. j ,U .) . C- i n- zi -7 CD Z- c c c c c I a D- do 0. CL C a- JaJ - LA a) IC= -=1 -4...w N M’ it ’.o r’. M O’ 0 td M ’ 3aW 0 00 0 00 0 0 .- - .4 14 LaJ4 W4V L" Z- Z C3 1=z C= CD U IS LL L W N m’ t U) M 0. 0 . ’-U> CDn I-0 00CSI-W0C S6
Investigation of the 6 p 2(3 P 0) n p Rydberg series of bismuth by multiphoton excitation

NASA Astrophysics Data System (ADS)

Bühler, B.; Cremer, C.; Gerber, G.

1985-03-01

Rydberg states of the odd-parity series 6 p 2(3 p 0) n p of BiI are excited by a three-photon process. A two-photon dissociation of Bi2 into excited atomic states followed by a one-photon absorption leads to highly excited atomic Rydberg states up to n = 32. States of the even-parity Rydberg series 6 p 2(3 p 0) nsJ=1/2, ndJ=3/2 and ndJ=5/2 are also observed. In order to avoid the background caused by ionization of the bismuth molecules we performed a two-color excitation with pulsed dye lasers. With this experiment the 6 p 2(3 p 0) npJ=3/2 Rydberg series could be resolved up to n=75. The increasing quantum defect of this series is due to a perturbing state close to the first ionization limit. By a MQDT analysis we obtain the energy of the perturbing state and a value of 58,761.68±0.1 cm-1 for the first ionization limit of atomic bismuth.
Excitation of lowest electronic states of thymine by slow electrons

NASA Astrophysics Data System (ADS)

Chernyshova, I. V.; Kontros, E. J.; Markush, P. P.; Shpenik, O. B.

2013-11-01

Excitation of lowest electronic states of the thymine molecules in the gas phase is studied by elec- tron energy loss spectroscopy. In addition to dipole-allowed transitions to singlet states, transitions to the lowest triplet states were observed. The low-energy features of the spectrum at 3.66 and 4.61 eV are identified with the excitation of the first triplet states 13 A' (π → π*) and 13 A″ ( n → π*). The higher-lying features at 4.96, 5.75, 6.17, and 7.35 eV are assigned mainly to the excitation of the π → π* transitions to the singlet states of the molecule. The excitation dynamics of the lowest states is studied. It is found that the first triplet state 13 A'(π → π*) is most efficiently excited at a residual energy close to zero, while the singlet 21 A'(π → π*) state is excited with almost identical efficiency at different residual energies.
Coulomb excitation of the proton-dripline nucleus Na20

NASA Astrophysics Data System (ADS)

Schumaker, M. A.; Cline, D.; Hackman, G.; Pearson, C. J.; Svensson, C. E.; Wu, C. Y.; Andreyev, A.; Austin, R. A. E.; Ball, G. C.; Bandyopadhyay, D.; Becker, J. A.; Boston, A. J.; Boston, H. C.; Buchmann, L.; Churchman, R.; Cifarelli, F.; Cooper, R. J.; Cross, D. S.; Dashdorj, D.; Demand, G. A.; Dimmock, M. R.; Drake, T. E.; Finlay, P.; Gallant, A. T.; Garrett, P. E.; Green, K. L.; Grint, A. N.; Grinyer, G. F.; Harkness, L. J.; Hayes, A. B.; Kanungo, R.; Lisetskiy, A. F.; Leach, K. G.; Lee, G.; Maharaj, R.; Martin, J.-P.; Moisan, F.; Morton, A. C.; Mythili, S.; Nelson, L.; Newman, O.; Nolan, P. J.; Orce, J. N.; Padilla-Rodal, E.; Phillips, A. A.; Porter-Peden, M.; Ressler, J. J.; Roy, R.; Ruiz, C.; Sarazin, F.; Scraggs, D. P.; Waddington, J. C.; Wan, J. M.; Whitbeck, A.; Williams, S. J.; Wong, J.

2009-10-01

The low-energy structure of the proton dripline nucleus Na20 has been studied using Coulomb excitation at the TRIUMF-ISAC radioactive ion beam facility. A 1.7-MeV/nucleon Na20 beam of ~5×106 ions/s was Coulomb excited by a 0.5-mg/cm2natTi target. Scattered beam and target particles were detected by the BAMBINO segmented Si detector while γ rays were detected by two TIGRESS HPGe clover detectors set perpendicular to the beam axis. Coulomb excitation from the 2+ ground state to the first excited 3+ and 4+ states was observed, and B(λL) values were determined using the 2+→0+ de-excitation in Ti48 as a reference. The resulting B(λL)↓ values are B(E2;3+→2+)=55±6e2fm4 (17.0±1.9 W.u.), B(E2;4+→2+)=35.7±5.7e2fm4 (11.1±1.8 W.u.), and B(M1;4+→3+)=0.154±0.030μN2 (0.086±0.017 W.u.). These measurements provide the first experimental determination of B(λL) values for this proton dripline nucleus of astrophysical interest.
Biogenic CH4 and N2O emissions overwhelm land CO2 sink in Asia: Toward a full GHG budget

NASA Astrophysics Data System (ADS)

Tian, H.

2017-12-01

The recent global assessment indicates the terrestrial biosphere as a net source of greenhouse gases to the atmosphere (Tian et al Nature 2016). The fluxes of greenhouse gases (GHG) vary by region. Both TD and BU approaches indicate that human-caused biogenic fluxes of CO2, CH4 and N2O in the biosphere of Southern Asia led to a large net climate warming effect, because the 100-year cumulative effects of CH4 and N2O emissions together exceed that of the terrestrial CO2 sink. Southern Asia has about 90% of the global rice fields and represents more than 60% of the world's nitrogen fertilizer consumption, with 64%-81% of CH4 emissions and 36%-52% of N2O emissions derived from the agriculture and waste sectors. Given the large footprint of agriculture in Southern Asia, improved fertilizer use efficiency, rice management and animal diets could substantially reduce global agricultural N2O and CH4 emissions. This study highlights the importance of including all three major GHGs in regional climate impact assessments, mitigation option and climate policy development.
Quasiclassical trajectory studies of the O(3P) + CX4(vk = 0, 1) → OXv + CX3(n1n2n3n4) [X = H and D] reactions on an ab initio potential energy surface.

PubMed

Czakó, Gábor; Liu, Rui; Yang, Minghui; Bowman, Joel M; Guo, Hua

2013-08-01

We report quasiclassical trajectory calculations of the integral and differential cross sections and the mode-specific product state distributions for the "central-barrier" O((3)P) + CH4/CD4(vk = 0, 1) [k = 1, 2, 3, 4] reactions using a full-dimensional ab initio potential energy surface. The mode-specific vibrational distributions for the polyatomic methyl products are obtained by doing a normal-mode analysis in the Eckart frame, followed by standard histogram binning (HB) and energy-based Gaussian binning (1GB). The reactant bending excitations slightly enhance the reactivity, whereas stretching excitations activate the reaction more efficiently. None of the reactant vibrational excitations is as efficient as an equivalent amount of translational energy to promote the reactions. The excitation functions without product zero-point energy (ZPE) constraint are in good agreement with previous 8-dimensional quantum mechanical (QM) results for the ground-state and stretching-excited O + CH4 reactions, whereas for the bending-excited reactions the soft ZPE constraint, which is applied to the sum of the product vibrational energies, provides better agreement with the QM cross sections. All angular distributions show the dominance of backward scattering indicating a direct rebound mechanism, in agreement with experiment. The title reactions produce mainly OH/OD(v = 0) products for all the initial states. HB significantly overestimates the populations of OH/OD(v = 1), especially in the energetic threshold regions, whereas 1GB provides physically correct results. The CH3/CD3 vibrational distributions show dominant populations for ground (v = 0), umbrella-excited (v2 = 1, 2), in-plane-bending-excited (v4 = 1), and v2 + v4 methyl product states. Neither translational energy nor reactant vibrational excitation transfers significantly into product vibrations.
Effects of GaN/AlGaN/Sputtered AlN nucleation layers on performance of GaN-based ultraviolet light-emitting diodes

PubMed Central

Hu, Hongpo; Zhou, Shengjun; Liu, Xingtong; Gao, Yilin; Gui, Chengqun; Liu, Sheng

2017-01-01

We report on the demonstration of GaN-based ultraviolet light-emitting diodes (UV LEDs) emitting at 375 nm grown on patterned sapphire substrate (PSS) with in-situ low temperature GaN/AlGaN nucleation layers (NLs) and ex-situ sputtered AlN NL. The threading dislocation (TD) densities in GaN-based UV LEDs with GaN/AlGaN/sputtered AlN NLs were determined by high-resolution X-ray diffraction (XRD) and cross-sectional transmission electron microscopy (TEM), which revealed that the TD density in UV LED with AlGaN NL was the highest, whereas that in UV LED with sputtered AlN NL was the lowest. The light output power (LOP) of UV LED with AlGaN NL was 18.2% higher than that of UV LED with GaN NL owing to a decrease in the absorption of 375 nm UV light in the AlGaN NL with a larger bandgap. Using a sputtered AlN NL instead of the AlGaN NL, the LOP of UV LED was further enhanced by 11.3%, which is attributed to reduced TD density in InGaN/AlInGaN active region. In the sputtered AlN thickness range of 10–25 nm, the LOP of UV LED with 15-nm-thick sputtered AlN NL was the highest, revealing that optimum thickness of the sputtered AlN NL is around 15 nm. PMID:28294166
Td Vaccine (Tetanus and Diphtheria): What You Need to Know

MedlinePlus

... protect adolescents and adults from both of these diseases. Both tetanus and diphtheria are infections caused by bacteria. Diphtheria ... cases of diphtheria and hundreds of cases of tetanus were reported in the United ... both diseases have dropped by about 99%. 2 Td vaccine ...
Improved in silico prediction of carcinogenic potency (TD50) and the risk specific dose (RSD) adjusted Threshold of Toxicological Concern (TTC) for genotoxic chemicals and pharmaceutical impurities.

PubMed

Contrera, Joseph F

2011-02-01

The Threshold of Toxicological Concern (TTC) is a level of exposure to a genotoxic impurity that is considered to represent a negligible risk to humans. The TTC was derived from the results of rodent carcinogenicity TD50 values that are a measure of carcinogenic potency. The TTC currently sets a default limit of 1.5 μg/day in food contact substances and pharmaceuticals for all genotoxic impurities without carcinogenicity data. Bercu et al. (2010) used the QSAR predicted TD50 to calculate a risk specific dose (RSD) which is a carcinogenic potency adjusted TTC for genotoxic impurities. This promising approach is currently limited by the software used, a combination of MC4PC (www.multicase.com) and a Lilly Inc. in-house software (VISDOM) that is not available to the public. In this report the TD50 and RSD were predicted using a commercially available software, SciQSAR (formally MDL-QSAR, www.scimatics.com) employing the same TD50 training data set and external validation test set that was used by Bercu et al. (2010). The results demonstrate the general applicability of QSAR predicted TD50 values to determine the RSDs for genotoxic impurities and the improved performance of SciQSAR for predicting TD50 values. Copyright Â© 2010 Elsevier Inc. All rights reserved.
CLAS N* Excitation Results from Pion and Kaon Electroproduction

DOE PAGES

Carman, Daniel S.

2018-05-24

The study of the structure of excited nucleonmore » $N^*$ states employing the electroproduction of exclusive reactions is an important avenue for exploring the nature of the non-perturbative strong interaction. The electrocouplings of $N^*$ states in the mass range below $W$=1.8~GeV have been determined from analyses of CLAS $$\\pi N$$, $$\\eta N$$, and $$\\pi \\pi N$$ data at four-momentum transfers $Q^2$ up to 5~GeV$^2$. The work has made it clear that consistent results from independent analyses of several exclusive channels with different couplings and non-resonant backgrounds but the same $N^*$ electroexcitation amplitudes, is essential to have confidence in the extracted results. In terms of hadronic couplings, many high-lying $N^*$ states preferentially decay through the $$\\pi \\pi N$$ channel, while couplings to $$\\pi N$$ final states become rather small. The resonance parameters determined from $$\\pi N$$ and $$\\pi \\pi N$$ electroproduction can be checked in independent studies of the $KY$ ($$Y = \\Lambda, \\Sigma^0$$) channels. Therefore, data from the $KY$ channels already measured with CLAS will play an important role in $N^*$ structure studies. These comparisons await the development of suitable reaction models. Starting in 2018, a program to study the structure of $N^*$ states in various exclusive electroproduction channels using the new CLAS12 spectrometer will get underway. These studies will probe the structure of $N^*$ states in the mass range up to $W$=3~GeV and $Q^2$ up to 12~GeV$^2$, thus providing a means to access $N^*$ structure information spanning a broad regime encompassing both low- and high-energy degrees of freedom.« less

CLAS N* Excitation Results from Pion and Kaon Electroproduction

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

Carman, Daniel S.

The study of the structure of excited nucleonmore » $N^*$ states employing the electroproduction of exclusive reactions is an important avenue for exploring the nature of the non-perturbative strong interaction. The electrocouplings of $N^*$ states in the mass range below $W$=1.8~GeV have been determined from analyses of CLAS $$\\pi N$$, $$\\eta N$$, and $$\\pi \\pi N$$ data at four-momentum transfers $Q^2$ up to 5~GeV$^2$. The work has made it clear that consistent results from independent analyses of several exclusive channels with different couplings and non-resonant backgrounds but the same $N^*$ electroexcitation amplitudes, is essential to have confidence in the extracted results. In terms of hadronic couplings, many high-lying $N^*$ states preferentially decay through the $$\\pi \\pi N$$ channel, while couplings to $$\\pi N$$ final states become rather small. The resonance parameters determined from $$\\pi N$$ and $$\\pi \\pi N$$ electroproduction can be checked in independent studies of the $KY$ ($$Y = \\Lambda, \\Sigma^0$$) channels. Therefore, data from the $KY$ channels already measured with CLAS will play an important role in $N^*$ structure studies. These comparisons await the development of suitable reaction models. Starting in 2018, a program to study the structure of $N^*$ states in various exclusive electroproduction channels using the new CLAS12 spectrometer will get underway. These studies will probe the structure of $N^*$ states in the mass range up to $W$=3~GeV and $Q^2$ up to 12~GeV$^2$, thus providing a means to access $N^*$ structure information spanning a broad regime encompassing both low- and high-energy degrees of freedom.« less
Picosecond excite-and-probe absorption measurement of the 4T2 state nonradiative lifetime in ruby

NASA Technical Reports Server (NTRS)

Gayen, S. K.; Wang, W. B.; Petricevic, V.; Dorsinville, R.; Alfano, R. R.

1985-01-01

In a picosecond excite-and-probe absorption measurement, a 527-nm picosecond pulse excites the 4T2 state of the Cr(3+) ion in ruby and a 3.4-micron picosecond probe pulse monitors the growth and decay of population in the 2E state as a function of pump-probe delay. From the growth of population in the metastable 2E state, an upper limit of 7 ps for the nonradiative lifetime of the 4T2 state is determined.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Verma, Prakash; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu

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 energymore » 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.« less
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.
Measurement of relative cross sections for simultaneous ionization and excitation of the helium 4 2s and 4 2p states

NASA Technical Reports Server (NTRS)

Sutton, J. F.

1972-01-01

The relative cross sections for simultaneous ionization and excitation of helium by 200-eV electrons into the 4 2s and 4 2p states were measured via a fast delayed coincidence technique. Results show good agreement with the relative cross sections for single electron excitation of helium and hydrogen. An application of the results of the measurement to the development of ultraviolet intensity standard is suggested. This technique involves the use of known branching ratios, a visible light flux reference, and the measured relative cross sections.
Final Phase Flight Performance and Touchdown Time Assessment of TDV in RLV-TD HEX-01 Mission

NASA Astrophysics Data System (ADS)

Yadav, Sandeep; Jayakumar, M.; Nizin, Aziya; Kesavabrahmaji, K.; Shyam Mohan, N.

2017-12-01

RLV-TD HEX-01 mission was configured as a precursor flight to actual two stages to orbit vehicle. In this mission RLV-TD was designed as a two stage vehicle for demonstrating the hypersonic flight of a winged body vehicle at Mach No. 5. One of the main objectives of this mission was to generate data for better understanding of new technologies required to design the future vehicle. In this mission, the RLV-TD vehicle was heavily instrumented to get data related to performance of different subsystems. As per the mission design, RLV-TD will land in sea after flight duration of 700 s and travelling a distance of nearly 500 km in Bay of Bengal from the launch site for a nominal trajectory. The visibility studies for telemetry data of vehicle for the nominal and off nominal trajectories were carried out. Based on that, three ground stations were proposed for the telemetry data reception (including one in sea). Even with this scheme it was seen that during the final phase of the flight there will not be any ground station visible to the flight due to low elevation. To have the mission critical data during final phase of the flight, telemetry through INSAT scheme was introduced. During the end of the mission RLV-TD will be landing in the sea on a hypothetical runway. To know the exact time of touchdown for the flight in sea, there was no direct measurement available. Simultaneously there were all chances of losing ground station visibility just before touchdown, making it difficult to assess flight performance during that phase. In this work, telemetry and instrumentation scheme of RLV-TD HEX-01 mission is discussed with an objective to determine the flight performance during the final phase. Further, using various flight sensor data the touchdown time of TDV is assessed for this mission.
Hybrid excitations due to crystal field, spin-orbit coupling, and spin waves in LiFePO4

NASA Astrophysics Data System (ADS)

Yiu, Yuen; Le, Manh Duc; Toft-Peterson, Rasmus; Ehlers, Georg; McQueeney, Robert J.; Vaknin, David

2017-03-01

We report on the spin waves and crystal field excitations in single crystal LiFePO4 by inelastic neutron scattering over a wide range of temperatures, below and above the antiferromagnetic transition of this system. In particular, we find extra excitations below TN=50 K that are nearly dispersionless and are most intense around magnetic zone centers. We show that these excitations correspond to transitions between thermally occupied excited states of Fe2 + due to splitting of the S =2 levels that arise from the crystal field and spin-orbit interactions. These excitations are further amplified by the highly distorted nature of the oxygen octahedron surrounding the iron atoms. Above TN, magnetic fluctuations are observed up to at least 720 K, with an additional inelastic excitation around 4 meV, which we attribute to single-ion effects, as its intensity weakens slightly at 720 K compared to 100 K, which is consistent with the calculated cross sections using a single-ion model. Our theoretical analysis, using the MF-RPA model, provides both detailed spectra of the Fe d shell and estimates of the average ordered magnetic moment and TN. By applying the MF-RPA model to a number of existing spin-wave results from other Li M PO4 (M =Mn , Co, and Ni), we are able to obtain reasonable predictions for the moment sizes and transition temperatures.
Impulsive excitation of mechanoluminescence in gamma-irradiated CaSO4:Eu phosphors

NASA Astrophysics Data System (ADS)

Kher, R. S.; Dhoble, S. J.; Pandey, R. K.; Upadhyay, A. K.; Khokhar, M. S. K.

2011-01-01

The mechanoluminescence (ML) and thermoluminescence (TL) of γ-irradiated CaSO4:Eu phosphor have been studied. CaSO4 samples having different concentrations of Eu were prepared by dissolving CaSO4.2H2O in sulphuric acid and evaporating the excess acid around 300 °C. ML was excited impulsively by dropping a load onto the sample. Three distinct peaks have been observed in the ML intensity versus time curve. The ML intensity increases with the increasing concentration of the dopant. The effect of temperature on the shape and peak of ML intensity was also recorded. Growth, saturation and broadening in an ML peak were observed. TL glow curves of CaSO4:Eu phosphors at different concentrations contain two TL peaks: the first peak was observed at around 110 °C and the other at 210 °C. Experimental results suggest that the ML excitation is related to the movement of dislocation with defect centres, the increase in ML with temperature is due to the enhancement in dislocation capture probability, and the reduction is due to the thermal bleaching of defect centres.
Department of the Navy Justification of Estimates FY 1991 Budget Estimates Submitted to Congress January 1990, Operation & Maintenance, Navy. Book 1. Budget Activity 1. Strategic Forces. Budget Activity 2. General Purpose Forces. Budget Activity 3. Intelligence & Communications. Budget Activity 4. Airlift and Sealift.

DTIC Science & Technology

1990-01-01

W a jwý 0 c! l U) to 0 C: C3 tdl &-j 𔃺 10 0 r r -" .-4GJ -4 w 4-𔃼w w .- 4 W &a’’ 0 󈧰 0 >1V) ( td ’- ~u 0 4 b W -4 a)i 0 1l-4 a, .. n (I = 0 -4 ý...to0 d)r- $4. 0)0 r. cd .,-~~ 4 C:s o a) (n44E-𔃺C W 0. 44CLH td c~ - 0ý 0r a;i w-4’-4 0’r0.. 12O4’w.. X-.41m C0) en (d 3)b-%- u s~~ -40r n 0- 1 0 0...c- ~ Li * to wC~C 0’~ -4 L)CrO0-40 CLTý -4 14 CLU L> w)i VQ. V) Li)- td -III.- 0 U -4 W ed Q C U - H bOC E 0 w u -𔃾 r-4 w &J.- w 4 0-I kw -H = IV -4
Doping dependence of the magnetic excitations in La 2 - x Sr x CuO 4

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

Meyers, D.; Miao, H.; Walters, A. C.

The magnetic correlations within the cuprates have undergone intense scrutiny as part of efforts to understand high-temperature superconductivity. We explore the evolution of the magnetic correlations along the nodal direction of the Brillouin zone in La 2–xSr xCuO 4, spanning the doping phase diagram from the antiferromagnetic Mott insulator at x = 0 to the metallic phase at x = 0.26. Magnetic excitations along this direction are found to be systematically softened and broadened with doping, at a higher rate than the excitations along the antinodal direction. This phenomenology is discussed in terms of the nature of the magnetism inmore » the doped cuprates. As a result, survival of the high-energy magnetic excitations, even in the overdoped regime, indicates that these excitations are marginal to pairing, while the influence of the low-energy excitations remains ambiguous.« less
Doping dependence of the magnetic excitations in La 2 - x Sr x CuO 4

DOE PAGES

Meyers, D.; Miao, H.; Walters, A. C.; ...

2017-02-15

The magnetic correlations within the cuprates have undergone intense scrutiny as part of efforts to understand high-temperature superconductivity. We explore the evolution of the magnetic correlations along the nodal direction of the Brillouin zone in La 2–xSr xCuO 4, spanning the doping phase diagram from the antiferromagnetic Mott insulator at x = 0 to the metallic phase at x = 0.26. Magnetic excitations along this direction are found to be systematically softened and broadened with doping, at a higher rate than the excitations along the antinodal direction. This phenomenology is discussed in terms of the nature of the magnetism inmore » the doped cuprates. As a result, survival of the high-energy magnetic excitations, even in the overdoped regime, indicates that these excitations are marginal to pairing, while the influence of the low-energy excitations remains ambiguous.« less
Atmospheric Pressure-Thermal Desorption (AP-TD)/Electrospray Ionization-Mass Spectrometry for the Rapid Analysis of Bacillus Spores

USDA-ARS?s Scientific Manuscript database

A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry are coupled and used for the rapid analysis of Bacillus spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile co...
Elucidation of the new generation fluorescent protein tdTomato for space related radiobiological research

NASA Astrophysics Data System (ADS)

Chishti, Arif Ali; Baumstark-Khan, Christa; Hellweg, Christine; Reitz, Guenther

Astronauts in space are exposed to a potentially harmful radiation field, which does not exist in its quality and quantity on earth. Radiation exposure in space can lead to delayed or acute health effects. A successful long-term space mission requires better risk estimation and development of appropriate countermeasures, therefore study of the cellular radiation response is necessary. Ionizing radiation can provoke active cellular responses (cell cycle arrest, DNA repair, apoptosis or other forms of cell type). Exposure to ionizing radiation also activates various signaling pathways in human cells. In the cellular radiation-response, two pivotal signal transduction pathways have to be comprehensively studied i.e. the p53-pathway and NF-κB-pathway. Discovery of fluorescent proteins has revolutionized biological research by making it possible to carry out functional studies in living cells and understanding complex signaling pathways. Previously the green fluorescent proteins EGFP and d2EGFP were used for signaling pathway studies. In this work the new red fluorescent protein tdTomato will be used for comprehensive investigation of NF-κB and other transcription factor activation after exposure of human cells to ionizing radiation (X-rays, heavy ions; space conditions). tdTomato has many advantages over EGFP because of its high fluorescence signals and a better signal/noise ratio in human cells. The previously constructed reporter system with d2EGFP was used to evaluate NF-kB activation after exposure to heavy ion particles of different biological effectiveness. The sensitivity threshold of this system was determined to be 2 particle traversals per cell nucleus. In the current study a more sensitive reporter assay will be constructed using a GAL4-VP16 turbo system that comprises a receptor plasmid and a reporter plasmid. This reporter assay will be designed and constructed with tdTomato and evaluation will be done with different molecular techniques.
Applications of the Coulomb-modified Glauber approximation to n = 2 and n = 3 excitation of hydrogenlike ions by incident electrons. II

NASA Technical Reports Server (NTRS)

Thomas, B. K.

1978-01-01

The Coulomb-modified form of the Glauber approximation is applied to the n = 2 and n = 3 excitation of hydrogenlike ions by incident electrons for various values of the target-ion nuclear charge Z sub n. The properly computed e(-)-He(+) 1s - 2s,2p Glauber predictions, including appropriate cascade effects, are compared with available experiment. The Z sub n dependence of the scaled integrated (over scattering angles) cross section is discussed, including the limit as Z sub n approaches infinity.
Effect of threading defects on InGaN /GaN multiple quantum well light emitting diodes

NASA Astrophysics Data System (ADS)

Ferdous, M. S.; Wang, X.; Fairchild, M. N.; Hersee, S. D.

2007-12-01

Photoelectrochemical etching was used to measure the threading defect (TD) density in InGaN multiple quantum well light-emitting diodes (LEDs) fabricated from commercial quality epitaxial wafers. The TD density was measured in the LED active region and then correlated with the previously measured characteristics of these LEDs. It was found that the reverse leakage current increased exponentially with TD density. The temperature dependence of this dislocation-related leakage current was consistent with a hopping mechanism at low reverse-bias voltage and Poole-Frenkel emission at higher reverse-bias voltage. The peak intensity and spectral width of the LED electroluminescence were found to be only weakly dependent on TD density for the measured TD range of 1×107-2×108cm-2.
Fast gas heating and radial distribution of active species in nanosecond capillary discharge in pure nitrogen and N2:O2 mixtures

NASA Astrophysics Data System (ADS)

Lepikhin, N. D.; Popov, N. A.; Starikovskaia, S. M.

2018-05-01

Fast gas heating is studied experimentally and numerically using pulsed nanosecond capillary discharge in pure nitrogen and N2:O2 mixtures under the conditions of high specific deposited energy (up to 1 eV/molecule) and high reduced electric fields (100–300 Td). Deposited energy, electric field and gas temperature are measured as functions of time. The radial distribution of active species is analyzed experimentally. The roles of processes involving {{{N}}}2({{B}}) ={{{N}}}2({{{B}}}3{{{\\Pi }}}{{g}},{{{W}}}3{{{Δ }}}{{u}},{{B}}{{\\prime} }3{{{Σ }}}{{u}}-), {{{N}}}2({{{A}}}3{{{Σ }}}{{u}}+) and N(2D) excited nitrogen species leading to heat release are analyzed using numerical modeling in the framework of 1D axial approximation.
Assessment of TD-DFT methods and of various spin scaled CIS(D) and CC2 versions for the treatment of low-lying valence excitations of large organic dyes

NASA Astrophysics Data System (ADS)

Goerigk, Lars; Grimme, Stefan

2010-05-01

We present an extension of our previously published benchmark set for low-lying valence transitions of large organic dyes [L. Goerigk et al., Phys. Chem. Chem. Phys. 11, 4611 (2009)]. The new set comprises in total 12 molecules, including two charged species and one with a clear charge-transfer transition. Our previous study on TD-DFT methods is repeated for the new test set with a larger basis set. Additionally, we want to shed light on different spin-scaled variants of the configuration interaction singles with perturbative doubles correction [CIS(D)] and the approximate coupled cluster singles and doubles method (CC2). Particularly for CIS(D) we want to clarify, which of the proposed versions can be recommended. Our results indicate that an unpublished SCS-CIS(D) variant, which is implemented into the TURBOMOLE program package, shows worse results than the original CIS(D) method, while other modified versions perform better. An SCS-CIS(D) version with a parameterization, that has already been used in an application by us recently [L. Goerigk and S. Grimme, ChemPhysChem 9, 2467 (2008)], yields the best results. Another SCS-CIS(D) version and the SOS-CIS(D) method [Y. M. Rhee and M. Head-Gordon, J. Phys. Chem. A 111, 5314 (2007)] perform very similar, though. For the electronic transitions considered herein, there is no improvement observed when going from the original CC2 to the SCS-CC2 method but further adjustment of the latter seems to be beneficial. Double-hybrid density functionals belong to best methods tested here. Particularly B2GP-PLYP provides uniformly good results for the complete set and is considered to be close to chemical accuracy within an ab initio theory of color. For conventional hybrid functionals, a Fock-exchange mixing parameter of about 0.4 seems to be optimum in TD-DFT treatments of large chromophores. A range-separated functional such as, e.g., CAM-B3LYP seems also to be promising.
Direct Electron Impact Excitation of Rydberg-Valence States of Molecular Nitrogen

NASA Astrophysics Data System (ADS)

Malone, C. P.; Johnson, P. V.; Liu, X.; Ajdari, B.; Muleady, S.; Kanik, I.; Khakoo, M. A.

2012-12-01

Collisions between electrons and neutral N2 molecules result in emissions that provide an important diagnostic probe for understanding the ionospheric energy balance and the effects of space weather in upper atmospheres. Also, transitions to singlet ungerade states cause N2 to be a strong absorber of solar radiation in the EUV spectral range where many ro-vibrational levels of these Rydberg-valence (RV) states are predissociative. Thus, their respective excitation and emission cross sections are important parameters for understanding the [N]/[N2] ratio in the thermosphere of nitrogen dominated atmospheres. The following work provides improved constraints on absolute and relative excitation cross sections of numerous RV states of N2, enabling more physically accurate atmospheric modeling. Here, we present recent integral cross sections (ICSs) for electron impact excitation of RV states of N2 [6], which were based on the differential cross sections (DCSs) derived from electron energy-loss (EEL) spectra of [5]. This work resulted in electronic excitation cross sections over the following measured vibrational levels: b 1Πu (v‧=0-14), c3 1Πu (v‧=0-3), o3 1Πu (v‧=0-3), b‧ 1Σu+ (v‧=0-10), c‧4 1Σu+ (v‧=0-3), G 3Πu (v‧=0-3), and F 3Πu (v‧=0-3). We further adjusted the cross sections of the RV states by extending the vibronic contributions to unmeasured v‧-levels via the relative excitation probabilities (REPs) as discussed in [6]. This resulted in REP-scaled ICSs over the following vibrational levels for the singlet ungerade states: b(0-19), c3(0-4), o3(0-4), b‧(0-16), and c‧4(0-8). Comparison of the ICSs of [6] with available EEL based measurements, theoretical calculations, and emission based work generally shows good agreement within error estimations, except with the recent reevaluation provided by [1]. Further, we have extended these results, using the recent EEL data of [3], to include the unfolding of better resolved features above ~13
Cob(I)alamin: insight into the nature of electronically excited states elucidated via quantum chemical computations and analysis of absorption, CD and MCD data.

PubMed

Kornobis, Karina; Ruud, Kenneth; Kozlowski, Pawel M

2013-02-07

The nature of electronically excited states of the super-reduced form of vitamin B(12) (i.e., cob(I)alamin or B(12s)), a ubiquitous B(12) intermediate, was investigated by performing quantum-chemical calculations within the time-dependent density functional theory (TD-DFT) framework and by establishing their correspondence to experimental data. Using response theory, the electronic absorption (Abs), circular dichroism (CD) and magnetic CD (MCD) spectra of cob(I)alamin were simulated and directly compared with experiment. Several issues have been taken into considerations while performing the TD-DFT calculations, such as strong dependence on the applied exchange-correlation (XC) functional or structural simplification imposed on the cob(I)alamin. In addition, the low-lying transitions were also validated by performing CASSCF/MC-XQDPT2 calculations. By comparing computational results with existing experimental data a new level of understanding of electronic excitations has been established at the molecular level. The present study extends and confirms conclusions reached for other cobalamins. In particular, the better performance of the BP86 functional, rather than hybrid-type, was observed in terms of the excitations associated with both Co d and corrin π localized transitions. In addition, the lowest energy band was associated with multiple metal-to-ligand charge transfer excitations as opposed to the commonly assumed view of a single π → π* transition followed by vibrational progression. Finally, the use of the full cob(I)alamin structure, instead of simplified molecular models, shed new light on the spectral analyses of cobalamin systems and revealed new challenges of this approach related to long-range charge transfer excitations involving side chains.
Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity

DOE PAGES

Leto, Domenick F.; Massie, Allyssa A.; Rice, Derek B.; ...

2016-11-01

The mononuclear Mn(IV)-oxo complex [Mn IV(O)(N4py)] 2+, where N4py is the pentadentate ligand N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine, we propose to attack C–H bonds by an excited-state reactivity pattern [Cho, K.-B.; Shaik, S.; Nam, W. J. Phys. Chem. Lett. 2012, 3, 2851-2856 (DOI: 10.1021/jz301241z)]. In this model, a 4E excited state is utilized to provide a lower-energy barrier for hydrogen-atom transfer. This proposal is intriguing, as it offers both a rationale for the relatively high hydrogen-atom-transfer reactivity of [Mn IV(O)(N4py)] 2+ and a guideline for creating more reactive complexes through ligand modification. Here we employ a combination of electronic absorption and variable-temperature magnetic circularmore » dichroism (MCD) spectroscopy to experimentally evaluate this excited-state reactivity model. Using these spectroscopic methods, in conjunction with time-dependent density functional theory (TD-DFT) and complete-active space self-consistent-field calculations (CASSCF), we define the ligand-field and charge-transfer excited states of [MnIV(O)(N4py)]2+. Through a graphical analysis of the signs of the experimental C-term MCD signals, we unambiguously assign a low-energy MCD feature of [Mn IV(O)(N4py)] 2+ as the 4E excited state predicted to be involved in hydrogen-atom-transfer reactivity. The CASSCF calculations predict enhanced Mn III-oxyl character on the excited-state 4E surface, consistent with previous DFT calculations. Potential-energy surfaces, developed using the CASSCF methods, are used to determine how the energies and wave functions of the ground and excited states evolved as a function of Mn=O distance. Furthermore, the unique insights into ground- and excited-state electronic structure offered by these spectroscopic and computational studies are harmonized with a thermodynamic model of hydrogen-atom-transfer reactivity, which predicts a correlation between transition-state barriers and driving force« less

Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity

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

Leto, Domenick F.; Massie, Allyssa A.; Rice, Derek B.

The mononuclear Mn(IV)-oxo complex [Mn IV(O)(N4py)] 2+, where N4py is the pentadentate ligand N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine, we propose to attack C–H bonds by an excited-state reactivity pattern [Cho, K.-B.; Shaik, S.; Nam, W. J. Phys. Chem. Lett. 2012, 3, 2851-2856 (DOI: 10.1021/jz301241z)]. In this model, a 4E excited state is utilized to provide a lower-energy barrier for hydrogen-atom transfer. This proposal is intriguing, as it offers both a rationale for the relatively high hydrogen-atom-transfer reactivity of [Mn IV(O)(N4py)] 2+ and a guideline for creating more reactive complexes through ligand modification. Here we employ a combination of electronic absorption and variable-temperature magnetic circularmore » dichroism (MCD) spectroscopy to experimentally evaluate this excited-state reactivity model. Using these spectroscopic methods, in conjunction with time-dependent density functional theory (TD-DFT) and complete-active space self-consistent-field calculations (CASSCF), we define the ligand-field and charge-transfer excited states of [MnIV(O)(N4py)]2+. Through a graphical analysis of the signs of the experimental C-term MCD signals, we unambiguously assign a low-energy MCD feature of [Mn IV(O)(N4py)] 2+ as the 4E excited state predicted to be involved in hydrogen-atom-transfer reactivity. The CASSCF calculations predict enhanced Mn III-oxyl character on the excited-state 4E surface, consistent with previous DFT calculations. Potential-energy surfaces, developed using the CASSCF methods, are used to determine how the energies and wave functions of the ground and excited states evolved as a function of Mn=O distance. Furthermore, the unique insights into ground- and excited-state electronic structure offered by these spectroscopic and computational studies are harmonized with a thermodynamic model of hydrogen-atom-transfer reactivity, which predicts a correlation between transition-state barriers and driving force« less
Discrete and continuum modeling of solvent effects in a twisted intramolecular charge transfer system: The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule.

PubMed

Modesto-Costa, Lucas; Borges, Itamar

2018-08-05

The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule is a prototypical system displaying twisted intramolecular (TICT) charge transfer effects. The ground and the first four electronic excited states (S 1 -S 4 ) in gas phase and upon solvation were studied. Charge transfer values as function of the torsion angle between the donor group (dimethylamine) and the acceptor moiety (benzonitrile) were explicitly computed. Potential energy curves were also obtained. The algebraic diagrammatic construction method at the second-order [ADC(2)] ab initio wave function was employed. Three solvents of increased polarities (benzene, DMSO and water) were investigated using discrete (average solvent electrostatic configuration - ASEC) and continuum (conductor-like screening model - COSMO) models. The results for the S 3 and S 4 excited states and the S 1 -S 4 charge transfer curves were not previously available in the literature. Electronic gas phase and solvent vertical spectra are in good agreement with previous theoretical and experimental results. In the twisted (90°) geometry the optical oscillator strengths have negligible values even for the S 2 bright state. Potential energy curves show two distinct pairs of curves intersecting at decreasing angles or not crossing in the more polar solvents. Charge transfer and electric dipole values allowed the rationalization of these results. The former effects are mostly independent of the solvent model and polarity. Although COSMO and ASEC solvent models mostly lead to similar results, there is an important difference: some crossings of the excitation energy curves appear only in the ASEC solvation model, which has important implications to the photochemistry of DMABN. Copyright © 2018 Elsevier B.V. All rights reserved.
Ultrafast Excited-State Dynamics of Cytosine Aza-Derivative and Analogues.

PubMed

Zhou, Zhongneng; Zhou, Xueyao; Wang, Xueli; Jiang, Bin; Li, Yongle; Chen, Jinquan; Xu, Jianhua

2017-04-13

Excited state dynamics of 5-azacytosine (5-AC), 2,4-diamino-1,3,5-triazine (2,4-DT), and 2-amino-1,3,5-triazine (2-AT) were comprehensively investigated by steady state absorption, fluorescence, and femtosecond transient absorption measurements. Time-dependent density functional theory (TDDFT) calculations were performed to help assign the absorption bands and understand the excited state decay mechanisms. The experimental results of excited singlet state dynamics for 5-AC, 2,4-DT, and 2-AT with femtosecond time resolution were reported for the first time. Two distinct decay pathways, with ∼1 ps and tens of picosecond lifetimes, were observed in 5-AC. Only one decay pathway with 17 ps lifetime was observed in 2,4-DT while an emissive state was found in 2-AT. TDDFT calculations suggest that 5-AC has a dark nπ* (S 1 ) state below the first allowed ππ* (S 2 ) state, which leads to the ultrafast decay of the ππ* state. In 2,4-DT, there is no dark nπ* state below the bright ππ* (S 1 ) state and the 17 ps lifetime is assigned to the relaxation from the ππ* (S 1 ) state to ground state. Two dark nπ* states (S 1 and S 2 ) were found in 2-AT, which exhibits much more complex excited state dynamics compared with the other two. Photoluminescence in 2-AT has been confirmed to be fluorescence emission from its bright ππ* (S 3 ) state. Our results strongly suggest that electronic structures are very sensitive to the substitution on the triazine ring and that the photophysical properties of nucleic acid analogues depend highly on their molecular structures.
Excitation energies, radiative and autoionization rates, dielectronic satellite lines, and dielectronic recombination rates for excited states of Rb-like W from Kr-like W [Relativistic atomic data for Rb-like tungsten

DOE PAGES

Safronova, U. I.; Safronova, A. S.; Beiersdorfer, P.

2016-11-02

Energy levels, radiative transition probabilities, and autoionization rates for [Ni]more » $$4{s}^{2}4{p}^{6}{nl}$$, [Ni]$$4{s}^{2}4{p}^{5}4l^{\\prime} {nl}$$ ($$l^{\\prime} =d,f,n$$ = 4–7), [Ni]$$4s4{p}^{6}4l^{\\prime} {nl}$$, ($$l^{\\prime} =d,f,n$$ = 4–7), [Ni]$$4{s}^{2}4{p}^{5}5l^{\\prime} {nl}$$ (n = 5–7), and [Ni]$$4s4{p}^{6}6l^{\\prime} {nl}$$ (n = 6–7) states in Rb-like tungsten (W37+) are calculated using the relativistic many-body perturbation theory method (RMBPT code) and the Hartree–Fock-relativistic method (COWAN code). Autoionizing levels above the [Ni]$$4{s}^{2}4{p}^{6}$$ threshold are considered. It is found that configuration mixing among [Ni]$$4{s}^{2}4{p}^{5}4l^{\\prime} {nl}$$ and [Ni]$$4s4{p}^{6}4l^{\\prime} {nl}$$ plays an important role for all atomic characteristics. Branching ratios relative to the first threshold and intensity factors are calculated for satellite lines, and dielectronic recombination (DR) rate coefficients are determined for the [Ni]$$4{s}^{2}4{p}^{6}{nl}$$ (n = 4–7) singly excited states, as well as the [Ni]$$4{s}^{2}4{p}^{5}4{dnl}$$, [Ni]$$4{s}^{2}4{p}^{5}4{fnl}$$, [Ni]$$4s4{p}^{6}4{dnl}$$, [Ni]$$4{s}^{2}4{p}^{6}4{fnl}$$, (n = 4–6), and [Ni]$$4{s}^{2}4{p}^{5}5l^{\\prime} 5l$$ doubly excited nonautoionizing states in Rb-like W37+ ion. Contributions from the [Ni]$$4s24{p}^{6}4{fnl}$$ (n = 6–7), [Ni]$$4{s}^{2}4{p}^{5}5l^{\\prime} {nl}$$ (n = 5–6), and [Ni]$$4{s}^{2}4{p}^{5}6l^{\\prime} {nl}$$ (n = 6–7) doubly excited autoionizing states are evaluated numerically. The high-n state (with n up to 500) contributions are very important for high temperatures. These contributions are determined by using a scaling procedure. Synthetic dielectronic satellite spectra from Rb-like W are simulated in a broad spectral range from 8 to 70 Å. Here, these calculations provide highly accurate values for a number of W 37+ properties useful for a variety of applications including for fusion applications.« less
Identification of rat Rosa26 locus enables generation of knock-in rat lines ubiquitously expressing tdTomato.

PubMed

Kobayashi, Toshihiro; Kato-Itoh, Megumi; Yamaguchi, Tomoyuki; Tamura, Chihiro; Sanbo, Makoto; Hirabayashi, Masumi; Nakauchi, Hiromitsu

2012-11-01

Recent discovery of a method for derivation and culture of germline-competent rat pluripotent stem cells (PSCs) enables generation of transgenic rats or knock-out rats via genetic modification of such PSCs. This opens the way to use rats, as is routine in mice, for analyses of gene functions or physiological features. In mouse or human, one widely used technique to express a gene of interest stably and ubiquitously is to insert that gene into the Rosa26 locus via gene targeting of PSCs. Rosa26 knock-in mice conditionally expressing a reporter or a toxin gene have contributed to tracing or ablation of specific cell lineages. We successfully identified a rat orthologue of the mouse Rosa26 locus. Insertion of tdTomato, a variant of red fluorescent protein, into the Rosa26 locus of PSCs of various rat strains allows ubiquitous expression of tdTomato. Through germline transmission of one Rosa26-tdTomato knock-in embryonic stem cell line, we also obtained tdTomato knock-in rats. These expressed tdTomato ubiquitously throughout their bodies, which indicates that the rat Rosa26 locus conserves functions of its orthologues in mouse and human. The new tools described here (targeting vectors, knock-in PSCs, and rats) should be useful for a variety of research using rats.
Dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT formation and decay after picosecond pulsed X-ray excitation and femtosecond UV excitation.

PubMed

Zhao, Liyan; Odaka, Hideho; Ono, Hiroshi; Kajimoto, Shinji; Hatanaka, Koji; Hobley, Jonathan; Fukumura, Hiroshi

2005-01-01

The dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT state formation and decay were determined after femtosecond UV laser excitation and picosecond pulsed X-ray excitation, in an N,N-dimethylformamide (DMF) solution as well as in its solid form. At room temperature, after UV excitation, this MLCT excited state emits both in DMF solution and in the solid form. Transient absorption spectra were measured in solution at various delay times following excitation by a 160 fs, 390 nm laser pulse. There was a prompt absorption increase at around 460 nm occurring within the pump probe convolution (<1 ps), which was assigned to the formation of the 3MLCT state. This transient absorbance was constant over 100 ps. In contrast to the solution state, in the solid state, the emission maximum slightly red-shifts with increasing time after laser excitation. In both solid and solution the emission rises within the system response time. The solid sample exhibited a 1.4 ns emission decay that was not observed for the solution sample. The emission rise from a solid sample after 20 ps pulsed X-ray excitation was significantly slower than the system's time resolution. It is proposed that kinetically energetic electrons are ejected following X-ray induced ionisation, creating ionised tracks in which energetic cations and electrons take time to recombine yielding delayed 3MLCT states that emit.
Electronic excitations in finite and infinite polyenes

NASA Astrophysics Data System (ADS)

Tavan, Paul; Schulten, Klaus

1987-09-01

We study electronic excitations in long polyenes, i.e., in one-dimensional strongly correlated electron systems which are neither infinite nor small. The excitations are described within Hubbard and Pariser-Parr-Pople (PPP) models by means of a multiple-reference double-excitation expansion [P. Tavan and K. Schulten, J. Chem. Phys. 85, 6602 (1986)]. We find that quantized ``transition'' momenta can be assigned to electronic excitations in finite chains. These momenta link excitation energies of finite chains to dispersion relations of infinite chains, i.e., they bridge the gap between finite and infinite systems. A key result is the following: Excitation energies E in polyenes with N carbon atoms are described very accurately by the formula Eβ=ΔEβ0+αβk(N)q, q=1,2,..., where β denotes the excitation class, ΔEβ0 the energy gap in the infinite system [αβk(N)>0], and k(N) the elementary transition momentum. The parameters ΔEβ0 and αβ are determined for covalent and ionic excitations in alternating and nonalternating polyenes. The covalent excitations are combinations of triplet excitations T, i.e., T, TT, TTT, . . . . The lowest singlet excitations in the infinite polyene, e.g., in polyacetylene or polydiacetylene, are TT states. Available evidence proves that these states can dissociate into separate triplets. The bond structure of TT states is that of a neutral soliton-antisoliton pair. The level density of TT states in long polyenes is high enough to allow dissociation into separate solitons.
Proton-transfer reaction mass spectrometry (PTRMS) in combination with thermal desorption (TD) for sensitive off-line analysis of volatiles.

PubMed

Crespo, Elena; Devasena, Samudrala; Sikkens, Cor; Centeno, Raymund; Cristescu, Simona M; Harren, Frans J M

2012-04-30

When performing trace gas analysis, it is not always possible to bring the source of volatiles and the gas analyzer together. In these cases, volatile storage containers, such as thermal desorption (TD) tubes, can be used for off-line measurement. TD is routinely combined with gas chromatography/mass spectrometry (GC/MS), but so far not with proton-transfer reaction mass spectrometry (PTRMS), which has a faster response. A PTR-quadrupole-MS instrument and a PTR-ion-trap-MS instrument were separately coupled to a TD unit for off-line analysis of trace volatiles in air. Carbograph 1TD/Carbopack X sorbent tubes were filled with different concentrations of a trace gas mixture containing low molecular weight volatiles (32 g/mol up to 136 g/mol) and measured with the above-mentioned combinations. The carrier gas in the TD unit was changed from helium to nitrogen to be able to combine this instrument with the mass spectrometer. Good linearity and reproducibility with the amount of gas stored were obtained. The storage capacity over time (up to 14 days) showed larger variability (<11% for all compounds, except for acetone 27%). Several tubes were filled with breath of different persons, and the breath of a smoker showed increased levels of acetonitrile and benzene. The combination of the PTR ion-trap instrument with the TD unit was also investigated. Due to its higher sampling rate, the ion-trap system showed higher throughput capabilities than the quadrupole system. The combination of TD with PTRMS using both a quadrupole and an ion trap for off-line volatile analysis has been validated. TD tubes can be a robust and compact volatile storage method when the mass spectrometry and the sampling cannot be performed in the same place, for example in large screening studies. In addition, a higher measurement throughput than with GC/MS could be obtained. Copyright © 2012 John Wiley & Sons, Ltd.
Spin-vibronic quantum dynamics for ultrafast excited-state processes.

PubMed

Eng, Julien; Gourlaouen, Christophe; Gindensperger, Etienne; Daniel, Chantal

2015-03-17

Ultrafast intersystem crossing (ISC) processes coupled to nuclear relaxation and solvation dynamics play a central role in the photophysics and photochemistry of a wide range of transition metal complexes. These phenomena occurring within a few hundred femtoseconds are investigated experimentally by ultrafast picosecond and femtosecond transient absorption or luminescence spectroscopies, and optical laser pump-X-ray probe techniques using picosecond and femtosecond X-ray pulses. The interpretation of ultrafast structural changes, time-resolved spectra, quantum yields, and time scales of elementary processes or transient lifetimes needs robust theoretical tools combining state-of-the-art quantum chemistry and developments in quantum dynamics for solving the electronic and nuclear problems. Multimode molecular dynamics beyond the Born-Oppenheimer approximation has been successfully applied to many small polyatomic systems. Its application to large molecules containing a transition metal atom is still a challenge because of the nuclear dimensionality of the problem, the high density of electronic excited states, and the spin-orbit coupling effects. Rhenium(I) α-diimine carbonyl complexes, [Re(L)(CO)3(N,N)](n+) are thermally and photochemically robust and highly flexible synthetically. Structural variations of the N,N and L ligands affect the spectroscopy, the photophysics, and the photochemistry of these chromophores easily incorporated into a complex environment. Visible light absorption opens the route to a wide range of applications such as sensors, probes, or emissive labels for imaging biomolecules. Halide complexes [Re(X)(CO)3(bpy)] (X = Cl, Br, or I; bpy = 2,2'-bipyridine) exhibit complex electronic structure and large spin-orbit effects that do not correlate with the heavy atom effects. Indeed, the (1)MLCT → (3)MLCT intersystem crossing (ISC) kinetics is slower than in [Ru(bpy)3](2+) or [Fe(bpy)3](2+) despite the presence of a third-row transition metal
Vibrational dynamics of aniline (N2)1 clusters in their first excited singlet state

NASA Astrophysics Data System (ADS)

Hineman, M. F.; Kim, S. K.; Bernstein, E. R.; Kelley, D. F.

1992-04-01

The first excited singlet state S1 vibrational dynamics of aniline(N2)1 clusters are studied and compared to previous results on aniline(CH4)1 and aniline(Ar)1. Intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) rates fall between the two extremes of the CH4 (fast IVR, slow VP) and Ar (slow IVR, fast VP) cluster results as is predicted by a serial IVR/VP model using Fermi's golden rule to describe IVR processes and a restricted Rice-Ramsperger-Kassel-Marcus (RRKM) theory to describe unimolecular VP rates. The density of states is the most important factor determining the rates. Two product states, 00 and 10b1, of bare aniline and one intermediate state ˜(00) in the overall IVR/VP process are observed and time resolved measurements are obtained for the 000 and ˜(000) transitions. The results are modeled with the serial mechanism described above.
Relative Stability of the La and Lb Excited States in Adenine and Guanine: Direct Evidence from TD-DFT Calculations of MCD Spectra.

PubMed

Santoro, Fabrizio; Improta, Roberto; Fahleson, Tobias; Kauczor, Joanna; Norman, Patrick; Coriani, Sonia

2014-06-05

The relative position of La and Lb ππ* electronic states in purine nucleobases is a much debated topic, since it can strongly affect our understanding of their photoexcited dynamics. To assess this point, we calculated the absorption and magnetic circular dichroism (MCD) spectra of adenine, guanine, and their nucleosides in gas-phase and aqueous solution, exploiting recent developments in MCD computational technology within time-dependent density functional theory. MCD spectroscopy allows us to resolve the intense S0→ La transition from the weak S0→ Lb transition. The spectra obtained in water solution, by using B3LYP and CAM-B3LYP functionals and describing solvent effect by cluster models and by the polarizable continuum model (PCM), are in very good agreement with the experimental counterparts, thus providing direct and unambiguous evidence that the energy ordering predicted by TD-DFT, La < Lb, is the correct one.
SrAl2O4:Eu2+ (1%) luminescence under UV, VUV and electron beam excitation

NASA Astrophysics Data System (ADS)

Nazarov, M.; Mammadova, S.; Spassky, D.; Vielhauer, S.; Abdullayeva, S.; Huseynov, A.; Jabbarov, R.

2018-01-01

This paper reports the luminescence properties of nanosized SrAl2O4:Eu2+ (1%) phosphors. The samples were prepared by combustion method at 600 °C, followed by annealing of the resultant combustion ash at 1000 °C in a reductive (Ar + H2) atmosphere. X-ray diffraction (XRD), photo luminescence (PL) and cathodoluminescence (CL) analysis and thermal stimulated luminescence (TSL) method were applied to characterize the phosphor. For the first time a peak at 375 nm was observed in CL spectra of SrAl2O4:Eu2+ (1%) nanophosphors. Luminescence excitation spectra analysis have shown that this peak is related to crystal defects. Also in TSL curve one strong peak was observed in the region above room temperature (T = 325 K), which is attributed to lattice defects, namely oxygen vacancies. A green LED was fabricated by the combination of the SrAl2O4:Eu2+ (1%) nanosized phosphor and a 365 nm UV InGaN chip.
Oxidation of TD nickel at 1050 C and 1200 C as compared with three grades of nickel of different purity

NASA Technical Reports Server (NTRS)

Lowell, C. E.; Grisaffe, S. J.; Deadmore, D. L.

1972-01-01

The isothermal oxidation of three nickels of different purity, Ni-200, Ni-270, and JM-Ni, was compared with that of TD-Ni in air at 1050 and 1200 C. The samples were oxidized as ground, as polished, or as annealed and polished. Weight change, metal loss, scale thickness, oxide morphology, and scale texture were determined. In degree of oxidation, TD-Ni was nearly the same as the higher purity materials, Ni-270 and JM-Ni; and less pure Ni-200 oxidized more than the others. However, in microstructure and scale texture the TD-Ni more closely resembled Ni-200. Grinding only charged the texture of the oxides of Ni_200 and TD-Ni.
Electron-impact dissociative excitation and ionization of N{sub 2}D{sup +}

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

Fogle, M.; Bahati, E. M.; Bannister, M. E.

Absolute cross sections for electron-impact dissociation of N{sub 2}D{sup +} producing N{sub 2}{sup +}, ND{sup +}, and N{sup +} ion fragments were measured in the 5- to 100-eV range using a crossed electron-ion beams technique. In the 5- to 20-eV region, in which dissociative excitation (DE) is the principal contributing mechanism, N{sub 2}{sup +} production dominates. The N{sub 2}{sup +} + D dissociation channel shows a large resonant-like structure in the DE cross section, as observed previously in electron impact dissociation of triatomic dihydride species [M. Fogle, E. M. Bahati, M. E. Bannister, S. H. M. Deng, C. R. Vane,more » R. D. Thomas, and V. Zhaunerchyk, Phys. Rev. A 82, 042720 (2010)]. In the dissociative ionization (DI) region, 20- to 100-eV, N{sub 2}{sup +}, ND{sup +}, and N{sup +} ion fragment production are comparable. The observance of the ND{sup +} and N{sup +} ion fragments indicate breaking of the N - N bond along certain dissociation channels.« less
Word Criticality Analysis. MOS: 67N. Skill Levels 1 & 2

DTIC Science & Technology

1981-09-01

12 1 , lat 0.. 71N 4 1 s,1 󈧅 119 *I .!Ill4 r ITr L34 U., p I*. 1, r-*44,1I6 C. I ", il. TD %T i - 96’ !04- 2,1 -i: l st a64 1104 121! tio 2...14 1’.1 !$04 4:4 11.1* :74 :’~ ~4 te 4 , 4?. 4.. 7 ., !:j-q1 , **)4 1Q3 *2 .1 .~ 4134 . 1.,’ 4- 1 41st -74 Ott. 󈧒 *4 . ,4 4,7Y t 1 46520 n190 37.1
Ground and excited states of NH4: Electron propagator and quantum defect analysis

NASA Astrophysics Data System (ADS)

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

2004-05-01

Vertical excitation energies of the Rydberg radical NH4 are inferred from ab initio electron propagator calculations on the electron affinities of NH4+. The adiabatic ionization energy of NH4 is evaluated with coupled-cluster calculations. These predictions provide optimal parameters for the molecular-adapted quantum defect orbital method, which is used to determine Einstein emission coefficients and radiative lifetimes. Comparisons with spectroscopic data and previous calculations are discussed.
Mission Management Computer and Sequencing Hardware for RLV-TD HEX-01 Mission

NASA Astrophysics Data System (ADS)

Gupta, Sukrat; Raj, Remya; Mathew, Asha Mary; Koshy, Anna Priya; Paramasivam, R.; Mookiah, T.

2017-12-01

Reusable Launch Vehicle-Technology Demonstrator Hypersonic Experiment (RLV-TD HEX-01) mission posed some unique challenges in the design and development of avionics hardware. This work presents the details of mission critical avionics hardware mainly Mission Management Computer (MMC) and sequencing hardware. The Navigation, Guidance and Control (NGC) chain for RLV-TD is dual redundant with cross-strapped Remote Terminals (RTs) interfaced through MIL-STD-1553B bus. MMC is Bus Controller on the 1553 bus, which does the function of GPS aided navigation, guidance, digital autopilot and sequencing for the RLV-TD launch vehicle in different periodicities (10, 20, 500 ms). Digital autopilot execution in MMC with a periodicity of 10 ms (in ascent phase) is introduced for the first time and successfully demonstrated in the flight. MMC is built around Intel i960 processor and has inbuilt fault tolerance features like ECC for memories. Fault Detection and Isolation schemes are implemented to isolate the failed MMC. The sequencing hardware comprises Stage Processing System (SPS) and Command Execution Module (CEM). SPS is `RT' on the 1553 bus which receives the sequencing and control related commands from MMCs and posts to downstream modules after proper error handling for final execution. SPS is designed as a high reliability system by incorporating various fault tolerance and fault detection features. CEM is a relay based module for sequence command execution.
Proposed Project Selection Method for Human Support Research and Technology Development (HSR&TD)

NASA Technical Reports Server (NTRS)

Jones, Harry

2005-01-01

The purpose of HSR&TD is to deliver human support technologies to the Exploration Systems Mission Directorate (ESMD) that will be selected for future missions. This requires identifying promising candidate technologies and advancing them in technology readiness until they are acceptable. HSR&TD must select an may of technology development projects, guide them, and either terminate or continue them, so as to maximize the resulting number of usable advanced human support technologies. This paper proposes an effective project scoring methodology to support managing the HSR&TD project portfolio. Researchers strongly disagree as to what are the best technology project selection methods, or even if there are any proven ones. Technology development is risky and outstanding achievements are rare and unpredictable. There is no simple formula for success. Organizations that are satisfied with their project selection approach typically use a mix of financial, strategic, and scoring methods in an open, established, explicit, formal process. This approach helps to build consensus and develop management insight. It encourages better project proposals by clarifying the desired project attributes. We propose a project scoring technique based on a method previously used in a federal laboratory and supported by recent research. Projects are ranked by their perceived relevance, risk, and return - a new 3 R's. Relevance is the degree to which the project objective supports the HSR&TD goal of developing usable advanced human support technologies. Risk is the estimated probability that the project will achieve its specific objective. Return is the reduction in mission life cycle cost obtained if the project is successful. If the project objective technology performs a new function with no current cost, its return is the estimated cash value of performing the new function. The proposed project selection scoring method includes definitions of the criteria, a project evaluation
Electronic Excited States of Tungsten(0) Arylisocyanides.

PubMed

Kvapilová, Hana; Sattler, Wesley; Sattler, Aaron; Sazanovich, Igor V; Clark, Ian P; Towrie, Michael; Gray, Harry B; Záliš, Stanislav; Vlček, Antonín

2015-09-08

W(CNAryl)6 complexes containing 2,6-diisopropylphenyl isocyanide (CNdipp) are powerful photoreductants with strongly emissive long-lived excited states. These properties are enhanced upon appending another aryl ring, e.g., W(CNdippPh(OMe2))6; CNdippPh(OMe2) = 4-(3,5-dimethoxyphenyl)-2,6-diisopropylphenylisocyanide (Sattler et al. J. Am. Chem. Soc. 2015, 137, 1198-1205). Electronic transitions and low-lying excited states of these complexes were investigated by time-dependent density functional theory (TDDFT); the lowest triplet state was characterized by time-resolved infrared spectroscopy (TRIR) supported by density functional theory (DFT). The intense absorption band of W(CNdipp)6 at 460 nm and that of W(CNdippPh(OMe2))6 at 500 nm originate from transitions of mixed ππ*(C≡N-C)/MLCT(W → Aryl) character, whereby W is depopulated by ca. 0.4 e(-) and the electron-density changes are predominantly localized along two equatorial molecular axes. The red shift and intensity rise on going from W(CNdipp)6 to W(CNdippPh(OMe2))6 are attributable to more extensive delocalization of the MLCT component. The complexes also exhibit absorptions in the 300-320 nm region, owing to W → C≡N MLCT transitions. Electronic absorptions in the spectrum of W(CNXy)6 (Xy = 2,6-dimethylphenyl), a complex with orthogonal aryl orientation, have similar characteristics, although shifted to higher energies. The relaxed lowest W(CNAryl)6 triplet state combines ππ* excitation of a trans pair of C≡N-C moieties with MLCT (0.21 e(-)) and ligand-to-ligand charge transfer (LLCT, 0.24-0.27 e(-)) from the other four CNAryl ligands to the axial aryl and, less, to C≡N groups; the spin density is localized along a single Aryl-N≡C-W-C≡N-Aryl axis. Delocalization of excited electron density on outer aryl rings in W(CNdippPh(OMe2))6 likely promotes photoinduced electron-transfer reactions to acceptor molecules. TRIR spectra show an intense broad bleach due to ν(C≡N), a prominent transient
4,4\\'-Methylene bis(N,N\\'-dimethyl)aniline

Integrated Risk Information System (IRIS)

4,4 ' - Methylene bis ( N , N ' - dimethyl ) aniline ; CASRN 101 - 61 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Haz

Energy transfer of highly vibrationally excited naphthalene: collisions with CHF3, CF4, and Kr.

PubMed

Chen Hsu, Hsu; Tsai, Ming-Tsang; Dyakov, Yuri A; Ni, Chi-Kung

2011-08-07

Energy transfer of highly vibrationally excited naphthalene in the triplet state in collisions with CHF(3), CF(4), and Kr was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. Highly vibrationally excited naphthalene (2.0 eV vibrational energy) was formed via the rapid intersystem crossing of naphthalene initially excited to the S(2) state by 266 nm photons. The shapes of the collisional energy-transfer probability density functions were measured directly from the scattering results of highly vibrationally excited naphthalene. In comparison to Kr atoms, the energy transfer in collisions between CHF(3) and naphthalene shows more forward scatterings, larger cross section for vibrational to translational (V → T) energy transfer, smaller cross section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation, especially in the range -ΔE(d) = -100 to -800 cm(-1). On the other hand, the difference of energy transfer properties between collisional partners Kr and CF(4) is small. The enhancement of the V → T energy transfer in collisions with CHF(3) is attributed to the large attractive interaction between naphthalene and CHF(3) (1-3 kcal/mol).
Adaptation of the TdT assay for semi-quantitative flow cytometric detection of DNA strand breaks

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

Bromidge, T.J.; Howe, D.J.; Johnson, S.A.

The enzyme Terminal Deoxynucleotidyl Transferase (TdT) is a DNA polymerase which can be used to label DNA strand breaks by the incorporation of a labelled nucleotide followed by a fluorescent detection step. The amount of label incorporated can then be assessed by flow cytometry. The mechanism of action of TdT, however, will allow the addition of varying numbers of nucleotides to the free 3{prime} termini produced by DNA strand breaks. The substitution of Digoxigenin (DIG){trademark} labelled dideoxynucleotides for labelled deoxy-nucleotides in the TdT assay will limit the addition of label to a DNA break to a single nucleotide, thus ensuringmore » a direct relationship between an increase in DNA strand breaks and an increase in fluorescence. We have used this adaptation of the TdT assay to evaluate DNA damage incurred in lymphocytes, from patients with Chronic Lymphocytic Leukemia (CLL), on exposure to UV irradiation and apoptosis-inducing drugs, fludarabine and 2-Chloro-2{prime}-deoxyadenosine (2-CdA). This technique may give a good indication of the susceptibility of CLL patients to apoptosis inducing drugs, and hence an indication of the likely response to these therapies. 7 refs., 2 figs., 2 tabs.« less
Identification of potentially cytotoxic lesions induced by UVA photoactivation of DNA 4-thiothymidine in human cells

PubMed Central

Reelfs, Olivier; Macpherson, Peter; Ren, Xiaolin; Xu, Yao-Zhong; Karran, Peter; Young, Antony R.

2011-01-01

Photochemotherapy—in which a photosensitizing drug is combined with ultraviolet or visible radiation—has proven therapeutic effectiveness. Existing approaches have drawbacks, however, and there is a clinical need to develop alternatives offering improved target cell selectivity. DNA substitution by 4-thiothymidine (S4TdR) sensitizes cells to killing by ultraviolet A (UVA) radiation. Here, we demonstrate that UVA photoactivation of DNA S4TdR does not generate reactive oxygen or cause direct DNA breakage and is only minimally mutagenic. In an organotypic human skin model, UVA penetration is sufficiently robust to kill S4TdR-photosensitized epidermal cells. We have investigated the DNA lesions responsible for toxicity. Although thymidine is the predominant UVA photoproduct of S4TdR in dilute solution, more complex lesions are formed when S4TdR-containing oligonucleotides are irradiated. One of these, a thietane/S5-(6-4)T:T, is structurally related to the (6-4) pyrimidine:pyrimidone [(6-4) Py:Py] photoproducts induced by UVB/C radiation. These lesions are detectable in DNA from S4TdR/UVA-treated cells and are excised from DNA more efficiently by keratinocytes than by leukaemia cells. UVA irradiation also induces DNA interstrand crosslinking of S4TdR-containing duplex oligonucleotides. Cells defective in repairing (6-4) Py:Py DNA adducts or processing DNA crosslinks are extremely sensitive to S4TdR/UVA indicating that these lesions contribute significantly to S4TdR/UVA cytotoxicity. PMID:21890905
Using SpaceClaim/TD Direct for Modeling Components with Complex Geometries for the Thermal Desktop-Based Advanced Stirling Radioisotope Generator Model

NASA Technical Reports Server (NTRS)

Fabanich, William

2014-01-01

SpaceClaim/TD Direct has been used extensively in the development of the Advanced Stirling Radioisotope Generator (ASRG) thermal model. This paper outlines the workflow for that aspect of the task and includes proposed best practices and lessons learned. The ASRG thermal model was developed to predict component temperatures and power output and to provide insight into the prime contractors thermal modeling efforts. The insulation blocks, heat collectors, and cold side adapter flanges (CSAFs) were modeled with this approach. The model was constructed using mostly TD finite difference (FD) surfaces solids. However, some complex geometry could not be reproduced with TD primitives while maintaining the desired degree of geometric fidelity. Using SpaceClaim permitted the import of original CAD files and enabled the defeaturing repair of those geometries. TD Direct (a SpaceClaim add-on from CRTech) adds features that allowed the mark-up of that geometry. These so-called mark-ups control how finite element (FE) meshes were generated and allowed the tagging of features (e.g. edges, solids, surfaces). These tags represent parameters that include: submodels, material properties, material orienters, optical properties, and radiation analysis groups. TD aliases were used for most tags to allow analysis to be performed with a variety of parameter values. Domain-tags were also attached to individual and groups of surfaces and solids to allow them to be used later within TD to populate objects like, for example, heaters and contactors. These tools allow the user to make changes to the geometry in SpaceClaim and then easily synchronize the mesh in TD without having to redefine these objects each time as one would if using TD Mesher.The use of SpaceClaim/TD Direct has helped simplify the process for importing existing geometries and in the creation of high fidelity FE meshes to represent complex parts. It has also saved time and effort in the subsequent analysis.
Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine) 2(CN) 2

DOE PAGES

Kjaer, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto; ...

2017-07-06

Here, we have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy) 2(CN) 2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy) 2(CN) 2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a shortmore » lived metal-centered triplet transient species. These measurements of [Fe(bpy) 2(CN) 2] complement prior measurement performed on [Fe(bpy) 3] 2+ and [Fe(bpy)(CN) 4] 2– in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy) N(CN) 6–2N] 2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3 d transition metal complexes.« less
Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine) 2(CN) 2

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

Kjaer, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto

Here, we have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy) 2(CN) 2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy) 2(CN) 2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a shortmore » lived metal-centered triplet transient species. These measurements of [Fe(bpy) 2(CN) 2] complement prior measurement performed on [Fe(bpy) 3] 2+ and [Fe(bpy)(CN) 4] 2– in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy) N(CN) 6–2N] 2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3 d transition metal complexes.« less
Cholinergic modulation of neuronal excitability in the rat suprachiasmatic nucleus.

PubMed

Yang, Jyh-Jeen; Wang, Yu-Ting; Cheng, Pi-Cheng; Kuo, Yeh-Jung; Huang, Rong-Chi

2010-03-01

The central cholinergic system regulates both the circadian clock and sleep-wake cycle and may participate in the feedback control of vigilance states on neural excitability in the suprachiasmatic nucleus (SCN) that houses the circadian clock. Here we investigate the mechanisms for cholinergic modulation of SCN neuron excitability. Cell-attached recordings indicate that the nonspecific cholinergic agonist carbachol (CCh) inhibited 55% and excited 21% SCN neurons, leaving 24% nonresponsive. Similar response proportions were produced by two muscarinic receptor [muscarinic acetylcholine receptor (mAChR)] agonists, muscarine and McN-A-343 (M1/4 agonist), but not by two nicotinic receptor (nAChR) agonists, nicotine and choline (alpha7-nAChR agonist), which, however, produced similar response proportions. Whole cell and perforated-patch recordings indicate that CCh inhibition of firing was mediated by membrane hyperpolarization due to activation of background K(+) currents, which were sensitive to submillimolar concentrations of Ba(2+) and to millimolar concentrations of TEA. RT-PCR analysis demonstrated the presence of mRNA for M1 to M5 mAChRs in SCN. The CCh-induced hyperpolarization and activation of background K(+) currents were blocked by M4 antagonists and to a lesser degree by M1 antagonists but were insensitive to the antagonists for M2 or M3, suggesting the involvement of M4 and M1 mAChRs in mediating CCh inhibition of firing. CCh enhancement of firing was mediated by membrane depolarization, as a result of postsynaptic inhibition of background K(+) currents. The multiple actions of cholinergic modulation via multiple receptors and ion channels may allow acetylcholine to finely control SCN neuron excitability in different physiological settings.
Users manual and modeling improvements for axial turbine design and performance computer code TD2-2

NASA Technical Reports Server (NTRS)

Glassman, Arthur J.

1992-01-01

Computer code TD2 computes design point velocity diagrams and performance for multistage, multishaft, cooled or uncooled, axial flow turbines. This streamline analysis code was recently modified to upgrade modeling related to turbine cooling and to the internal loss correlation. These modifications are presented in this report along with descriptions of the code's expanded input and output. This report serves as the users manual for the upgraded code, which is named TD2-2.
Excited-state Raman spectroscopy with and without actinic excitation: S{sub 1} Raman spectra of trans-azobenzene

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

Dobryakov, A. L.; Quick, M.; Ioffe, I. N.

We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S{sub 1} and S{sub 0} spectra of trans-azobenzene in n-hexane. The S{sub 1} spectra were also measured conventionally, upon nπ* (S{sub 0} → S{sub 1}) actinic excitation. The results are discussed and compared to earlier reports.
Energy Dispersive XAFS: Characterization of Electronically Excited States of Copper(I) Complexes

PubMed Central

2013-01-01

Energy dispersive X-ray absorption spectroscopy (ED-XAS), in which the whole XAS spectrum is acquired simultaneously, has been applied to reduce the real-time for acquisition of spectra of photoinduced excited states by using a germanium microstrip detector gated around one X-ray bunch of the ESRF (100 ps). Cu K-edge XAS was used to investigate the MLCT states of [Cu(dmp)2]+ (dmp =2,9-dimethyl-1,10-phenanthroline) and [Cu(dbtmp)2]+ (dbtmp =2,9-di-n-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) with the excited states created by excitation at 450 nm (10 Hz). The decay of the longer lived complex with bulky ligands, was monitored for up to 100 ns. DFT calculations of the longer lived MLCT excited state of [Cu(dbp)2]+ (dbp =2,9-di-n-butyl-1,10-phenanthroline) with the bulkier diimine ligands, indicated that the excited state behaves as a Jahn–Teller distorted Cu(II) site, with the interligand dihedral angle changing from 83 to 60° as the tetrahedral coordination geometry flattens and a reduction in the Cu–N distance of 0.03 Å. PMID:23718738
Photochemical synthesis of the Fe0/C3N4/MoS2 heterostructure as a highly active and reusable photocatalyst

NASA Astrophysics Data System (ADS)

Wang, Xiu; Zhou, Zhiming; Liang, Zhiyu; Zhuang, Zanyong; Yu, Yan

2017-11-01

The Fe0/C3N4/MoS2 heterostructure was fabricated through photochemical synthesis that was free of NaBH4. Specifically, the g-C3N4/MoS2 (GCNM) composite was used as the substrate. Visible light excited the electrons from the valence band of the GCNM in the substrate, and the excited electrons reduced the Fe2+ ions in the solution nearby GCNM to Fe0 and then created the Fe0/C3N4/MoS2 heterostructure. Small Fe0 (<9 nm) dots well dispersed on the GCNM surface were obtained, because the diffusion of the Fe ions in the solution and the diffusion of the electrons on the GCNM substrate restricted the growth of Fe0 nanoparticles. The smaller size of Fe0 provided a larger number of active metal centers and improved the carrier separation efficiency. As a result, the Fe0/C3N4/MoS2 heterostructure exhibited superior catalytic properties in the redox reactions of rhodamine B, Cr(VI), Pb(II), and Cd(II). It could also be readily recycled without severe loss of catalytic performance.
New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N I

NASA Astrophysics Data System (ADS)

Tayal, S. S.

2006-03-01

The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N I lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strengths over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s22p3 4So, 2Do, 2Po, 2s2p4 4P, 2s22p23s 4P, and 2P terms and from these levels to the levels of the 2s22p23p 2So, 4Do, 4Po, 4So, 2Do, 2Po, 2s22p23s 2D, 2s22p24s 4P, 2P, 2s22p23d 2P, 4F, 2F, 4P, 4D, and 2D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.
Initial mechanisms for the dissociation of carbon from electronically-excited nitrotoluene molecules

NASA Astrophysics Data System (ADS)

Yuan, Bing; Eilers, Hergen

2017-12-01

We calculated the photoinduced decomposition of various nitrotoluene molecules, resulting in the formation of atomic carbon, at the B3LYP/6-311++G(d,p) level of theory using Gaussian 09. In addition, we used TD-DFT (B3LYP/6-311++G(d,p)) to calculate the excitation energies. The results confirm our previously reported experimental results. Specifically, we show that the absorption of 226 nm (5.49 eV) light can lead to the decomposition of nitrotoluene molecules and the formation of atomic carbon. One 226 nm photon is sufficient for the dissociation of carbon from 2-NT and 4-NT molecules. During the dissociation process, the CH3 group provides the dissociated carbon atom and the NO2 group accepts the H atoms from either the CH3 group or the benzene ring before carbon exits the molecular system. For the second and third carbon dissociation of 2-NT, the energy barriers are 6.70 eV and 7.43 eV, respectively, and two 226 nm photons would need to be absorbed by the molecule. If extra NO is present during the first carbon dissociation of 2-NT, it gets involved in the last two decomposition steps and forms a C=NH-N=O structure which stabilizes the decomposition products and lowers the energy barrier from 5.22 eV to 4.70 eV. However, for the second and third carbon dissociation of 2-NT, the NO molecules have no apparent effect. For nitrotoluene molecules with two or three NO2 groups (i.e., 2,4-DNT, 2,6-DNT, 3,4-DNT, and 2,4,6-TNT), the first carbon dissociation energies are between 5.26 eV and 5.57 eV. The carbon dissociation pathways for these molecules are similar to those of 2-NT. In 2,4-DNT, the lowest energy barriers for the second and third carbon dissociation are 6.54 eV and 6.60 eV, respectively, which are about 1 eV higher than the energy barrier for the first carbon dissociation. In case of 2,4-DNT/NO and 2,4,6-TNT/NO, NO acts as a catalyst in the first carbon dissociation processes and forms a C=NH-N=O structure which lowers the energy barriers by 0.48 eV and 0
Radiation pressure excitation of a low temperature atomic force/magnetic force microscope for imaging in 4-300 K temperature range

NASA Astrophysics Data System (ADS)

Ćelik, Ümit; Karcı, Özgür; Uysallı, Yiǧit; Özer, H. Özgür; Oral, Ahmet

2017-01-01

We describe a novel radiation pressure based cantilever excitation method for imaging in dynamic mode atomic force microscopy (AFM) for the first time. Piezo-excitation is the most common method for cantilever excitation, however it may cause spurious resonance peaks. Therefore, the direct excitation of the cantilever plays a crucial role in AFM imaging. A fiber optic interferometer with a 1310 nm laser was used both for the excitation of the cantilever at the resonance and the deflection measurement of the cantilever in a commercial low temperature atomic force microscope/magnetic force microscope (AFM/MFM) from NanoMagnetics Instruments. The laser power was modulated at the cantilever's resonance frequency by a digital Phase Locked Loop (PLL). The laser beam is typically modulated by ˜500 μW, and ˜141.8 nmpp oscillation amplitude is obtained in moderate vacuum levels between 4 and 300 K. We have demonstrated the performance of the radiation pressure excitation in AFM/MFM by imaging atomic steps in graphite, magnetic domains in CoPt multilayers between 4 and 300 K and Abrikosov vortex lattice in BSCCO(2212) single crystal at 4 K for the first time.
Radiation pressure excitation of a low temperature atomic force/magnetic force microscope for imaging in 4-300 K temperature range.

PubMed

Çelik, Ümit; Karcı, Özgür; Uysallı, Yiğit; Özer, H Özgür; Oral, Ahmet

2017-01-01

We describe a novel radiation pressure based cantilever excitation method for imaging in dynamic mode atomic force microscopy (AFM) for the first time. Piezo-excitation is the most common method for cantilever excitation, however it may cause spurious resonance peaks. Therefore, the direct excitation of the cantilever plays a crucial role in AFM imaging. A fiber optic interferometer with a 1310 nm laser was used both for the excitation of the cantilever at the resonance and the deflection measurement of the cantilever in a commercial low temperature atomic force microscope/magnetic force microscope (AFM/MFM) from NanoMagnetics Instruments. The laser power was modulated at the cantilever's resonance frequency by a digital Phase Locked Loop (PLL). The laser beam is typically modulated by ∼500 μW, and ∼141.8 nm pp oscillation amplitude is obtained in moderate vacuum levels between 4 and 300 K. We have demonstrated the performance of the radiation pressure excitation in AFM/MFM by imaging atomic steps in graphite, magnetic domains in CoPt multilayers between 4 and 300 K and Abrikosov vortex lattice in BSCCO(2212) single crystal at 4 K for the first time.
DFT/TD-DFT study of solvent effect as well the substituents influence on the different features of TPP derivatives for PDT application

NASA Astrophysics Data System (ADS)

Dulski, Mateusz; Kempa, Marta; Kozub, Patrycja; Wójcik, Justyna; Rojkiewicz, Marcin; Kuś, Piotr; Szurko, Agnieszka; Ratuszna, Alicja; Wrzalik, Roman

2013-03-01

Spectral characteristics study of meso-tetraphenylporphyrin derivatives (TPP1 and TPP2) used as photosensitizers for utilization in photodynamic therapy (PDT) has been performed by density functional theory (DFT) and time dependent DFT (TD-DFT) calculations at B3LYP/6-31G(d) level of theory using PCM solvation model. The geometrical parameters of porphyrins have been studied for ground and excited-state geometry to deduce the influence of various substituents as well as solvent effect on the deformation of porphyrin ring. Two theoretical approaches - linear response (LR) and external iteration (EI) - have been performed to replicate absorption and fluorescence emission spectra. Experimental and theoretical investigations have shown that EI method reproduces the absorption energies very well for both singlet-singlet and triplet-triplet transitions, whereas the LR approach is more coherent with experimental fluorescence emission spectra. Spectral features and HOMO-LUMO band gap analysis have shown that TPP1 can be more useful in PDT. Calculations have revealed that two the highest occupied and two the lowest unoccupied molecular orbitals are responsible for the Q-band absorption and are located mainly on the porphyrin ring. In order to verify the substituent effect on the activity of tested compounds in their ground and excited states, the molecular electrostatic potential surfaces have been analyzed.
Development of a HTS transceiver sub-system for 3G mobile communication TD-SCDMA base station

NASA Astrophysics Data System (ADS)

Zhang, Xueqiang; He, Xiaofeng; Wang, Yuehui; Duan, Tao; Wang, Guizhen; Zhang, Yan; Li, Chunguang; Zhang, Qiang; Li, Hong; He, Yusheng

2010-02-01

A prototype of a high temperature superconducting (HTS) transceiver sub-system for applications in a TD-SCDMA, one of the third generation (3G) communication standards, base station has been developed. Both the HTS sub-system and the conventional counterpart have been implemented into a TD-SCDMA commercial communication network and comparison test studies were carried out. The measured results showed that the HTS sub-system could remarkably improve the RF performance of both transmitting and receiving chains.
Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description.

PubMed

Guido, Ciro A; Jacquemin, Denis; Adamo, Carlo; Mennucci, Benedetta

2015-12-08

We critically analyze the performances of continuum solvation models when coupled to time-dependent density functional theory (TD-DFT) to predict solvent effects on both absorption and emission energies of chromophores in solution. Different polarization schemes of the polarizable continuum model (PCM), such as linear response (LR) and three different state specific (SS) approaches, are considered and compared. We show the necessity of introducing a SS model in cases where large electron density rearrangements are involved in the excitations, such as charge-transfer transitions in both twisted and quadrupolar compounds, and underline the very delicate interplay between the selected polarization method and the chosen exchange-correlation functional. This interplay originates in the different descriptions of the transition and ground/excited state multipolar moments by the different functionals. As a result, the choice of both the DFT functional and the solvent polarization scheme has to be consistent with the nature of the studied electronic excitation.
Collisional excitation of HC3N by para- and ortho-H2

NASA Astrophysics Data System (ADS)

Faure, Alexandre; Lique, François; Wiesenfeld, Laurent

2016-08-01

New calculations for rotational excitation of cyanoacetylene by collisions with hydrogen molecules are performed to include the lowest 38 rotational levels of HC3N and kinetic temperatures to 300 K. Calculations are based on the interaction potential of Wernli et al. whose accuracy is checked against spectroscopic measurements of the HC3N-H2 complex. The quantum coupled-channel approach is employed and complemented by quasi-classical trajectory calculations. Rate coefficients for ortho-H2 are provided for the first time. Hyperfine resolved rate coefficients are also deduced. Collisional propensity rules are discussed and comparisons between quantum and classical rate coefficients are presented. This collisional data should prove useful in interpreting HC3N observations in the cold and warm ISM, as well as in protoplanetary discs.
Spin dynamics and magnetoelectric coupling mechanism of C o4N b2O9

NASA Astrophysics Data System (ADS)

Deng, Guochu; Cao, Yiming; Ren, Wei; Cao, Shixun; Studer, Andrew J.; Gauthier, Nicolas; Kenzelmann, Michel; Davidson, Gene; Rule, Kirrily C.; Gardner, Jason S.; Imperia, Paolo; Ulrich, Clemens; McIntyre, Garry J.

2018-02-01

Neutron powder diffraction experiments reveal that C o4N b2O9 forms a noncollinear in-plane magnetic structure with C o2 + moments lying in the a b plane. The spin-wave excitations of this magnet were measured by using inelastic neutron scattering and soundly simulated by a dynamic model involving nearest- and next-nearest-neighbor exchange interactions, in-plane anisotropy, and the Dzyaloshinskii-Moriya interaction. The in-plane magnetic structure of C o4N b2O9 is attributed to the large in-plane anisotropy, while the noncollinearity of the spin configuration is attributed to the Dzyaloshinskii-Moriya interaction. The high magnetoelectric coupling effect of C o4N b2O9 in fields can be explained by its special in-plane magnetic structure.

Time-dependent density-functional tight-binding method with the third-order expansion of electron density

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

Nishimoto, Yoshio, E-mail: nishimoto.yoshio@fukui.kyoto-u.ac.jp

2015-09-07

We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of themore » third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.« less
Time-dependent density-functional tight-binding method with the third-order expansion of electron density.

PubMed

Nishimoto, Yoshio

2015-09-07

We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of the third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.
The doping sites in Eu2+-doped AIBIIPO4 phosphors and their consequence on the photoluminescence excitation spectra

NASA Astrophysics Data System (ADS)

Amer, M.; Boutinaud, P.

2018-02-01

The energy corresponding to the excitation edge in Eu2+-doped phosphate phosphors of the type AIBIIPO4 (AI = monovalent cation, BII = divalent cation) is calculated from the knowledge of two crystal-structure-related factors he(X(i)) and Fc(X(i)) which are connected respectively to the crystal field splitting (CFS) and the centroid energy (Ec) of the excited 4f65d1 electron configuration of Eu2+. The calculation is carried out for each cation site X(i) available for Eu2+ in 25 different compositions of AIBIIPO4 including NaZnPO4-Eu2+ for which the luminescence is firstly reported. Our results indicate (1) that is it possible to identify the nature of the cation site that contributes to the excitation edge of Eu2+ in AIBIIPO4 within an accuracy of±1000 cm-1 and (2) that the method can be used as a tool for the predictive design of AIBIIPO4 - Eu2+ phosphors applicable in solid state LED-based lighting.
Three-photon excitation of 2,5-bis(4-biphenyl)oxazole: steady-state and time-resolved intensities and anisotropies

NASA Astrophysics Data System (ADS)

Gryczynski, Ignacy; Malak, Henryk; Hell, Stefan W.; Lakowicz, Joseph R.

1996-10-01

Three-photon excitation of 2,5-bis(4-biphenyl) oxazole (BBO) was observed when it was excited with the fundamental output of a femtosecond Ti:sapphire laser above 820 nm. The emission spectrum of BBO was identical for one-, two-, and three-photon excitation at 320, 640, and 960 nm, respectively. In toluene and triacetin, the emission intensity of BBO depended on the square of the laser power for wavelengths below 820 nm and displayed a sharp transition to a cubic dependence at longer wavelengths. The spatial distribution of the emission of BBO with three- photon excitation was more strongly localized than for two- photon excitation of a coumarin fluorophore at the same wavelength. The same single exponential intensity decay was observed for one-, two-, and three-photon excitation. However, the frequency domain anisotropy decay with three- photon excitation at 960 nm revealed a larger time-zero anisotropy, larger differential polarized phase angle, and larger modulated anisotropy than is possible for two-photon excitation with colinear oscillators. In triacetin, the anisotropy is not constant for three-photon excitation at different wavelengths. Surprisingly, the fluorescence intensities for three-photon excitation were only about 100- fold less than for two-photon excitation. The increasing availability of Ti:sapphire lasers suggests that multiphoton excitation can become a common tool in fluorescence spectroscopy.
Signal-on electrochemical assay for label-free detection of TdT and BamHI activity based on grown DNA nanowire-templated copper nanoclusters.

PubMed

Hu, Yufang; Zhang, Qingqing; Xu, Lihua; Wang, Jiao; Rao, Jiajia; Guo, Zhiyong; Wang, Sui

2017-11-01

Electrochemical methods allow fast and inexpensive analysis of enzymatic activity. Here, a simple and yet efficient "signal-on" electrochemical assay for sensitive, label-free detection of DNA-related enzyme activity was established on the basis of terminal deoxynucleotidyl transferase (TdT)-mediated extension strategy. TdT, which is a template-independent DNA polymerase, can catalyze the sequential addition of deoxythymidine triphosphate (dTTP) at the 3'-OH terminus of single-stranded DNA (ssDNA); then, the TdT-yield T-rich DNA nanowires can be employed as the synthetic template of copper nanoclusters (CuNCs). Grown DNA nanowires-templated CuNCs (noted as DNA-CuNCs) were attached onto graphene oxide (GO) surface and exhibited unique electrocatalytic activity to H 2 O 2 reduction. Under optimal conditions, the proposed biosensor was utilized for quantitatively monitoring TdT activity, with the observed LOD of 0.1 U/mL. It also displayed high selectivity to TdT with excellent stability, and offered a facile, convenient electrochemical method for TdT-relevant inhibitors screening. Moreover, the proposed sensor was successfully used for BamHI activity detection, in which a new 3'-OH terminal was exposed by the digestion of a phosphate group. Ultimately, it has good prospects in DNA-related enzyme-based biochemical studies, disease diagnosis, and drug discovery. Graphical Abstract Extraordinary TdT-generated DNA-CuNCs are synthesized and act as a novel electrochemical sensing platform for sensitive detection of TdT and BamHI activity in biological environments.
Excitations and relaxation dynamics in multiferroic GeV4S8 studied by terahertz and dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Reschke, S.; Wang, Zhe; Mayr, F.; Ruff, E.; Lunkenheimer, P.; Tsurkan, V.; Loidl, A.

2017-10-01

We report on THz time-domain spectroscopy on multiferroic GeV4S8 , which undergoes orbital ordering at a Jahn-Teller transition at 30.5 K and exhibits antiferromagnetic order below 14.6 K. The THz experiments are complemented by dielectric experiments at audio and radio frequencies. We identify a low-lying excitation close to 0.5 THz, which is only weakly temperature dependent and probably corresponds to a molecular excitation within the electronic level scheme of the V4 clusters. In addition, we detect complex temperature-dependent behavior of a low-lying phononic excitation, closely linked to the onset of orbitally driven ferroelectricity. In the high-temperature cubic phase, which is paramagnetic and orbitally disordered, this excitation is of relaxational character becomes an overdamped Lorentzian mode in the orbitally ordered phase below the Jahn-Teller transition, and finally appears as well-defined phonon excitation in the antiferromagnetic state. Abrupt changes in the real and imaginary parts of the complex dielectric permittivity show that orbital ordering appears via a structural phase transition with strong first-order character and that the onset of antiferromagnetic order is accompanied by significant structural changes, which are of first-order character, too. Dielectric spectroscopy documents that at low frequencies, significant dipolar relaxations are present in the orbitally ordered, paramagnetic phase only. In contrast to the closely related GaV4S8 , this relaxation dynamics that most likely mirrors coupled orbital and polar fluctuations does not seem to be related to the dynamic processes detected in the THz regime.
The development of siblings of children with autism at 4 and 14 months: social engagement, communication, and cognition.

PubMed

Yirmiya, Nurit; Gamliel, Ifat; Pilowsky, Tammy; Feldman, Ruth; Baron-Cohen, Simon; Sigman, Marian

2006-05-01

To compare siblings of children with autism (SIBS-A) and siblings of children with typical development (SIBS-TD) at 4 and 14 months of age. At 4 months, mother-infant interactional synchrony during free play, infant gaze and affect during the still-face paradigm, and infant responsiveness to a name-calling paradigm were examined (n = 21 in each group). At 14 months, verbal and nonverbal communication skills were examined as well as cognition (30 SIBS-A and 31 SIBS-TD). Most SIBS-A were functioning as well as the SIBS-TD at 4 and 14 months of age. However, some differences in early social engagement and later communicative and cognitive skills emerged. Synchrony was weaker in the SIBS-A dyads, but only for infant-led interactions. Infant SIBS-A revealed more neutral affect during the still-face procedure and were less upset by it than was true for the SIBS-TD. A surprising result was that significantly more SIBS-A responded to their name being called by their mothers compared to SIBS-TD. At 14 months, SIBS-A made fewer nonverbal requesting gestures and achieved lower language scores on the Bayley Scale. Six SIBS-A revealed a language delay of 5 months and were responsible for some of the significant differences between SIBS-A and SIBS-TD. Furthermore, infant SIBS-A who showed more neutral affect to the still face and were less able to respond to their name being called by their mothers initiated fewer nonverbal joint attention and requesting behaviors at 14 months, respectively. Focused on the genetic liability for the broad phenotype of autism as well as the possible influence of having a sibling with autism.
Using SpaceClaimTD Direct for Modeling Components with Complex Geometries for the Thermal Desktop-Based Advanced Stirling Radioisotope Generator Model

NASA Technical Reports Server (NTRS)

Fabanich, William A., Jr.

2014-01-01

SpaceClaim/TD Direct has been used extensively in the development of the Advanced Stirling Radioisotope Generator (ASRG) thermal model. This paper outlines the workflow for that aspect of the task and includes proposed best practices and lessons learned. The ASRG thermal model was developed to predict component temperatures and power output and to provide insight into the prime contractor's thermal modeling efforts. The insulation blocks, heat collectors, and cold side adapter flanges (CSAFs) were modeled with this approach. The model was constructed using mostly TD finite difference (FD) surfaces/solids. However, some complex geometry could not be reproduced with TD primitives while maintaining the desired degree of geometric fidelity. Using SpaceClaim permitted the import of original CAD files and enabled the defeaturing/repair of those geometries. TD Direct (a SpaceClaim add-on from CRTech) adds features that allowed the "mark-up" of that geometry. These so-called "mark-ups" control how finite element (FE) meshes are to be generated through the "tagging" of features (e.g. edges, solids, surfaces). These tags represent parameters that include: submodels, material properties, material orienters, optical properties, and radiation analysis groups. TD aliases were used for most tags to allow analysis to be performed with a variety of parameter values. "Domain-tags" were also attached to individual and groups of surfaces and solids to allow them to be used later within TD to populate objects like, for example, heaters and contactors. These tools allow the user to make changes to the geometry in SpaceClaim and then easily synchronize the mesh in TD without having to redefine the objects each time as one would if using TDMesher. The use of SpaceClaim/TD Direct helps simplify the process for importing existing geometries and in the creation of high fidelity FE meshes to represent complex parts. It also saves time and effort in the subsequent analysis.
A novel yellow-emitting SrAlSi4N7:Ce3+ phosphor for solid state lighting: Synthesis, electronic structure and photoluminescence properties

NASA Astrophysics Data System (ADS)

Ruan, Jian; Xie, Rong-Jun; Funahashi, Shiro; Tanaka, Yoshinori; Takeda, Takashi; Suehiro, Takayuki; Hirosaki, Naoto; Li, Yuan-Qiang

2013-12-01

Ce3+-doped and Ce3+/Li+-codoped SrAlSi4N7 phosphors were synthesized by gas pressure sintering of powder mixtures of Sr3N2, AlN, α-Si3N4, CeN and Li3N. The phase purity, electronic crystal structure, photoluminescence properties of SrAlSi4N7:Ce3+(Ce3+/Li+) were investigated in this work. The band structure calculated by the DMol3 code shows that SrAlSi4N7 has a direct band gap of 3.87 eV. The single crystal analysis of Ce3+-doped SrAlSi4N7 indicates a disordered Si/Al distribution and nitrogen vacnacy defects. SrAlSi4N7 was identified as a major phase of the fired powders, and Sr5Al5Si21N35O2 and AlN as minor phases. Both Ce3+ and Ce3+/Li+ doped SrAlSi4N7 phosphors can be efficiently excited by near-UV or blue light and show a broadband yellow emission peaking around 565 nm. A highest external quantum efficiency of 38.3% under the 450 nm excitation was observed for the Ce3+/Li+-doped SrAlSi4N7 (5 mol%). A white light LED lamp with color temperature of 6300 K and color rendering index of Ra=78 was achieved by combining Sr0.97Al1.03Si3.997N\\94\\maccounttest14=t0005_18193 7:Ce3+0.03 with a commercial blue InGaN chip. It indicates that SrAlSi4N7:Ce3+ is a promising yellow emitting down-conversion phosphor for white LEDs.
TRPC6-mediated ERK1/2 Activation Regulates Neuronal Excitability via Subcellular Kv4.3 Localization in the Rat Hippocampus

PubMed Central

Kim, Ji-Eun; Park, Jin-Young; Kang, Tae-Cheon

2017-01-01

Recently, we have reported that transient receptor potential channel-6 (TRPC6) plays an important role in the regulation of neuronal excitability and synchronization of spiking activity in the dentate granule cells (DGC). However, the underlying mechanisms of TRPC6 in these phenomena have been still unclear. In the present study, we investigated the role of TRPC6 in subcellular localization of Kv4.3 and its relevance to neuronal excitability in the rat hippocampus. TRPC6 knockdown increased excitability and inhibitory transmission in the DGC and the CA1 neurons in response to a paired-pulse stimulus. However, TRPC6 knockdown impaired γ-aminobutyric acid (GABA)ergic inhibition in the hippocampus during and after high-frequency stimulation (HFS). TRPC6 knockdown reduced the Kv4.3 clusters in membrane fractions and its dendritic localization on DGC and GABAergic interneurons. TRPC6 knockdown also decreased extracellular signal-regulated kinase 1/2 (ERK1/2) phosphorylation and the efficacy of 4-aminopyridine (4-AP) in neuronal excitability. An ERK1/2 inhibitor generated multiple population spikes in response to a paired-pulse stimulus, concomitant with reduced membrane Kv4.3 translocation. A TRPC6 activator (hyperforin) reversed the effects of TRPC knockdown, except paired-pulse inhibition. These findings provide valuable clues indicating that TRPC6-mediated ERK1/2 activation may regulate subcellular Kv4.3 localization in DGC and interneurons, which is cause-effect relationship between neuronal excitability and seizure susceptibility. PMID:29326557
In Vitro Activity of TD-1792, a Multivalent Glycopeptide-Cephalosporin Antibiotic, against 377 Strains of Anaerobic Bacteria and 34 Strains of Corynebacterium Species

PubMed Central

Citron, Diane M.; Warren, Yumi A.; Goldstein, Ellie J. C.

2012-01-01

TD-1792 is a multivalent glycopeptide-cephalosporin heterodimer antibiotic with potent activity against Gram-positive bacteria. We tested TD-1792 against 377 anaerobes and 34 strains of Corynebacterium species. Against nearly all Gram-positive strains, TD-1792 had an MIC90 of 0.25 μg/ml and was typically 3 to 7 dilutions more active than vancomycin and daptomycin. PMID:22290981
RNA chaperone StpA loosens interactions of the tertiary structure in the td group I intron in vivo

PubMed Central

Waldsich, Christina; Grossberger, Rupert; Schroeder, Renée

2002-01-01

Efficient splicing of the td group I intron in vivo is dependent on the ribosome. In the absence of translation, the pre-mRNA is trapped in nonnative-splicing-incompetent conformations. Alternatively, folding of the pre-mRNA can be promoted by the RNA chaperone StpA or by the group I intron-specific splicing factor Cyt-18. To understand the mechanism of action of RNA chaperones, we probed the impact of StpA on the structure of the td intron in vivo. Our data suggest that StpA loosens tertiary interactions. The most prominent structural change was the opening of the base triples, which are involved in the correct orientation of the two major intron core domains. In line with the destabilizing activity of StpA, splicing of mutant introns with a reduced structural stability is sensitive to StpA. In contrast, Cyt-18 strengthens tertiary contacts, thereby rescuing splicing of structurally compromised td mutants in vivo. Our data provide direct evidence for protein-induced conformational changes within catalytic RNA in vivo. Whereas StpA resolves tertiary contacts enabling the RNA to refold, Cyt-18 contributes to the overall compactness of the td intron in vivo. PMID:12208852
Designed Er(3+)-singly doped NaYF4 with double excitation bands for simultaneous deep macroscopic and microscopic upconverting bioimaging.

PubMed

Wen, Xuanyuan; Wang, Baoju; Wu, Ruitao; Li, Nana; He, Sailing; Zhan, Qiuqiang

2016-06-01

Simultaneous deep macroscopic imaging and microscopic imaging is in urgent demand, but is challenging to achieve experimentally due to the lack of proper fluorescent probes. Herein, we have designed and successfully synthesized simplex Er(3+)-doped upconversion nanoparticles (UCNPs) with double excitation bands for simultaneous deep macroscopic and microscopic imaging. The material structure and the excitation wavelength of Er(3+)-singly doped UCNPs were further optimized to enhance the upconversion emission efficiency. After optimization, we found that NaYF4:30%Er(3+)@NaYF4:2%Er(3+) could simultaneously achieve efficient two-photon excitation (2PE) macroscopic tissue imaging and three-photon excitation (3PE) deep microscopic when excited by 808 nm continuous wave (CW) and 1480 nm CW lasers, respectively. In vitro cell imaging and in vivo imaging have also been implemented to demonstrate the feasibility and potential of the proposed simplex Er(3+)-doped UCNPs as bioprobe.
Electronic structure, hydrogen bonding and spectroscopic profile of a new 1,2,4-triazole-5(4H)-thione derivative: A combined experimental and theoretical (DFT) analysis

NASA Astrophysics Data System (ADS)

Al-Tamimi, Abdul-Malek S.

2016-09-01

Density functional theory has been implemented to study the electronic structure, molecular properties and vibrational spectra of 3-(adamantan-1-yl)-4-(4-chlorophenyl)-1H-1,2,4-triazole-5(4H)-thione, a novel 1,2,4-triazole-5(4H)-thione derivative. Hydrogen bonded dimer of the title molecule has been studied using B3LYP, M06-2X and X3LYP functionals at 6-311++ G(d,p) level of theory. The intermolecular hydrogen bonding has been studied using NBO analysis of the dimer. Bader's AIM theory was also used to evaluate the strength as well as the hydrogen bonding characteristics. Experimental FT-IR and FT-Raman spectra of the title molecule were related with the spectral data obtained with DFT/B3LYP method. The 1H NMR chemical shifts of the title molecule were calculated by the GIAO method and compared with experimental results. Dipole moment, polarizability (α), first order static hyperpolarizability (β) along with molecular electrostatic potential surface have been calculated. Frequency-dependent first hyperpolarizabilities, β(-2ω;ω,ω) and β(-ω;ω,0) have also been evaluated to study the non-linear optical behavior of the title compound. UV-Vis spectrum of the title molecule was recorded and TD-DFT method has been used to calculate six lowest excited states and the corresponding excitation energies.
Damping of Bogoliubov excitations in optical lattices

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

Tsuchiya, Shunji; Department of Physics, Waseda University, 3-4-1 Okubo, Tokyo 169-8555; Griffin, Allan

2004-08-01

Extending recent work to finite temperatures, we calculate the Landau damping of a Bogoliubov excitation in an optical lattice, due to the coupling to a thermal cloud of such excitations. For simplicity, we consider a one-dimensional Bose-Hubbard model and restrict ourselves to the first energy band. For energy conservation to be satisfied, the excitations in the collision processes must exhibit ''anomalous dispersion,'' analogous to phonons in superfluid {sup 4}He. This leads to the disappearance of all damping processes when Un{sup c0}{>=}6J, where U is the on-site interaction, J is the hopping matrix element, and n{sup c0}(T) is the number ofmore » condensate atoms at a lattice site. This phenomenon also occurs in two-dimensional and three-dimensional optical lattices. The disappearance of Beliaev damping above a threshold wave vector is noted.« less
Mobility spectrum analytical approach for the type-II Weyl semimetal Td-MoTe2

NASA Astrophysics Data System (ADS)

Pei, Q. L.; Luo, X.; Chen, F. C.; Lv, H. Y.; Sun, Y.; Lu, W. J.; Tong, P.; Sheng, Z. G.; Han, Y. Y.; Song, W. H.; Zhu, X. B.; Sun, Y. P.

2018-02-01

The extreme magnetoresistance (XMR) in orthorhombic W/MoTe2 arises from the combination of the perfect electron-hole (e-h) compensation effect and the unique orbital texture topology, which have comprised an intriguing research field in materials physics. Herein, we apply a special analytical approach as a function of mobility (μ-spectrum) without any hypothesis. Based on the interpretations of longitudinal and transverse electric transport of Td-MoTe2, the types and the numbers of carriers can be obtained. There are three observations: the large residual resistivity ratio can be observed in the MoTe2 single crystal sample, which indicates that the studied crystal is of high quality; we observed three electron-pockets and three hole-ones from the μ-spectrum and that the ratio of h/e is much less than 1, which shows that MoTe2 is more e-like; different from the separated peaks obtained from the hole-like μ-spectrum, those of the electron-like one are continuous, which may indicate the topological feature of electron-pockets in Td-MoTe2. The present results may provide an important clue to understanding the mechanism of the XMR effect in Td-MoTe2.
Excited state properties of the astaxanthin radical cation: A quantum chemical study

NASA Astrophysics Data System (ADS)

Dreuw, Andreas; Starcke, Jan Hendrik; Wachtveitl, Josef

2010-07-01

Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT rad + ) are investigated. While the optically allowed excited D 1 and D 3 states are typical ππ∗ excited states, the D 2 and D 4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.
Initial mechanisms for the unimolecular decomposition of electronically excited bisfuroxan based energetic materials.

PubMed

Yuan, Bing; Bernstein, Elliot R

2017-01-07

Unimolecular decomposition of energetic molecules, 3,3'-diamino-4,4'-bisfuroxan (labeled as A) and 4,4'-diamino-3,3'-bisfuroxan (labeled as B), has been explored via 226/236 nm single photon laser excitation/decomposition. These two energetic molecules, subsequent to UV excitation, create NO as an initial decomposition product at the nanosecond excitation energies (5.0-5.5 eV) with warm vibrational temperature (1170 ± 50 K for A, 1400 ± 50 K for B) and cold rotational temperature (<55 K). Initial decomposition mechanisms for these two electronically excited, isolated molecules are explored at the complete active space self-consistent field (CASSCF(12,12)/6-31G(d)) level with and without MP2 correction. Potential energy surface calculations illustrate that conical intersections play an essential role in the calculated decomposition mechanisms. Based on experimental observations and theoretical calculations, NO product is released through opening of the furoxan ring: ring opening can occur either on the S 1 excited or S 0 ground electronic state. The reaction path with the lowest energetic barrier is that for which the furoxan ring opens on the S 1 state via the breaking of the N1-O1 bond. Subsequently, the molecule moves to the ground S 0 state through related ring-opening conical intersections, and an NO product is formed on the ground state surface with little rotational excitation at the last NO dissociation step. For the ground state ring opening decomposition mechanism, the N-O bond and C-N bond break together in order to generate dissociated NO. With the MP2 correction for the CASSCF(12,12) surface, the potential energies of molecules with dissociated NO product are in the range from 2.04 to 3.14 eV, close to the theoretical result for the density functional theory (B3LYP) and MP2 methods. The CASMP2(12,12) corrected approach is essential in order to obtain a reasonable potential energy surface that corresponds to the observed decomposition behavior of these
Photophysical Behavior and Computational Investigation of Novel 1,4-Bis(2-(2-Phenylpyrimido[1,2-a]Benzimidazol-4-Yl)Phenoxy)Butan (BPPB) Macromolecule.

PubMed

Saleh, Tamer S; Hussein, Mahmoud A; Osman, Osman I; Alamry, Khalid A; Mekky, Ahmed E M; Asiri, Abdullah M; El-Daly, Samy A

2016-09-01

A new macromolecule pyrimido[l,2-a]benzimidazole derivative named 1,4-bis(2-(2-phenylpyrimido[1,2-a]benzimidazol-4-yl)phenoxy)butan (BPPB) has been synthesized in accepted yield using microwave assistance. The new compound BPPB has been formed by the interaction of 3,3'-((butane-1,4-diylbis(oxy))bis(2,1-phenylene))bis(1-phenylprop-2-en-1-one) (3) with 2- aminobenzimidazole (4) in the presence of potassium hydroxide as a basic catalyst in dimethylformamide (DMF) under microwave radiation for 20 min. The chemical structure of this novel compound was elucidated by elemental and spectral techniques including: FT-IR, (1)H-NMR, (13)C-NMR and mass spectra. The electronic absorption and emission spectra of BPPB were measured in different solvents. BPPB displayed a solvatochromic effect of the emission spectrum that is reflected by red shifts of its fluorescence emission maxima on increasing the solvent polarity, indicating a change of electronic charge distribution upon excitation. BPPB crystalline solids gave excimer-like emission at 535 nm with a bandwidth of ca. 60 nm. Ground and excited states electronic geometry optimizations using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively, complemented these spectral findings. The intramolecular charge transfer was investigated by natural bond orbital (NBO) technique.
Excited State Charge Transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

NASA Astrophysics Data System (ADS)

Jana, Sankar; Dalapati, Sasanka; Ghosh, Shalini; Kar, Samiran; Guchhait, Nikhil

2011-07-01

The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G( d, p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations.

Oxidation behavior of TD-NiCr in a dynamic high temperature environment

NASA Technical Reports Server (NTRS)

Tenney, D. R.; Young, C. T.; Herring, H. W.

1974-01-01

The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.
Single-photon cesium Rydberg excitation spectroscopy using 318.6-nm UV laser and room-temperature vapor cell.

PubMed

Wang, Jieying; Bai, Jiandong; He, Jun; Wang, Junmin

2017-09-18

We demonstrate a single-photon Rydberg excitation spectroscopy of cesium (Cs) atoms in a room-temperature vapor cell. Cs atoms are excited directly from 6S 1/2 ground state to nP 3/2 (n = 70 - 100) Rydberg states with a 318.6 nm ultraviolet (UV) laser, and Rydberg excitation spectra are obtained by transmission enhancement of a probe beam resonant to Cs 6S 1/2 , F = 4 - 6P 3/2 , F' = 5 transition as partial population on F = 4 ground state are transferred to Rydberg state. Analysis reveals that the observed spectra are velocity-selective spectroscopy of Rydberg state, from which the amplitude and linewidth influenced by lasers' Rabi frequency have been investigated. Fitting to energies of Cs nP 3/2 (n = 70 -100) states, the determined quantum defect is 3.56671(42). The demodulated spectra can also be employed as frequency references to stabilize the UV laser frequency to specific Cs Rydberg transition.
Structural, photophysical, and theoretical studies of imidazole-based excited-state intramolecular proton transfer molecules

NASA Astrophysics Data System (ADS)

Somasundaram, Sivaraman; Kamaraj, Eswaran; Hwang, Su Jin; Park, Sanghyuk

2018-02-01

Imidazole-based excited state intramolecular proton transfer (ESIPT) blue fluorescent molecules, 2-(1-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Cl) and 2-(1-(4-bromophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Br) were designed and synthesized by Debus-Radziszewski method through a one-pot multicomponent reaction in high yield. The synthesized compounds were fully characterized by 1H NMR, 13C NMR, FT-IR, FT-Raman, GC-Mass, and elemental analysis. The molecular structures in single crystal lattice were studied by X-ray crystallographic analysis. Because of the intramolecular hydrogen bonding, hydroxyphenyl group is planar to the central imidazole ring, while the other phenyl rings gave distorted conformations to the central heterocyclic ring. BHPI-Cl and BHPI-Br molecules showed intense ESIPT fluorescence at 480 nm, because the two twisted phenyl rings on 4- and 5-positions have reduced intermolecular interaction between adjacent molecules in each crystal through a head-to-tail packing manner. Quantum chemical calculations of energies were carried out by (TD-)DFT using B3LYP/6-31G(d, p) basis set to predict the electronic absorption spectra of the compounds, and they showed good agreement between the computational and the experimental values. The thermal analyses of the synthesized molecules were also carried out by TGA/DSC method.
LETTER TO THE EDITOR: Differential electron scattering from the (010) excited vibrational mode of N2O

NASA Astrophysics Data System (ADS)

Akther, P.; Johnstone, W. M.; El-Zein, A. A. A.; Campbell, L.; Teubner, P. J. O.; Brunger, M. J.; Newell, W. R.

2002-11-01

In this letter we report differential superelastic, elastic and inelastic electron scattering measurements from nitrous oxide (N2O) in its (010)* excited vibrational quantum. The incident electron energy was 2.5 eV and the scattered electron angular range was 10°- 40°. Unlike our previous results (1999 J. Phys. B: At. Mol. Opt. Phys. 32 5779) with the isoelectronic molecule carbon dioxide (CO2), where the elastic differential cross sections (DCSs) for scattering from the (010)* mode were 2.3 times larger than those for elastic scattering from the ground (000) state, in N2O the corresponding (010)* elastic cross sections are usually only a fraction of those for the ground state. To the best of our knowledge, the present data are the first DCSs which have been reported in the literature for electron scattering from an excited vibrational level of the N2O molecule.
Positive Selection and Multiple Losses of the LINE-1-Derived L1TD1 Gene in Mammals Suggest a Dual Role in Genome Defense and Pluripotency

PubMed Central

Yang, Lei; Neme, Rafik; Wichman, Holly A.; Malik, Harmit S.

2014-01-01

Mammalian genomes comprise many active and fossilized retroelements. The obligate requirement for retroelement integration affords host genomes an opportunity to ‘domesticate’ retroelement genes for their own purpose, leading to important innovations in genome defense and placentation. While many such exaptations involve retroviruses, the L1TD1 gene is the only known domesticated gene whose protein-coding sequence is almost entirely derived from a LINE-1 (L1) retroelement. Human L1TD1 has been shown to play an important role in pluripotency maintenance. To investigate how this role was acquired, we traced the origin and evolution of L1TD1. We find that L1TD1 originated in the common ancestor of eutherian mammals, but was lost or pseudogenized multiple times during mammalian evolution. We also find that L1TD1 has evolved under positive selection during primate and mouse evolution, and that one prosimian L1TD1 has ‘replenished’ itself with a more recent L1 ORF1 from the prosimian genome. These data suggest that L1TD1 has been recurrently selected for functional novelty, perhaps for a role in genome defense. L1TD1 loss is associated with L1 extinction in several megabat lineages, but not in sigmodontine rodents. We hypothesize that L1TD1 could have originally evolved for genome defense against L1 elements. Later, L1TD1 may have become incorporated into pluripotency maintenance in some lineages. Our study highlights the role of retroelement gene domestication in fundamental aspects of mammalian biology, and that such domesticated genes can adopt different functions in different lineages. PMID:25211013
The Upconversion Luminescence of Er3+/Yb3+/Nd3+ Triply-Doped β-NaYF4 Nanocrystals under 808-nm Excitation

PubMed Central

Tian, Lijiao; Xu, Zheng; Zhao, Suling; Cui, Yue; Liang, Zhiqin; Zhang, Junjie; Xu, Xurong

2014-01-01

In this paper, Nd3+–Yb3+–Er3+-doped β-NaYF4 nanocrystals with different Nd3+ concentrations are synthesized, and the luminescence properties of the upconversion nanoparticles (UCNPs) have been studied under 808-nm excitation for sensitive biological applications. The upconversion luminescence spectra of NaYF4 nanoparticles with different dopants under 808-nm excitation proves that the Nd3+ ion can absorb the photons effectively, and the Yb3+ ion can play the role of an energy-transfer bridging ion between the Nd3+ ion and Er3+ ion. To investigate the effect of the Nd3+ ion, the decay curves of the 4S3/2 → 4I15/2 transition at 540 nm are measured and analyzed. The NaYF4: 20% Yb3+, 2% Er3+, 0.5% Nd3+ nanocrystals have the highest emission intensity among all samples under 808-nm excitation. The UC (upconversion) mechanism under 808-nm excitation is discussed in terms of the experimental results. PMID:28788246
Ultrafast intramolecular charge transfer with N-(4-cyanophenyl)carbazole. Evidence for a LE precursor and dual LE + ICT fluorescence.

PubMed

Galievsky, Victor A; Druzhinin, Sergey I; Demeter, Attila; Mayer, Peter; Kovalenko, Sergey A; Senyushkina, Tamara A; Zachariasse, Klaas A

2010-12-09

The photophysics of N-(4-cyanophenyl)carbazole (NP4CN) was investigated by using absorption and fluorescence spectra, picosecond fluorescence decays, and femtosecond transient absorption. In the nonpolar n-hexane as well as in the polar solvent acetonitrile (MeCN), a locally excited (LE) state is detected, as a precursor for the intramolecular charge transfer (ICT) state. A LE → ICT reaction time τ(2) at 22 °C of 0.95 ps in ethyl cyanide (EtCN) and 0.32 ps in MeCN is determined from the decay of the LE excited state absorption (ESA) maximum around 620 nm. In the ESA spectrum of NP4CN in n-hexane at a pump-probe delay time of 100 ps, an important contribution of the LE band remains alongside the ICT band, in contrast to what is observed in EtCN and MeCN. This shows that a LE ⇄ ICT equilibrium is established in this solvent and the ICT reaction time of 0.5 ps is equal to the reciprocal of the sum of the forward and backward ICT rate constants 1/(k(a) + k(d)). In the photostationary S(0) → S(n) absorption spectrum of NP4CN in n-hexane and MeCN, an additional CT absorption band appears, absent in the sum of the spectra of its electron donor (D) and acceptor (A) subgroups carbazole and benzonitrile. This CT band is located at an energy of ∼4000 cm(-1) lower than for N-phenylcarbazole (NPC), due to the larger electron affinity of the benzonitrile moiety of NP4CN than the phenyl subunit of NPC. The fluorescence spectrum of NP4CN in n-hexane at 25 °C mainly consists of a structured LE emission, with a small ICT admixture, indicating that a LE → ICT reaction just starts to occur under these conditions. In di-n-pentyl ether (DPeE) and di-n-butyl ether (DBE), a LE emission is found upon cooling at the high-energy edge of the ICT fluorescence band, caused by the onset of dielectric solvent relaxation. This is not the case in more polar solvents, such as diethyl ether (DEE) and MeCN, in which a structureless ICT emission band fully overlaps the strongly quenched LE
Ultralow threading dislocation density in GaN epilayer on near-strain-free GaN compliant buffer layer and its applications in hetero-epitaxial LEDs

PubMed Central

Shih, Huan-Yu; Shiojiri, Makoto; Chen, Ching-Hsiang; Yu, Sheng-Fu; Ko, Chung-Ting; Yang, Jer-Ren; Lin, Ray-Ming; Chen, Miin-Jang

2015-01-01

High threading dislocation (TD) density in GaN-based devices is a long unresolved problem because of the large lattice mismatch between GaN and the substrate, which causes a major obstacle for the further improvement of next-generation high-efficiency solid-state lighting and high-power electronics. Here, we report InGaN/GaN LEDs with ultralow TD density and improved efficiency on a sapphire substrate, on which a near strain-free GaN compliant buffer layer was grown by remote plasma atomic layer deposition. This “compliant” buffer layer is capable of relaxing strain due to the absorption of misfit dislocations in a region within ~10 nm from the interface, leading to a high-quality overlying GaN epilayer with an unusual TD density as low as 2.2 × 105 cm−2. In addition, this GaN compliant buffer layer exhibits excellent uniformity up to a 6” wafer, revealing a promising means to realize large-area GaN hetero-epitaxy for efficient LEDs and high-power transistors. PMID:26329829
Ultralow threading dislocation density in GaN epilayer on near-strain-free GaN compliant buffer layer and its applications in hetero-epitaxial LEDs.

PubMed

Shih, Huan-Yu; Shiojiri, Makoto; Chen, Ching-Hsiang; Yu, Sheng-Fu; Ko, Chung-Ting; Yang, Jer-Ren; Lin, Ray-Ming; Chen, Miin-Jang

2015-09-02

High threading dislocation (TD) density in GaN-based devices is a long unresolved problem because of the large lattice mismatch between GaN and the substrate, which causes a major obstacle for the further improvement of next-generation high-efficiency solid-state lighting and high-power electronics. Here, we report InGaN/GaN LEDs with ultralow TD density and improved efficiency on a sapphire substrate, on which a near strain-free GaN compliant buffer layer was grown by remote plasma atomic layer deposition. This "compliant" buffer layer is capable of relaxing strain due to the absorption of misfit dislocations in a region within ~10 nm from the interface, leading to a high-quality overlying GaN epilayer with an unusual TD density as low as 2.2 × 10(5) cm(-2). In addition, this GaN compliant buffer layer exhibits excellent uniformity up to a 6" wafer, revealing a promising means to realize large-area GaN hetero-epitaxy for efficient LEDs and high-power transistors.
Bottom-up excited state dynamics of two cinnamate-based sunscreen filter molecules.

PubMed

Peperstraete, Yoann; Staniforth, Michael; Baker, Lewis A; Rodrigues, Natércia D N; Cole-Filipiak, Neil C; Quan, Wen-Dong; Stavros, Vasilios G

2016-10-12

Methyl-E-4-methoxycinnamate (E-MMC) is a model chromophore of the commonly used commercial sunscreen agent, 2-ethylhexyl-E-4-methoxycinnamate (E-EHMC). In an effort to garner a molecular-level understanding of the photoprotection mechanisms in operation with E-EHMC, we have used time-resolved pump-probe spectroscopy to explore E-MMC's and E-EHMC's excited state dynamics upon UV-B photoexcitation to the S 1 (1 1 ππ*) state in both the gas- and solution-phase. In the gas-phase, our studies suggest that the excited state dynamics are driven by non-radiative decay from the 1 1 ππ* to the S 3 (1 1 nπ*) state, followed by de-excitation from the 1 1 nπ* to the ground electronic state (S 0 ). Using both a non-polar-aprotic solvent, cyclohexane, and a polar-protic solvent, methanol, we investigated E-MMC and E-EHMC's photochemistry in a more realistic, 'closer-to-shelf' environment. A stark change to the excited state dynamics in the gas-phase is observed in the solution-phase suggesting that the dynamics are now driven by efficient E/Z isomerisation from the initially photoexcited 1 1 ππ* state to S 0 .
Electron-Impact Cross Sections for Ground State to np Excitations of Sodium and Potassium.

PubMed

Stone, Philip M; Kim, Yong-Ki

2004-01-01

Cross sections for electron impact excitation of atoms are important for modeling of low temperature plasmas and gases. While there are many experimental and theoretical results for excitation to the first excited states, little information is available for excitation to higher states. We present here calculations of excitations from the ground state to the np levels of sodium (n = 3 through 11) and potassium (n = 4 through 12). We also present a calculation for a transition from the excited sodium level 3p to 3d to show the generality of the method. Scaling formulas developed earlier by Kim [Phys. Rev. A 64, 032713 (2001)] for plane-wave Born cross sections are used. These formulas have been shown to be remarkably accurate yet simple to use. We have used a core polarization potential in a Dirac-Fock wave function code to calculate target atom wave functions and a matching form of the dipole transition operator to calculate oscillator strengths and Born cross sections. The scaled Born results here for excitation to the first excited levels are in very good agreement with experimental and other theoretical data, and the results for excitation to the next few levels are in satisfactory agreement with the limited data available. The present results for excitation to the higher levels are believed to be the only data available.
A One-Dimensional Organic Lead Chloride Hybrid with Excitation-Dependent Broadband Emissions

DOE PAGES

Wu, Guanhong; Zhou, Chenkun; Ming, Wenmei; ...

2018-05-23

Organic–inorganic metal halide hybrids have emerged as a new class of materials with fascinating optical and electronic properties. The exceptional structure tunability has enabled the development of materials with various dimensionalities at the molecular level, from three-dimensional (3D) to 2D, 1D, and 0D. Here, we report a new 1D lead chloride hybrid, C 4N 2H 14PbCl 4, which exhibits unusual inverse excitation-dependent broadband emission from bluish-green to yellow. Density functional theory calculations were performed to better understand the mechanism of this excitation-dependent broadband emission. This 1D hybrid material is found to have two emission centers, corresponding to the self-trapped excitonsmore » (STEs) and vacancy-bound excitons. The excitation-dependent emission is due to different populations of these two types of excitons generated at different excitation wavelengths. Furthermore, this work shows the rich chemistry and physics of organic–inorganic metal halide hybrids and paves the way to achieving novel light emitters with excitation-dependent broadband emissions at room temperature.« less
A One-Dimensional Organic Lead Chloride Hybrid with Excitation-Dependent Broadband Emissions

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

Wu, Guanhong; Zhou, Chenkun; Ming, Wenmei

Organic–inorganic metal halide hybrids have emerged as a new class of materials with fascinating optical and electronic properties. The exceptional structure tunability has enabled the development of materials with various dimensionalities at the molecular level, from three-dimensional (3D) to 2D, 1D, and 0D. Here, we report a new 1D lead chloride hybrid, C 4N 2H 14PbCl 4, which exhibits unusual inverse excitation-dependent broadband emission from bluish-green to yellow. Density functional theory calculations were performed to better understand the mechanism of this excitation-dependent broadband emission. This 1D hybrid material is found to have two emission centers, corresponding to the self-trapped excitonsmore » (STEs) and vacancy-bound excitons. The excitation-dependent emission is due to different populations of these two types of excitons generated at different excitation wavelengths. Furthermore, this work shows the rich chemistry and physics of organic–inorganic metal halide hybrids and paves the way to achieving novel light emitters with excitation-dependent broadband emissions at room temperature.« less
Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: A density functional theory

NASA Astrophysics Data System (ADS)

Govindasamy, P.; Gunasekaran, S.; Ramkumaar, G. R.

2014-09-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator’s strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated.
Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine)2(CN)2

PubMed Central

Kjær, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe; Chollet, Matthieu; Hadt, Ryan G.; Hartsock, Robert W.; Harlang, Tobias; Kroll, Thomas; Kubiček, Katharina; Lemke, Henrik T.; Liang, Huiyang W.; Liu, Yizhu; Nielsen, Martin M.; Robinson, Joseph S.; Solomon, Edward I.; Sokaras, Dimosthenis; van Driel, Tim B.; Weng, Tsu-Chien; Zhu, Diling; Persson, Petter; Wärnmark, Kenneth; Sundström, Villy; Gaffney, Kelly J.

2017-01-01

We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2′-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy)2(CN)2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy)2(CN)2] complement prior measurement performed on [Fe(bpy)3]2+ and [Fe(bpy)(CN)4]2− in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy)N(CN)6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes. PMID:28653021
Towards first-principles calculation of electronic excitations in the ring of the protein-bound bacteriochlorophylls

NASA Astrophysics Data System (ADS)

Polyakov, Igor V.; Khrenova, Maria G.; Moskovsky, Alexander A.; Shabanov, Boris M.; Nemukhin, Alexander V.

2018-04-01

Modeling electronic excitation of bacteriochlorophyll (BChl) molecules in light-harvesting (LH) antennae from photosynthetic centers presents a challenge for the quantum theory. We report on a quantum chemical study of the ring of 32 BChl molecules from the bacterial core complex LH1-RC. Diagonal and off-diagonal elements of the excitonic Hamiltonian matrices are estimated in quantum chemical calculations of relevant fragments using the TD-DFT and CIS approaches. The deviation of the computed excitation energy of this BChl system from the experimental data related to the Qy band maximum of this LH1-RC complex is about 0.2 eV. We demonstrate that corrections due to improvement in modeling of an individual BChl molecule and due to contributions from the protein environment are in the range of the obtained discrepancy between theory and experiment. Differences between results of the excitonic model and direct quantum chemical calculations of BChl aggregates fall in the same range.
Energetic oxygen precipitation as a source of vibrationally excited N/sub 2//sup +/ in emissions observed at low latitudes

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

Tinsley, B.A.; Rohrbaugh, R.P.; Sahai, Y.

Observations have been made at Mt. Haleakala, Hawaii (dip lat.approx.22/sup 0/N) and Cachoeira Paulista, Brasil (dip lat.approx.12/sup 0/S) of emissions excited by particle precipitation during periods of magnetic activity. The first negative bands of N/sub 2//sup +/ were found to have a high degree of vibrational excitation at both sites, and withi the absence of emissions attributable to hydrogen and helium, this finding leads to the interpretation that the excitation was due to a flux of precipitating oxygen atoms or ions, more plausibly the former, produced by charge exchange of ring current O/sup +/ ions with exospheric neutral constituents. Moremore » laboratory work is needed to properly interpret the data, but crude estimates of the associated energy deposition and ionization production fall in the range 10/sup -1/ to 10/sup +1/mWm/sup -2/, and 10/sup 0/-10/sup 2/ cm/sup -3/s/sup -1/ respectively.« less
40 CFR 721.1085 - Benzenamine,4,4′-methylenebis[N-ethyl-N-methyl-.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzenamine,4,4â²-methylenebis[N-ethyl-N-methyl-. 721.1085 Section 721.1085 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1085 Benzenamine,4,4′-methylenebis[N-ethyl-N-methyl-. (a) Chemical...
40 CFR 721.1085 - Benzenamine,4,4′-methylenebis[N-ethyl-N-methyl-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzenamine,4,4â²-methylenebis[N-ethyl-N-methyl-. 721.1085 Section 721.1085 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1085 Benzenamine,4,4′-methylenebis[N-ethyl-N-methyl-. (a) Chemical...
Excited states of 4He

NASA Astrophysics Data System (ADS)

Aoyama, Shigeyoshi

2013-04-01

The study of the 4He nucleus is important because it is the most basic sub-unit (cluster) in nuclei. We have investigated the structures and the reaction mechanisms in 4He by using the correlated Gaussian basis function with the global vector representation. In order to treat the boundary condition for the ab-initio calculation of the four nucleons, we employ the Microscopic R-matrix Method (MRM) and the Complex Scaling Method (CSM) . Elastic-scattering phase shifts for four-nucleon systems are studied in an ab-initio type cluster model with MRM in order to clarify the role of the tensor force and to investigate cluster distortions in low energy d+d and t+p scattering. For 1S0, the calculated phase shifts show that the t+p and h+n channels are strongly coupled to the d+d channel for the case of the realistic interaction.

Signature of chaos in the 4 f -core-excited states for highly-charged tungsten ions

NASA Astrophysics Data System (ADS)

Safronova, Ulyana; Safronova, Alla

2014-05-01

We evaluate radiative and autoionizing transition rates in highly charged W ions in search for the signature of chaos. In particularly, previously published results for Ag-like W27+, Tm-like W5+, and Yb-like W4+ ions as well as newly obtained for I-like W21+, Xe-like W20+, Cs-like W19+, and La-like W17+ ions (with ground configuration [Kr] 4d10 4fk with k = 7, 8, 9, and 11, respectively) are considered that were calculated using the multiconfiguration relativistic Hebrew University Lawrence Livermore Atomic Code (HULLAC code) and the Hartree-Fock-Relativistic method (COWAN code). The main emphasis was on verification of Gaussian statistics of rates as a function of transition energy. There was no evidence of such statistics for above mentioned previously published results as well as for the transitions between the excited and autoionizing states for newly calculated results. However, we did find the Gaussian profile for the transitions between excited states such as the [Kr] 4d10 4fk - [Kr] 4d10 4f k - 1 5 d transitions , for newly calculated W ions. This work is supported in part by DOE under NNSA Cooperative Agreement DE-NA0001984.
UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C-Y (Y = halogen) and O-H bond fission

NASA Astrophysics Data System (ADS)

Sage, Alan G.; Oliver, Thomas A. A.; King, Graeme A.; Murdock, Daniel; Harvey, Jeremy N.; Ashfold, Michael N. R.

2013-04-01

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n/π)σ*) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ˜11 000 cm-1. For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n/π)σ* PES, but no Cl/Cl* products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I/I* product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n/π)σ* potentials across the series Y = I < Br < Cl and the concomitant reduction in C-Y bond strength, cf. that of the rival O-H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in
Probabilistic solutions of nonlinear oscillators excited by combined colored and white noise excitations

NASA Astrophysics Data System (ADS)

Siu-Siu, Guo; Qingxuan, Shi

2017-03-01

In this paper, single-degree-of-freedom (SDOF) systems combined to Gaussian white noise and Gaussian/non-Gaussian colored noise excitations are investigated. By expressing colored noise excitation as a second-order filtered white noise process and introducing colored noise as an additional state variable, the equation of motion for SDOF system under colored noise is then transferred artificially to multi-degree-of-freedom (MDOF) system under white noise excitations with four-coupled first-order differential equations. As a consequence, corresponding Fokker-Planck-Kolmogorov (FPK) equation governing the joint probabilistic density function (PDF) of state variables increases to 4-dimension (4-D). Solution procedure and computer programme become much more sophisticated. The exponential-polynomial closure (EPC) method, widely applied for cases of SDOF systems under white noise excitations, is developed and improved for cases of systems under colored noise excitations and for solving the complex 4-D FPK equation. On the other hand, Monte Carlo simulation (MCS) method is performed to test the approximate EPC solutions. Two examples associated with Gaussian and non-Gaussian colored noise excitations are considered. Corresponding band-limited power spectral densities (PSDs) for colored noise excitations are separately given. Numerical studies show that the developed EPC method provides relatively accurate estimates of the stationary probabilistic solutions, especially the ones in the tail regions of the PDFs. Moreover, statistical parameter of mean-up crossing rate (MCR) is taken into account, which is important for reliability and failure analysis. Hopefully, our present work could provide insights into the investigation of structures under random loadings.
Excitation and De-Excitation Mechanisms of Er-Doped GaAs and A1GaAs.

DTIC Science & Technology

1992-12-01

AD-A258 814 EXCITATION AND DE -EXCITATION MECHANISMS OF Er-DOPED GaAs AND A1GaAs DISSERTATION David W. Elsaesser, Captain, USAF DTICY. ft £ICTE’’ )AN...0 8 1993U -o Wo- .%Approved for public release; Distribution unlimited 93 1 04 022 AFIT/DS/ENP/92-5 EXCITATION AND DE -EXCITATION MECHANISMS OF Er...public release; Distribution unlimited AFIT/DS/ENP/92D-005 EXCITATION AND DE -EXCITATION MECHANISMS OF Er-DOPED GaAs AND A1GaAs 4 toFlor -- David W
Nitric oxide excited under auroral conditions: Excited state densities and band emissions

NASA Astrophysics Data System (ADS)

Cartwright, D. C.; Brunger, M. J.; Campbell, L.; Mojarrabi, B.; Teubner, P. J. O.

2000-09-01

Electron impact excitation of vibrational levels in the ground electronic state and nine excited electronic states in NO has been simulated for an IBC II aurora (i.e., ˜10 kR in 3914 Å radiation) in order to predict NO excited state number densities and band emission intensities. New integral electron impact excitation cross sections for NO were combined with a measured IBC II auroral secondary electron distribution, and the vibrational populations of 10 NO electronic states were determined under conditions of statistical equilibrium. This model predicts an extended vibrational distribution in the NO ground electronic state produced by radiative cascade from the seven higher-lying doublet excited electronic states populated by electron impact. In addition to significant energy storage in vibrational excitation of the ground electronic state, both the a 4Π and L2 Φ excited electronic states are predicted to have relatively high number densities because they are only weakly connected to lower electronic states by radiative decay. Fundamental mode radiative transitions involving the lowest nine excited vibrational levels in the ground electronic state are predicted to produce infrared (IR) radiation from 5.33 to 6.05 μm with greater intensity than any single NO electronic emission band. Fundamental mode radiative transitions within the a 4Π electronic state, in the 10.08-11.37 μm region, are predicted to have IR intensities comparable to individual electronic emission bands in the Heath and ɛ band systems. Results from this model quantitatively predict the vibrational quantum number dependence of the NO IR measurements of Espy et al. [1988].
Selective Modulation of K+ Channel Kv7.4 Significantly Affects the Excitability of DRN 5-HT Neurons.

PubMed

Zhao, Chen; Su, Min; Wang, Yingzi; Li, Xinmeng; Zhang, Yongxue; Du, Xiaona; Zhang, Hailin

2017-01-01

The serotonin (5-HT) system originating in the dorsal raphe nucleus (DRN) is implicated in various mood- and emotion-related disorders, such as anxiety, fear and stress. Abnormal activity of DRN 5-HT neurons is the key factor in the development of these disorders. Here, we describe a crucial role for the Kv7.4 potassium channel in modulating DRN 5-HT neuronal excitability. We demonstrate that Kv7.4 is selectively expressed in 5-HT neurons of the DRN. Using selective Kv7.4 opener fasudil and Kv7.4 knock-out mice, we demonstrate that Kv7.4 is a potent modulator of DRN 5-HT neuronal excitability. Furthermore, we demonstrate that the cellular redox signaling mechanism is involved in this 5-HT activation of Kv7.4. The current study suggests a new strategy for treating psychiatric disorders related to altered activity of DRN 5-HT neurons using K + channel modulators.
Selective Modulation of K+ Channel Kv7.4 Significantly Affects the Excitability of DRN 5-HT Neurons

PubMed Central

Zhao, Chen; Su, Min; Wang, Yingzi; Li, Xinmeng; Zhang, Yongxue; Du, Xiaona; Zhang, Hailin

2017-01-01

The serotonin (5-HT) system originating in the dorsal raphe nucleus (DRN) is implicated in various mood- and emotion-related disorders, such as anxiety, fear and stress. Abnormal activity of DRN 5-HT neurons is the key factor in the development of these disorders. Here, we describe a crucial role for the Kv7.4 potassium channel in modulating DRN 5-HT neuronal excitability. We demonstrate that Kv7.4 is selectively expressed in 5-HT neurons of the DRN. Using selective Kv7.4 opener fasudil and Kv7.4 knock-out mice, we demonstrate that Kv7.4 is a potent modulator of DRN 5-HT neuronal excitability. Furthermore, we demonstrate that the cellular redox signaling mechanism is involved in this 5-HT activation of Kv7.4. The current study suggests a new strategy for treating psychiatric disorders related to altered activity of DRN 5-HT neurons using K+ channel modulators. PMID:29311835
Site-Selective Benzannulation of N-Heterocycles in Bidentate Ligands Leads to Blue-Shifted Emission from [( P^N)Cu]2(μ-X)2 Dimers.

PubMed

Mondal, Rajarshi; Lozada, Issiah B; Davis, Rebecca L; Williams, J A Gareth; Herbert, David E

2018-05-07

Benzannulated bidentate pyridine/phosphine ( P^N) ligands bearing quinoline or phenanthridine (3,4-benzoquinoline) units have been prepared, along with their halide-bridged, dimeric Cu(I) complexes of the form [( P^N)Cu] 2 (μ-X) 2 . The copper complexes are phosphorescent in the orange-red region of the spectrum in the solid-state under ambient conditions. Structural characterization in solution and the solid-state reveals a flexible conformational landscape, with both diamond-like and butterfly motifs available to the Cu 2 X 2 cores. Comparing the photophysical properties of complexes of (quinolinyl)phosphine ligands with those of π-extended (phenanthridinyl)phosphines has revealed a counterintuitive impact of site-selective benzannulation. Contrary to conventional assumptions regarding π-extension and a bathochromic shift in the lowest energy absorption maxima, a blue shift of nearly 40 nm in the emission wavelength is observed for the complexes with larger ligand π-systems, which is assigned as phosphorescence on the basis of emission energies and lifetimes. Comparison of the ground-state and triplet excited state structures optimized from DFT and TD-DFT calculations allows attribution of this effect to a greater rigidity for the benzannulated complexes resulting in a higher energy emissive triplet state, rather than significant perturbation of orbital energies. This study reveals that ligand structure can impact photophysical properties for emissive molecules by influencing their structural rigidity, in addition to their electronic structure.
A 4.8 kbps code-excited linear predictive coder

NASA Technical Reports Server (NTRS)

Tremain, Thomas E.; Campbell, Joseph P., Jr.; Welch, Vanoy C.

1988-01-01

A secure voice system STU-3 capable of providing end-to-end secure voice communications (1984) was developed. The terminal for the new system will be built around the standard LPC-10 voice processor algorithm. The performance of the present STU-3 processor is considered to be good, its response to nonspeech sounds such as whistles, coughs and impulse-like noises may not be completely acceptable. Speech in noisy environments also causes problems with the LPC-10 voice algorithm. In addition, there is always a demand for something better. It is hoped that LPC-10's 2.4 kbps voice performance will be complemented with a very high quality speech coder operating at a higher data rate. This new coder is one of a number of candidate algorithms being considered for an upgraded version of the STU-3 in late 1989. The problems of designing a code-excited linear predictive (CELP) coder to provide very high quality speech at a 4.8 kbps data rate that can be implemented on today's hardware are considered.
New interpretation of the Gran Dolina-TD6 bearing Homo antecessor deposits through sedimentological analysis

PubMed Central

Campaña, I.; Pérez-González, A.; Benito-Calvo, A.; Rosell, J.; Blasco, R.; de Castro, J. M. Bermúdez; Carbonell, E.; Arsuaga, J. L.

2016-01-01

Gran Dolina is a cavity infilled by at least 25 m of Pleistocene sediments. This sequence contains the TD6 stratigraphic unit, whose records include around 170 hominin bones that have allowed the definition of a new species, Homo antecessor. This fossil accumulation was studied as a single assemblage and interpreted as a succession of several human home bases. We propose a complete stratigraphic context and sedimentological interpretation for TD6, analyzing the relationships between the sedimentary facies, the clasts and archaeo-palaeontological remains. The TD6 unit has been divided into three sub-units and 13 layers. Nine sedimentary facies have been defined. Hominin remains appear related to three different sedimentary facies: debris flow facies, channel facies and floodplain facies. They show three kinds of distribution: first a group of scattered fossils, then a group with layers of fossils in fluvial facies, and third a group with a layer of fossils in mixed fluvial and gravity flow facies. The results of this work suggest that some of these hominin remains accumulated in the cave by geological processes, coming from the adjacent slope above the cave or the cave entry, as the palaeogeography and sedimentary characteristics of these allochthonous facies suggest. PMID:27713562
Increases in human motoneuron excitability after cervical spinal cord injury depend on the level of injury.

PubMed

Thomas, Christine K; Häger, Charlotte K; Klein, Cliff S

2017-02-01

After human spinal cord injury (SCI), motoneuron recruitment and firing rate during voluntary and involuntary contractions may be altered by changes in motoneuron excitability. Our aim was to compare F waves in single thenar motor units paralyzed by cervical SCI to those in uninjured controls because at the single-unit level F waves primarily reflect the intrinsic properties of the motoneuron and its initial segment. With intraneural motor axon stimulation, F waves were evident in all 4 participants with C 4 -level SCI, absent in 8 with C 5 or C 6 injury, and present in 6 of 12 Uninjured participants (P < 0.001). The percentage of units that generated F waves differed across groups (C 4 : 30%, C 5 or C 6 : 0%, Uninjured: 16%; P < 0.001). Mean (±SD) proximal axon conduction velocity was slower after C 4 SCI [64 ± 4 m/s (n = 6 units), Uninjured: 73 ± 8 m/s (n = 7 units); P = 0.037]. Mean distal axon conduction velocity differed by group [C 4 : 40 ± 8 m/s (n = 20 units), C 5 or C 6 : 49 ± 9 m/s (n = 28), Uninjured: 60 ± 7 m/s (n = 45); P < 0.001]. Motor unit properties (EMG amplitude, twitch force) only differed after SCI (P ≤ 0.004), not by injury level. Motor units with F waves had distal conduction velocities, M-wave amplitudes, and twitch forces that spanned the respective group range, indicating that units with heterogeneous properties produced F waves. Recording unitary F waves has shown that thenar motoneurons closer to the SCI (C 5 or C 6 ) have reduced excitability whereas those further away (C 4 ) have increased excitability, which may exacerbate muscle spasms. This difference in motoneuron excitability may be related to the extent of membrane depolarization following SCI. Unitary F waves were common in paralyzed thenar muscles of people who had a chronic spinal cord injury (SCI) at the C 4 level compared with uninjured people, but F waves did not occur in people that had SCI at the C 5 or C 6 level. These results highlight that intrinsic motoneuron
Isolation and molecular characterization of a novel WIN1/SHN1 ethylene-responsive transcription factor TdSHN1 from durum wheat (Triticum turgidum. L. subsp. durum).

PubMed

Djemal, Rania; Khoudi, Habib

2015-11-01

Over the last decade, APETALA2/Ethylene Responsive Factor (AP2/ERF) proteins have become the subject of intensive research activity due to their involvement in a variety of biological processes. This research led to the identification of AP2/ERF genes in many species; however, little is known about these genes in durum wheat, one of the most important cereal crops in the world. In this study, a new member of the AP2/ERF transcription factor family, designated TdSHN1, was isolated from durum wheat using thermal asymetric interlaced PCR (TAIL-PCR) method. Protein sequence analysis showed that TdSHN1 contained an AP2/ERF domain of 63 amino acids and a putative nuclear localization signal (NLS). Phylogenetic analysis showed that TdSHN1 belongs to a group Va protein in the ERF subfamily which contains the Arabidopsis ERF proteins (SHN1, SHN2, and SHN3). Expression of TdSHN1 was strongly induced by salt, drought, abscisic acid (ABA), and cold. In planta, TdSHN1 protein was able to activate the transcription of GUS reporter gene driven by the GCC box and DRE element sequences. In addition, TdSHN1 was targeted to the nucleus when transiently expressed in tobacco epidermal cells. In transgenic yeast, overexpression of TdSHN1 increased tolerance to multiple abiotic stresses. Taken together, the results showed that TdSHN1 encodes an abiotic stress-inducible, transcription factor which confers abiotic stress tolerance in yeast. TdSHN1 is therefore a promising candidate for improvement of biotic and abiotic stress tolerance in wheat as well as other crops.
Integral cross sections for electron impact excitation of electronic states of N2

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Nolan, A. M.; Kelly, L. J.; Wedding, A. B.; Harrison, J.; Teubner, P. J. O.; Cartwright, D. C.; McLaughlin, B.

2001-04-01

We report integral cross sections (ICSs) for electron impact excitation of the A 3Σ+u, B 3Πg, W 3Δu, B' 3Σ-u, a' 1Σ-u, a 1Πg, ω1Δu, C 3Πu, E 3Σ+g and a'' 1Σ+g electronic states of N2. The present data, for each state, were derived at five incident electron energies in the range 15-50 eV, from the earlier crossed-beam differential cross section (DCS) measurements of our group. This was facilitated by using a molecular phase shift analysis technique to extrapolate the measured DCSs to 0° and 180°, before performing the integration. A comprehensive comparison of the present ICSs with the results of earlier experimental studies, both crossed beam and electron swarm, and theoretical calculations is provided. This comparison clearly indicates that some of the previous estimates for these excited electronic-state cross sections need to be reassessed. In addition, we have used the present ICSs in a Monte Carlo simulation for modelling the behaviour of an electron swarm in the bulk of a low current N2 discharge. The macroscopic transport parameters determined from this simulation are compared against those measured from independent swarm-based experiments and the self-consistency of our ICSs evaluated.
Photoelectron spectroscopy and electronic structure of ScO{sub n}{sup {minus}}(n = 1--4) and YO{sub n}{sup {minus}}(n = 1--5): Strong electron correlation effects in ScO{sup {minus}} and YO{sup {minus}}

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

Wu, H.; Wang, L.S.

A photoelectron spectroscopic study of ScO{sub n}{sup {minus}} (n = 1--4) and YO{sub n}{sup {minus}} (n = 1--5) was carried out at three photon energies: 532, 355, and 266 nm. Vibrationally resolved photoelectron spectra were obtained for ScO{sup {minus}} and YO{sup {minus}}. The electron affinities of both ScO and YO were measured to be identical (1.35 eV) within the experimental accuracy ({+-}0.02 eV). Three low-lying excited states were observed for the monoxides, {Alpha}{prime}{sup 2}{Delta}, {Alpha}{sup 2}{Pi}, and {Beta}{sup 2}{Sigma}{sup +}. The latter two excited states resulted from two-electron detachment, suggesting unusually strong electron correlation (configuration interaction) effects in the groundmore » state of the anions. The excitation energies of the low-lying states were also found to be similar for the two monoxides except that YO has a smaller vibrational frequency and larger spin-orbit splitting. The {Alpha}{prime}{sup 2}{Delta} states of both ScO and YO show very strong photon energy-dependent detachment cross sections. Four similar photoelectron features were observed for the dioxides with those of YO{sub 2}{sup {minus}} having lower binding energies. A second isomer due to an O{sub 2} complex was also observed for Sc and Y. Broad and featureless spectra were observed for the higher oxides. At least two isomers were present for the higher oxides, one with low and one with high binding energies.« less
Collective charge excitations of the two-dimensional electride Ca2N

NASA Astrophysics Data System (ADS)

Cudazzo, Pierluigi; Gatti, Matteo

2017-09-01

Ca2N is a layered material that has been recently identified as a two-dimensional (2D) electride, an unusual ionic compound in which electrons serve as anions. The electronic properties of 2D electrides attract considerable interest as the anionic electrons, which form a 2D layer sandwiched between atomic planes, are highly mobile as they are not attached to any ion. Here, on the basis of first-principles time-dependent density-functional theory calculations, we investigate the collective excitations of the electrons—i.e., the plasmons—in Ca2N as a function of wave vector q . Our calculations reveal an intrinsic negative in-plane dispersion of the anionic plasmon, in striking contrast with the homogeneous electron gas. Moreover, for wave vectors q normal to the planes, we find a long-lived plasmon that continues to exist well beyond the first Brillouin zone. This is a mark of the electronic inhomogeneities in the charge response that Ca2N shares with other layered materials like transition-metal dichalcogenides and MgB2. Finally, we compare the plasmon properties of Ca2N in its bulk and monolayer forms, which shows the effect of the different electronic structures and dimensionalities.
A randomized controlled trial [corrected] administration of tetanus toxoid (TT) versus tetanus and reduced diphtheria (Td) in pregnant women.

PubMed

Salama, Maha M; Hady, Osama A W; Ashour, Wael; Mostafa, Amal; El Alkamy, Sahar; El Sayed, Nehad; El Yazeed, Remon Abu

2009-07-01

The present study was designed as a randomized clinical trial to compare the immunogenicity, reactogenicity, and efficacy of tetanus toxoid (TT) and the combined tetanus and reduced diphtheria (Td) in pregnant women in four rural communities in Egypt. The pregnant women in each four villages received either TT or Td randomly. Both TT and Td vaccines are manufactured by the Egyptian Company for Biological Products & Vaccines (VACSERA) in Egypt. A total of 131 pregnant women were enrolled during the time of antenatal care visit (at 20 weeks gestational age of pregnancy) in one of four health units in Abu Homos district, Beheira Governorate, Egypt. Unimmunized women received two random doses of either TT or Td 8 weeks apart during their pregnancy. Outpatient follow-up for adverse reactions occurred at the third day after each vaccine dose as either local effects such as pain, redness, and swelling or systematic effects such as fever, malaise, and headache or body aches which was served as primary safety endpoint. Blood was collected three times from each woman for determination of antibody titer against tetanus and diphtheria by using enzyme-linked immunosorbent assay technique. The first sample was collected immediately before the first dose, the second before the second dose, and the third sample 1 week after delivery. Active surveillance home visits to all study participants were done twice: the first home visit during the first week after delivery and the second 1 month after labor to report the health status of the mother and the baby. A total of 122 pregnant women received two ordinary doses with interdose intervals within the allowable range and three blood samples were collected in each protocol analysis (62 in the TT group and 60 in the Td group). There was no statistically significant difference between groups in the percentage of reporting a primary safety endpoint (fever, malaise, body ache, headache) or local reactions at the site of injection as redness
Three-dimensional imaging of threading dislocations in GaN crystals using two-photon excitation photoluminescence

NASA Astrophysics Data System (ADS)

Tanikawa, Tomoyuki; Ohnishi, Kazuki; Kanoh, Masaya; Mukai, Takashi; Matsuoka, Takashi

2018-03-01

The three-dimensional imaging of threading dislocations in GaN films was demonstrated using two-photon excitation photoluminescence. The threading dislocations were shown as dark lines. The spatial resolutions near the surface were about 0.32 and 3.2 µm for the in-plane and depth directions, respectively. The threading dislocations with a density less than 108 cm-2 were resolved, although the aberration induced by the refractive index mismatch was observed. The decrease in threading dislocation density was clearly observed by increasing the GaN film thickness. This can be considered a novel method for characterizing threading dislocations in GaN films without any destructive preparations.
Green electroluminescence from Tb{sub 4}O{sub 7} films on silicon: Impact excitation of Tb{sup 3+} ions by hot carriers

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

Zhu, Chen; Jiang, Miaomiao; Zhou, Junwei

2016-02-01

We report on green electroluminescence (EL) due to the intra-4f transitions of the trivalent terbium (Tb{sup 3+}) ions inherent in a Tb{sub 4}O{sub 7} film that is sandwiched between the ITO film and heavily phosphorous- or boron-doped silicon (n{sup +}-Si or p{sup +}-Si) substrate, thus forming the so-called metal-oxide-semiconductor (MOS) device. The onset voltage of such EL is below 10 V. From the current-voltage characteristic and voltage-dependent EL spectra of the aforementioned MOS device, it is derived that the Tb-related green EL results from the impact excitation of Tb{sup 3+} ions by the hot electrons (holes), which stem from the electric-fieldmore » acceleration of the electrons (holes) injected from the n{sup +}-Si (p{sup +}-Si) substrate via the trap-assisted tunneling mechanism.« less
Emission Behavior of Crystalline 1,4-Bis(4-phenylthiophene-2-yl)benzene Film Under Optical Excitation with Ultra Short Pulses.

PubMed

Mochizuki, Hiroyuki; Kawaguchi, Yoshizo; Sasaki, Fumio; Hotta, Shu

2016-04-01

We evaluated emission behaviors of crystallized films of 1,4-bis(5-phenylthiophene-2-yl)benzene (AC5) in detail which was a representative thiophene/phenylene co-oligomer. The crystallized AC5 films were prepared by vapor deposition onto a substrate and thermal treatment. The AC5 films consisted of a crystalline domain with the size of several tens of micrometers. We used femtosecond laser pulses for the excitation of the AC5 films. As a result, the femtosecond laser pulses did not induce re-absorption above excitation energy densities of their laser threshold. The obtained gain value for AC5 crystallized film was large, over 150 cm-1. Furthermore, the emission cross section of the crystallized AC5 film was nearly 10(-16) cm2.
Dopamine Neurons Change the Type of Excitability in Response to Stimuli

PubMed Central

Gutkin, Boris S.; Lapish, Christopher C.; Kuznetsov, Alexey

2016-01-01

The dynamics of neuronal excitability determine the neuron’s response to stimuli, its synchronization and resonance properties and, ultimately, the computations it performs in the brain. We investigated the dynamical mechanisms underlying the excitability type of dopamine (DA) neurons, using a conductance-based biophysical model, and its regulation by intrinsic and synaptic currents. Calibrating the model to reproduce low frequency tonic firing results in N-methyl-D-aspartate (NMDA) excitation balanced by γ-Aminobutyric acid (GABA)-mediated inhibition and leads to type I excitable behavior characterized by a continuous decrease in firing frequency in response to hyperpolarizing currents. Furthermore, we analyzed how excitability type of the DA neuron model is influenced by changes in the intrinsic current composition. A subthreshold sodium current is necessary for a continuous frequency decrease during application of a negative current, and the low-frequency “balanced” state during simultaneous activation of NMDA and GABA receptors. Blocking this current switches the neuron to type II characterized by the abrupt onset of repetitive firing. Enhancing the anomalous rectifier Ih current also switches the excitability to type II. Key characteristics of synaptic conductances that may be observed in vivo also change the type of excitability: a depolarized γ-Aminobutyric acid receptor (GABAR) reversal potential or co-activation of α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptors (AMPARs) leads to an abrupt frequency drop to zero, which is typical for type II excitability. Coactivation of N-methyl-D-aspartate receptors (NMDARs) together with AMPARs and GABARs shifts the type I/II boundary toward more hyperpolarized GABAR reversal potentials. To better understand how altering each of the aforementioned currents leads to changes in excitability profile of DA neuron, we provide a thorough dynamical analysis. Collectively, these results imply that type I

Use of DEAD-box polypeptide-4 (Ddx4) gene promoter-driven fluorescent reporter mice to identify mitotically active germ cells in post-natal mouse ovaries

PubMed Central

Park, Eun-Sil; Tilly, Jonathan L.

2015-01-01

Several laboratories have independently isolated mitotically active germ cells, termed female germline stem cells or oogonial stem cells (OSCs), from adult mouse ovaries. However, a recent study using Ddx4-Cre;Rosa26 reporter mice concluded that such germ cells do not exist. Given the disparity in conclusions drawn in this study compared with others, we felt it was important to re-assess the utility of Ddx4-Cre;Rosa26 reporter mice for identification of OSCs in adult mouse ovaries. Transgenic Ddx4-Cre mice were crossed with Rosa26tdTm/tdTm mice to drive restricted tomato red (tdTm) gene expression in cells in which the Ddx4 gene promoter has been activated. Crude dispersion of ovaries from recombined offspring generated cell fractions containing tdTm-positive immature oocytes, which are incapable of proliferation and thus probably represent the uncharacterized reporter-positive ovarian cells identified in the paper Zhang et al. (2012) as being mitotically inactive. Dispersed ovaries further subjected to fluorescence-activated cell sorting yielded a large population of non-germline tdTm-positive cells, indicative of promoter ‘leakiness’ in the Ddx4-Cre mouse line. Nonetheless, a small percentage of these tdTm-positive cells exhibited externalized (extracellular, ec) expression of Ddx4 protein (ecDdx4-positive), expressed markers of primitive germ cells but not of oocytes, and actively proliferated in culture, all of which are characteristic features of OSCs. Thus, crude dispersion of ovaries collected from Ddx4 gene promoter-driven reporter mice is not, by itself, a reliable approach to identify OSCs, whereas the same ovarian dispersates further subjected to cell sorting strategies yield purified OSCs that can be expanded in culture. PMID:25147160
Examination of the first excited state of 4He as a potential breathing mode

NASA Astrophysics Data System (ADS)

Bacca, Sonia; Barnea, Nir; Leidemann, Winfried; Orlandini, Giuseppina

2015-02-01

The isoscalar monopole excitation of 4He is studied within a few-body ab initio approach. We consider the transition density to the low-lying and narrow 0+ resonance, as well as various sum rules and the strength energy distribution itself at different momentum transfers q . Realistic nuclear forces of chiral and phenomenological nature are employed. Various indications for a collective breathing mode are found: (i) the specific shape of the transition density, (ii) the high degree of exhaustion of the non-energy-weighted sum rule at low q , and (iii) the complete dominance of the resonance peak in the excitation spectrum. For the incompressibility K of the α particle, two different definitions give two rather small values (22 and 36 MeV).
Substituted N-(biphenyl-4'-yl)methyl (R)-2-acetamido-3-methoxypropionamides: potent anticonvulsants that affect frequency (use) dependence and slow inactivation of sodium channels.

PubMed

Lee, Hyosung; Park, Ki Duk; Torregrosa, Robert; Yang, Xiao-Fang; Dustrude, Erik T; Wang, Yuying; Wilson, Sarah M; Barbosa, Cindy; Xiao, Yucheng; Cummins, Theodore R; Khanna, Rajesh; Kohn, Harold

2014-07-24

We prepared 13 derivatives of N-(biphenyl-4'-yl)methyl (R)-2-acetamido-3-methoxypropionamide that differed in type and placement of a R-substituent in the terminal aryl unit. We demonstrated that the R-substituent impacted the compound's whole animal and cellular pharmacological activities. In rodents, select compounds exhibited excellent anticonvulsant activities and protective indices (PI=TD50/ED50) that compared favorably with clinical antiseizure drugs. Compounds with a polar, aprotic R-substituent potently promoted Na+ channel slow inactivation and displayed frequency (use) inhibition of Na+ currents at low micromolar concentrations. The possible advantage of affecting these two pathways to decrease neurological hyperexcitability is discussed.
Concept for polychromatic laser guide stars: one-photon excitation of the 4P3/2 level of a sodium atom.

PubMed

Pique, Jean-Paul; Moldovan, Ioana Cristina; Fesquet, Vincent

2006-11-01

One challenge for polychromatic laser guide stars is to create a sufficiently intense source in the UV. The flux required for the measurement of differential tip-tilt is the main issue that we address. We describe a model that has been validated using on-sky data. We present a method that excites the 4P3/2 sodium level using a one-photon excitation at 330 nm. It is more efficient than the two-photon excitation previously suggested since its power slope flux is 3 x 10(4) photons/s/m2/W instead of 1.3 x 10(3) photons/s/m2/W. This method is very promising both in terms of flux and system simplicity.
Structures, energetics, vibrational spectra of NH4+ (H2O)(n=4,6) clusters: Ab initio calculations and first principles molecular dynamics simulations.

PubMed

Karthikeyan, S; Singh, Jiten N; Park, Mina; Kumar, Rajesh; Kim, Kwang S

2008-06-28

Important structural isomers of NH(4) (+)(H(2)O)(n=4,6) have been studied by using density functional theory, Moller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH(4) (+)(H(2)O)(n=4,6) because otherwise wrong structures could be assigned for the most probable structures. For NH(4) (+)(H(2)O)(6), the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH(4) (+)(H(2)O)(4) and two lowest energy isomers of NH(4) (+)(H(2)O)(6) explains each experimental IR spectrum.
Structures, energetics, vibrational spectra of NH4+(H2O)n=4,6 clusters: Ab initio calculations and first principles molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Karthikeyan, S.; Singh, Jiten N.; Park, Mina; Kumar, Rajesh; Kim, Kwang S.

2008-06-01

Important structural isomers of NH4+(H2O)n=4,6 have been studied by using density functional theory, Møller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH4+(H2O)n=4,6 because otherwise wrong structures could be assigned for the most probable structures. For NH4+(H2O)6, the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH4+(H2O)4 and two lowest energy isomers of NH4+(H2O)6 explains each experimental IR spectrum.
Calculation of the total electron excitation cross section in the Born approximation using Slater wave functions for the Li (2s yields 2p), Li (2s yields 3p), Na (3s yields 4p), Mg (3p yields 4s), Ca (4s yields 4p) and K (4s yields 4p) excitations. M.S. Thesis

NASA Technical Reports Server (NTRS)

Simsic, P. L.

1974-01-01

Excitation of neutral atoms by inelastic scattering of incident electrons in gaseous nebulae were investigated using Slater Wave functions to describe the initial and final states of the atom. Total cross sections using the Born Approximation are calculated for: Li(2s yields 2p), Na(3s yields 4p), k(4s yields 4p). The intensity of emitted radiation from gaseous nebulae is also calculated, and Maxwell distribution is employed to average the kinetic energy of electrons.
TdERF1, an ethylene response factor associated with dehydration responses in durum wheat (Triticum turgidum L. subsp. durum).

PubMed

Makhloufi, Emna; Yousfi, Fatma-Ezzahra; Pirrello, Julien; Bernadac, Anne; Ghorbel, Abdelwahed; Bouzayen, Mondher

2015-01-01

Water deficit and increasing salinization reduce productivity of wheat, the leading crop for human diet. While the complete genome sequence of this crop has not been deciphered, a BAC library screening allowed the isolation of TdERF1, the first ethylene response factor gene from durum wheat. This gene is putatively involved in mediating salt stress tolerance and its characterization provides clues toward understanding the mechanisms underlying the adaptation/tolerance of durum wheat to suboptimal growth conditions. TdERF1 expression is differentially induced by high salt treatment in 2 durum wheat varieties, the salt-tolerant Grecale (GR) and the salt-sensitive Om Rabiaa (OR). To further extend these findings, we show here that the expression of this ERF is correlated with physiological parameters, such as the accumulation of osmo-regulators and membrane integrity, that discriminate between the 2 contrasted wheat genotypes. The data confirm that GR and OR are 2 contrasted wheat genotypes with regard to salt-stress and show that TdERF1 is also induced by water stress with an expression pattern clearly discriminating between the 2 genotypes. These findings suggest that TdERF1 might be involved in responses to salt and water stress providing a potential genetic marker discriminating between tolerant and sensitive wheat varieties.
New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N1

NASA Technical Reports Server (NTRS)

Tayal, S. S.

2006-01-01

The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N(I) lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strength over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s(sup 2)p(sup 3) (sup 4)S(sup 0), (sup 2)D(sup 0), (sup 2)P(sup 0), 2s2p(sup 4) (sup 4)P, 2s(sup 2)2p(sup 2)3s (sup 4)P, and (sup 2)P terms and from these levels to the levels of the 2s(sup 2)2p(sup 2)3p (sup 2)S(sup 0), (sup 4)D(sup 0), (sup 4)P(sup 0), (sup 4)S(sup 0), (sup 2)D(sup 0), (sup 2)P(sup 0),2s(sup 2)2p(sup 2)3s(sup 2)D, 2s(sup 2)2p(sup 2)4s(sup 4)P, (sup 2)P, 2s(sup 2)2p(sup 2)3d(sup 2)P, (sup 4)F,(sup 2)F,(sup 4)P, (sup 4)D, and (sup 2)D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.
Continuous excitations of the triangular-lattice quantum spin liquid YbMgGaO 4

DOE PAGES

Paddison, Joseph A.Â M.; Daum, Marcus; Dun, Zhiling; ...

2016-12-05

A quantum spin liquid (QSL) is an exotic state of matter in which electrons’ spins are quantum entangled over long distances, but do not show magnetic order in the zero-temperature limit. The observation of QSL states is a central aim of experimental physics, because they host collective excitations that transcend our knowledge of quantum matter; however, examples in real materials are scarce. We report neutron-scattering experiments on YbMgGaO 4, a QSL candidate in which Yb 3+ ions with effective spin-1/2 occupy a triangular lattice. Furthermore, our measurements reveal a continuum of magnetic excitations—the essential experimental hallmark of a QSL7—at verymore » low temperature (0.06 K). The origin of this peculiar excitation spectrum is a crucial question, because isotropic nearest-neighbour interactions do not yield a QSL ground state on the triangular lattice. In using measurements the field-polarized state, we identify antiferromagnetic next-nearest-neighbour interactions spin-space anisotropies and chemical disorder between the magnetic layers as key ingredients in YbMgGaO 4.« less
Electromagnetic Propagation in Multimode Optical Fibers, Excited by Sources of Finite Bandwidth.

DTIC Science & Technology

1980-08-15

21 + w’-itb + o(T2 - T2)/2 + wT2/2 exp(-4(T - T2)/21, (45) with tb - t - Z/h. After performing the two integrals over The expression of ( JaJ ) ,, and...53) r3 - T - 2 - T T/(2Tp + T2), (49) The other contribution can be put in a quantitative form by introducing the time delay Td between the centers of...mass o- =TI+ T1- (2T + TT)/(2T 2 + T1). (0) of the two pulses at a distance z; that is, An.analogous expression holds true for (JJ:),, which Td () - z
Experimental and theoretical (FT-IR, FT-Raman, UV-vis, NMR) spectroscopic analysis and first order hyperpolarizability studies of non-linear optical material: (2E)-3-[4-(methylsulfanyl) phenyl]-1-(4-nitrophenyl) prop-2-en-1-one using density functional theory.

PubMed

Kumar, Amit; Deval, Vipin; Tandon, Poonam; Gupta, Archana; Deepak D'silva, E

2014-09-15

A combined experimental and theoretical investigation on FT-IR, FT-Raman, NMR, UV-vis spectra of a chalcone derivative (2E)-3-[4-(methylsulfanyl) phenyl]-1-(4-nitrophenyl) prop-2-en-1-one (4N4MSP) has been reported. 4N4MSP has two planar rings connected through conjugated double bond and it provides a necessary configuration to show non-linear optical (NLO) response. The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) with B3LYP functional and 6-311++G(d,p) basis set combination. The analysis of the fundamental modes was made with the help of potential energy distribution (PED). Molecular electrostatic potential (MEP) surface was plotted over the geometry primarily for predicting sites and relative reactivities towards electrophilic and nucleophilic attack. The delocalization of electron density of various constituents of the molecule has been discussed with the aid of NBO analysis. The electronic properties, such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies, were calculated by time-dependent density functional theory (TD-DFT) and the results complement the experimental findings. The recorded and calculated 1H chemical shifts in gas phase and MeOD solution are gathered for reliable calculations of magnetic properties. Thermodynamic properties like heat capacity (C°p,m), entropy (S°m), enthalpy (H°m) have been calculated for the molecule at the different temperatures. Based on the finite-field approach, the non-linear optical (NLO) parameters such as dipole moment, mean polarizability, anisotropy of polarizability and first order hyperpolarizability of 4N4MSP molecule are calculated. The predicted first hyperpolarizability shows that the molecule has a reasonably good nonlinear optical (NLO) behavior. Copyright © 2014 Elsevier B.V. All
Studying breaking of inverted emulsions with thermolysis purification TD600

NASA Astrophysics Data System (ADS)

Tarasova, G. I.; Shevaga, O. N.; Grachyova, E. O.

2018-03-01

Currently, emulsions are used in many branches of industry and agriculture. It explains significant attention paid to issues in production, stabilization and breaking of emulsion. Besides, producing steady emulsions is of importance in many processes; the reverse problem, that of demulsification, is important as well in oil production and treatment of oil emulsion waste water. This paper studies the breaking (demulsification) of inverted emulsions with the help of thermolysis purification TD600, produced by thermal modification of purification, a large-scale waste of the sugar industry.
The role of carnivores and their relationship to hominin settlements in the TD6-2 level from Gran Dolina (Sierra de Atapuerca, Spain)

NASA Astrophysics Data System (ADS)

Saladié, Palmira; Rodríguez-Hidalgo, Antonio; Huguet, Rosa; Cáceres, Isabel; Díez, Carlos; Vallverdú, Josep; Canals, Antoni; Soto, María; Santander, Boris; Bermúdez de Castro, José María; Arsuaga, Juan Luis; Carbonell, Eudald

2014-06-01

Pleistocene level TD6-2 of the Gran Dolina site (Sierra de Atapuerca, Spain) is the result of anthropogenic accumulation. Hominin groups occupied the cave as a home base, where they brought in, butchered and consumed the carcasses of ungulates and other hominins. In this paper, we reassess the role of carnivores in the formation and/or modification of the assemblage. We employed different methods to explore the scenario in which the TD6-2 assemblage was formed: (1) identifying the actor responsible for tooth marks; (2) determining the frequency of carnivore tooth marks and their distribution; (3) identifying the co-occurrence of modifications (butchering marks and carnivore tooth marks); (4) calculating the percentage of change and the epiphysis to shaft ratio. Carnivore tooth marks are scarce, as is the co-occurrence of hominin and carnivore modifications. However, not all tooth marks have been attributed to a particular agent due to the high equifinality between human and carnivore tooth marks. For these reasons, the frequency of tooth marks and the co-occurrence of modifications have been of little help in interpreting the role of carnivores. Axial skeletal remains and the epiphyses of the long bones are in large part missing. The percentage of change and the epiphysis to shaft ratio suggest moderate carnivore ravaging activity. Our data indicate that the role of carnivores in TD6-2 seems to have had an impact on the original assemblage after hominins had extracted a large amount of nutrients from the carcasses. Cannibalized hominin remains showed no carnivore tooth marks and have a greater presence of low survival bones compared to ungulate remains. These findings point to a different taphonomic history suggesting that TD6-2 represents a succession of settlements having different characteristics.
Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: a density functional theory.

PubMed

Govindasamy, P; Gunasekaran, S; Ramkumaar, G R

2014-09-15

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm(-1) and 4000-50 cm(-1) respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.
Accuracy of Td-DFT in the Ultraviolet and Circular Dichroism Spectra of Deoxyguanosine and Uridine.

PubMed

Miyahara, Tomoo; Nakatsuji, Hiroshi

2018-01-11

Accuracy of the time-dependent density functional theory (Td-DFT) was examined for the ultraviolet (UV) and circular dichroism (CD) spectra of deoxyguanosine (dG) and uridine, using 11 different DFT functionals and two different basis sets. The Td-DFT results of the UV and CD spectra were strongly dependent on the functionals used. The basis-set dependence was observed only for the CD spectral calculations. For the UV spectra, the B3LYP and PBE0 functionals gave relatively good results. For the CD spectra, the B3LYP and PBE0 with 6-311G(d,p) basis gave relatively permissible result only for dG. The results of other functionals were difficult to be used for the studies of the UV and CD spectra, though the symmetry adapted cluster-configuration interaction (SAC-CI) method reproduced well the experimental spectra of these molecules. To obtain valuable information from the theoretical calculations of the UV and CD spectra, the theoretical tool must be able to reproduce correctly both of the intensities and peak positions of the UV and CD spectra. Then, we can analyze the reasons of the changes of the intensity and/or the peak position to clarify the chemistry involved. It is difficult to recommend Td-DFT as such tools of science, at least from the examinations using dG and uridine.
Intensities of the Venusian N2 electron-impact excited dayglow emissions

NASA Astrophysics Data System (ADS)

Fox, Jane L.; F. Hać, Nicholas E.

2013-12-01

Dayglow emissions are signatures of both the energy deposition into an atmosphere and the abundances of the species from which they arise. The first N2 dayglow emissions from Mars, the (0,5) and (0,6) bands of the N2 Vegard-Kaplan band system, were detected by the Spectroscopy for Investigations of the Characteristics of the Atmosphere of Mars (SPICAM) UV spectrometer on board the Mars Express spacecraft. The Vegard-Kaplan band system arises from the transition from the lowest N2 triplet state (A3Σu+;v') to the electronic ground state (X1Σg+;v″). It is populated by direct electron-impact excitation and by cascading from higher triplet states. The Venus UV dayglow is currently being probed by an instrument similar to SPICAM, the Spectroscopy for the Investigations of the Characteristics of the Atmosphere of Venus (SPICAV) UV spectrometer on Venus Express, but no N2 emissions have been detected. Because the N2 mixing ratios in the Venus thermosphere are larger than those in the thermosphere of Mars and the solar flux is greater at the orbit of Venus than that at Mars, we expect the Venus N2 emissions to be significantly more intense than those of Mars. A prediction of the intensities of various N2 emissions from Venus could be used to guide observations by the SPICAV and other instruments that are used to measure the Venus dayglow. Employing updated data, we here construct models of the low and high solar activity thermospheres of Venus, and we compute the integrated overhead intensities of 17 N2 band systems and limb profiles of the Vegard-Kaplan bands. The ratios of the predicted intensities of the various N2 bands at Venus to those at Mars are in the range 5.5-9.5.
Cortical afferents onto the nucleus Reticularis thalami promote plasticity of low-threshold excitability through GluN2C-NMDARs.

PubMed

Fernandez, Laura M J; Pellegrini, Chiara; Vantomme, Gil; Béard, Elidie; Lüthi, Anita; Astori, Simone

2017-09-25

Thalamus and cortex represent a highly integrated processing unit that elaborates sensory representations. Interposed between cortex and thalamus, the nucleus Reticularis thalami (nRt) receives strong cortical glutamatergic input and mediates top-down inhibitory feedback to thalamus. Despite growing appreciation that the nRt is integral for thalamocortical functions from sleep to attentional wakefulness, we still face considerable gaps in the synaptic bases for cortico-nRt communication and plastic regulation. Here, we examined modulation of nRt excitability by cortical synaptic drive in Ntsr1-Cre x ChR2 tg/+ mice expressing Channelrhodopsin2 in layer 6 corticothalamic cells. We found that cortico-nRt synapses express a major portion of NMDA receptors containing the GluN2C subunit (GluN2C-NMDARs). Upon repetitive photoactivation (10 Hz trains), GluN2C-NMDARs induced a long-term increase in nRt excitability involving a potentiated recruitment of T-type Ca 2+ channels. In anaesthetized mice, analogous stimulation of cortical afferents onto nRt produced long-lasting changes in cortical local field potentials (LFPs), with delta oscillations being augmented at the expense of slow oscillations. This shift in LFP spectral composition was sensitive to NMDAR blockade in the nRt. Our data reveal a novel mechanism involving plastic modification of synaptically recruited T-type Ca 2+ channels and nRt bursting and indicate a critical role for GluN2C-NMDARs in thalamocortical rhythmogenesis.
Selective Complexation of Cyanide and Fluoride Ions with Ammonium Boranes: A Theoretical Study on Sensing Mechanism Involving Intramolecular Charge Transfer and Configurational Changes.

PubMed

Bhat, Haamid R; Jha, Prakash C

2017-05-18

The anion binding selectivity and the recognition mechanism of two isomeric boranes, namely, 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 1, where "Mes" represents mesitylene and "Me" represents methyl) and 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 2) has been investigated using density functional theory (DFT) and time dependent-density functional theory (TD-DFT) methods. Natural population analysis indicates that the central boron atoms in 1 and 2 are the most active centers for nucleophilic addition of anions. The negative magnitude of free energy changes (ΔG) reveals that out of CN - , F - , Cl - , Br - , NO 3 - , and HSO 4 - only the binding of CN - and F - with 1 and 2 is thermodynamically feasible and spontaneous. In addition, the calculated binding energies reveal that the CN - is showing lesser binding affinity than F - both with 1 and 2, while other ions, viz. NO 3 - , HSO 4 - , Br - , and Cl - , either do not bind at all or show very insignificant binding energy. The first excited states (S 1 ) of 1 and 2 are shown to be the local excited states with π → σ* transition by frontier molecular orbital analysis, whereas fourth excited states (S 4 ) of 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline cyanide ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] CN, 1CN, the cyano form of 1) and 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 1F, the fluoro form of 1) and fifth excited state (S 5 ) of 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 2F, the fluoro form of 2) are charge separation states that are found to be responsible for the intramolecular charge transfer (ICT) process. The synergistic effect of ICT and partial configuration changes induce fluorescence quenching in 1CN, 1F, and 2F after a significant internal conversion (IC) from S 4 and
Theoretical and Experimental Studies of N,N-Dimethyl-N'-Picryl-4,4'-Stilbenediamine.

PubMed

Papper, Vladislav; Wu, Yuanyuan; Kharlanov, Vladimir; Sukharaharja, Ayrine; Steele, Terry W J; Marks, Robert S

2018-01-01

N,N-dimethyl-N'-picryl-4,4'-stilbenediamine (DMPSDA) was prepared, purified and crystallised in a form of black lustrous crystals, and its absorption and fluorescence spectra were recorded in cyclohexane, acetonitrile and dimethyl sulfoxide. Non-emissive intramolecular charge transfer state (ICT) was clearly observed in this molecule in all three solvents. Theoretical calculations demonstrating a betaine electronic structure of the trinitrophenyl group in the ground state of the molecule and a charge transfer nature of the long wavelength transition S 0 → S 1 supported the experimental observations of the ICT formation in the molecule.

Emittance of TD-NiCr after simulated reentry

NASA Technical Reports Server (NTRS)

Clark, R. K.; Dicus, D. L.; Lisagor, W. B.

1978-01-01

The effects of simulated reentry heating on the emittance of TD-NiCr were investigated. Groups of specimens with three different preconditioning treatments were exposed to 6, 24, and 30 half-hour simulated reentry exposure cycles in a supersonic arc tunnel at each of three conditions intended to produce surface temperatures of 1255, 1365, and 1475 K. Emittance was determined at 1300 K on specimens which were preconditioned only and specimens after completion of reentry simulation exposure. Oxide morphology and chemistry were studied by scanning electron microscopy and X-ray diffraction analysis. A consistent relationship was established between oxide morphology and total normal emittance. Specimens with coarser textured oxides tended to have lower emittances than specimens with finer textured oxides.
Excited state electronic polarization and reappraisal of the n ← π∗ emission of acetone in water

NASA Astrophysics Data System (ADS)

Orozco-González, Yoelvis; Coutinho, Kaline; Canuto, Sylvio

2010-10-01

Electronic polarization of the acetone molecule in the excited n → π∗ state is considered and its influence on the solvent shift in the emission spectrum is analyzed. Using an iterative procedure the electronic polarizations of both the ground and the excited states are included and compared with previous results obtained with Car-Parrinello dynamics. Analysis of the emission transition obtained using CIS(D)/aug-cc-pVDZ on statistically uncorrelated solute-solvent structures, composed of acetone and twelve explicit water molecules embedded in the electrostatic field of remaining 263 water molecules, corroborates that the solvent effect is mild, calculated here between 80 and 380 cm -1.
Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

PubMed

Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

2007-02-15

In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.
Substituted N-(Biphenyl-4′-yl)methyl (R)-2-Acetamido-3-methoxypropionamides: Potent Anticonvulsants That Affect Frequency (Use) Dependence and Slow Inactivation of Sodium Channels

PubMed Central

2015-01-01

We prepared 13 derivatives of N-(biphenyl-4′-yl)methyl (R)-2-acetamido-3-methoxypropionamide that differed in type and placement of a R-substituent in the terminal aryl unit. We demonstrated that the R-substituent impacted the compound’s whole animal and cellular pharmacological activities. In rodents, select compounds exhibited excellent anticonvulsant activities and protective indices (PI = TD50/ED50) that compared favorably with clinical antiseizure drugs. Compounds with a polar, aprotic R-substituent potently promoted Na+ channel slow inactivation and displayed frequency (use) inhibition of Na+ currents at low micromolar concentrations. The possible advantage of affecting these two pathways to decrease neurological hyperexcitability is discussed. PMID:25004277
Vibrationally Excited HCN in the Luminous Infrared Galaxy NGC 4418

NASA Astrophysics Data System (ADS)

Sakamoto, Kazushi; Aalto, Susanne; Evans, Aaron S.; Wiedner, Martina C.; Wilner, David J.

2010-12-01

Infrared pumping and its effect on the excitation of HCN molecules can be important when using rotational lines of HCN to probe dense molecular gas in galaxy nuclei. We report the first extragalactic detection of (sub)millimeter rotational lines of vibrationally excited HCN, in the dust-enshrouded nucleus of the luminous infrared galaxy NGC 4418. We estimate the excitation temperature of Tvib ≈ 230 K between the vibrational ground and excited (v 2 = 1) states. This excitation is most likely due to infrared radiation. At this high vibrational temperature the path through the v 2 = 1 state must have a strong impact on the rotational excitation in the vibrational ground level, although it may not be dominant for all rotational levels. Our observations also revealed nearly confusion-limited lines of CO, HCN, HCO+, H13CN, HC15N, CS, N2H+, and HC3N at λ ~ 1 mm. Their relative intensities may also be affected by the infrared pumping.
Prime Contract Awards by State or Country, Place and Contractor. Part 14 (West Warwick, Rhode Island - Katy, Texas), FY1991

DTIC Science & Technology

1991-01-01

34 : (0-1 4 " . C’N L- -4 -C 4 L L.4 ’N L-N 04 L--4 L.-4 L-4-4.-4-4 L. In 66 M(-4N4t iu U0 td ~ W 0( w 000 EU U COlw MN to>- 05UN #0 >. ENJNNN w0( H...0 o 10( td o CS1((00000(((((00000(((((00000((CC It 10- 4 M-(0 114- 000 Q -I4 o -4 -4 -4---I-4 -4 -4 - -44 -4 -4 -4 -4 -4 " 4 4 . 4 -4 -4 -4 -4 -4.-4...I. L-4-I4 L. -4 LO00 L- -4 11- r- L.- 4 L-(D LNN4"N4N4NN40 LN4CMN, H 4 01N0 IS ’N N td PI ’U3 IVN iu ( I" 4 ’UN WU VU~))W0)(A 400 (ON 1. I 0410 H022z
Detailed study of the structure of the low-energy magnetic excitations in overdoped La1.75Sr0.25CuO4

NASA Astrophysics Data System (ADS)

Ikeuchi, Kazuhiko; Kikuchi, Tatsuya; Nakajima, Kenji; Kajimoto, Ryoichi; Wakimoto, Shuichi; Fujita, Masaki

2018-05-01

To examine the detailed structure of low-energy magnetic excitations in a high-transition-temperature superconducting cuprate with heavily hole-doping, we performed inelastic neutron scattering experiments on La1.75Sr0.25CuO4. We observed clear dispersion relations of the previously reported incommensurate (IC) magnetic correlations at Qtet = (0.5 ± δ , 0.5) / (0.5 , 0.5 ± δ) [1]. In addition, we show the emergence of continuum magnetic excitations with a ring shape centered at Γ point Qtet = (0.5 , 0.5) in a constant energy spectrum at T = 50 K . The radius of the ring (r = 0.109) is smaller than the incommensurability (δ = 0.118) . This suggests that the origin of the ring-like excitations is different from that of the IC magnetic correlations, and the low-energy magnetic excitations of the La2-xSrxCuO4 system are inherently composed of these two kinds of excitations.
A visible-light-excited europium(III) complex-based luminescent probe for visualizing copper ions and hydrogen sulfide in living cells

NASA Astrophysics Data System (ADS)

Wang, Yiren; Wang, Huan; Yang, Mei; Yuan, Jingli; Wu, Jing

2018-01-01

Development of visible-light-excited lanthanide (III) complex-based luminescent probes is highly appealing due to their superiority of less damage to the living biosystems over the conventional UV-light-excited ones. In this work, a visible-light-excited europium (III) complex-based luminescent probe, BPED-BHHCT-Eu3+-BPT, has been designed and synthesized by conjugating the Cu2+-binding N,N-bis(2-pyridylmethyl)ethanediamine (BPED) to a tetradentate β-diketone ligand 4,4‧-bis(1″,1″,1″,2″,2″,3″,3″-heptafluoro-4″,6″-hexanedione-6″-yl)chlorosulfo-o-terphenyl (BHHCT) and coordinating with a coligand 2-(N,N-diethylanilin-4-yl)-4,6-bis(pyrazol-1-yl)-1,3,5-triazine) (BPT) for the time-gated luminescence detection of Cu2+ ions and hydrogen sulfide (H2S) in living cells. BPED-BHHCT-Eu3+-BPT exhibited a sharp excitation peak at 407 nm and a wide excitation window extending to beyond 460 nm. Upon its reaction with Cu2+ ions, the luminescence of BPED-BHHCT-Eu3+-BPT was efficiently quenched, which could be reversibly restored by the addition of H2S due to the strong affinity between Cu2+ ions and H2S. The "on-off-on" type luminescence behavior of BPED-BHHCT-Eu3+-BPT towards Cu2+ ions and H2S enabled the sensing of the two species with high sensitivity and selectivity. The performances of BPED-BHHCT-Eu3+-BPT for visualizing intracellular Cu2+ ions and H2S were investigated, and the results have demonstrated the practical applicability of the probe for molecular imaging of cells.
General Aviation Activity and Avionics Survey

DTIC Science & Technology

1988-01-01

tD to U) C’) m’ %0 V al Cm r. %0 H1 2:) ) C’) H 1; 1; U) 0 0) a; 0 N H; U; ) C) 0 H 0 0 Cl) CD M’ tD U) H1 r- U) U) A N N wD 0m w H...8217 r- w N - - H H N O z fz 4 OO O CO CO N 0 O fU D (A w’ r- tD 0 1 r4 (n 0 (0D CO t- m Hl -0 r D CO H4 N) N1 D C N it) N o 0A P4 E-4 H Hl ’r - ol u COC...l) ChH U) ’’ ’ 0H W) ) U) H- H N ON r o 1 tp 𔃺 Ne’ WW (󈧘 00 Oo U ChL ’I](N tD ca N C% O U)U 0(1 M~’ OW U) 1W N CIN40N H 020 L 00l’ C,, ’I 4 01IH’
Design of Servo Scheme and Drive Electronics for the Integrated Electrohydraulic Actuation System of RLV-TD

NASA Astrophysics Data System (ADS)

Kurian, Priya C.; Gopinath, Anish; Shinoy, K. S.; Santhi, P.; Sundaramoorthy, K.; Sebastian, Baby; Jaya, B.; Namboodiripad, M. N.; Mookiah, T.

2017-12-01

Reusable Launch Vehicle-Technology Demonstrator (RLV-TD) is a system which has the ability to carry a payload from the earth's surface to the outer space more than once. The control actuation forms the major component of the control system and it actuates the control surfaces of the RLV-TD based on the control commands. Eight electro hydraulic actuators were used in RLV-TD for vectoring the control surfaces about their axes. A centralised Hydraulic Power Generating Unit (HPU) was used for powering the eight actuators located in two stages. The actuation system had to work for the longest ever duration of about 850 s for an Indian launch vehicle. High bandwidth requirement from autopilot was met by the servo design using the nonlinear mathematical model. Single Control Electronics which drive four electrohydraulic actuators was developed for each stage. High power electronics with soft start scheme was realized for driving the BLDC motor which is the prime mover for hydraulic pump. Many challenges arose due to single HPU for two stages, uncertainty of aero load, higher bandwidth requirements etc. and provisions were incorporated in the design to successfully overcome them. This paper describes the servo design and control electronics architecture of control actuation system.
The relationship between anisotropic magnetoresistance and topology of Fermi surface in Td-MoTe2 crystal

NASA Astrophysics Data System (ADS)

Lv, Yang-Yang; Li, Xiao; Pang, Bin; Cao, Lin; Lin, Dajun; Zhang, Bin-Bin; Yao, Shu-Hua; Chen, Y. B.; Zhou, Jian; Dong, Song-Tao; Zhang, Shan-Tao; Lu, Ming-Hui; Chen, Yan-Feng

2017-07-01

Layered transition-metal dichalcogenides have been recently attracted a lot of attention because of their unique physical properties, such as extremely large and anisotropic magnetoresistance (MR) in WTe2. In this work, we observed the abnormally anisotropic MR on Td-MoTe2 crystal that is strongly dependent on the temperature, as well as the orientations of both magnetic field B and electric field E with respect to crystallographic axes of Td-MoTe2. When E//a-axis and B//c-axis, MR is parabolically dependent on B and is as high as 520% under 9 T and 2 K conditions; the MR is quasi-linearly dependent on B when E//a-axis and B//b-axis (E//b-axis and B//c-axis), and the corresponding MR is only 130% (220%); MR is initially parabolically dependent on B, then linearly on B, and finally shows a saturate trend under E//B//a-axis (or E//B//b-axis) conditions, and the MR is about 16% (30%). These anisotropic MR behaviors can be qualitatively explained by the features of the Fermi surface of Td-MoTe2. This work may demonstrate the rich anisotropic physical behavior in layered transition-metal dichalcognides.
Resonant Coherent Excitation of Hydrogen-Like Ar Ions to the n =: 3 States

NASA Astrophysics Data System (ADS)

Azuma, T.; Ito, T.; Takabayashi, Y.; Komaki, K.; Yamazaki, Y.; Yamazaki, Y.; Takada, E.; Murakami, T.

We have succeeded in observing resonant coherent excitaion (RCE) of 1s electrons to the n = 3 states in 390 MeV/u hydrogen-like Ar17+ ions planar channeled in a silicon crystal through measurements of the charge-state distribution of ions transmitting the crystal. Furthermore, we directly confirmed RCE to the n = 3 states by observing the enhancement of the de-excitation X-rays, i.e., Kβ X-rays under the resonance condition. The resonance profiles of the charge-state distribution as functions of the incident angle to the crystal, which uniquely relates with the transition energy, have a characteristic structure consisting of several peaks. Compared with the profile of RCE to the n = 2 states, the present profiles show a large peak shift from the j = 1/2 and 3/2 levels in vacuum, and the profiles are much wider than those expected from the Stark-split level structure of the n = 3 manifolds due to the position- (distance from the channel center in the planar channel) dependent strong static field in the crystal.
Coulomb excitation of radioactive Na21 and its stable mirror Ne21

NASA Astrophysics Data System (ADS)

Schumaker, M. A.; Cline, D.; Hackman, G.; Morton, A. C.; Pearson, C. J.; Svensson, C. E.; Wu, C. Y.; Andreyev, A.; Austin, R. A. E.; Ball, G. C.; Bandyopadhyay, D.; Becker, J. A.; Boston, A. J.; Boston, H. C.; Buchmann, L.; Churchman, R.; Cifarelli, F.; Cooper, R. J.; Cross, D. S.; Dashdorj, D.; Demand, G. A.; Dimmock, M. R.; Drake, T. E.; Finlay, P.; Gallant, A. T.; Garrett, P. E.; Green, K. L.; Grint, A. N.; Grinyer, G. F.; Harkness, L. J.; Hayes, A. B.; Kanungo, R.; Leach, K. G.; Lee, G.; Maharaj, R.; Martin, J.-P.; Moisan, F.; Mythili, S.; Nelson, L.; Newman, O.; Nolan, P. J.; Orce, J. N.; Padilla-Rodal, E.; Phillips, A. A.; Porter-Peden, M.; Ressler, J. J.; Roy, R.; Ruiz, C.; Sarazin, F.; Scraggs, D. P.; Waddington, J. C.; Wan, J. M.; Whitbeck, A.; Williams, S. J.; Wong, J.

2008-10-01

The low-energy structures of the mirror nuclei Ne21 and radioactive Na21 have been examined by using Coulomb excitation at the TRIUMF-ISAC radioactive ion beam facility. Beams of ~5×106 ions/s were accelerated to 1.7 MeV/A and Coulomb excited in a 0.5 mg/cm2 natTi target. Scattered beam and target particles were detected by the segmented Si detector BAMBINO, while γ rays were observed by using two TIGRESS HPGe clover detectors perpendicular to the beam axis. For each isobar, Coulomb excitation from the (3)/(2)+ ground state to the first excited (5)/(2)+ state was observed and B(E2) values were determined by using the 2+→0+ de-excitation in Ti48 as a reference. The ϕ segmentation of BAMBINO was used to deduce tentative assignments for the signs of the mixing ratios between the E2 and M1 components of the transitions. The resulting B(E2)↑ values are 131±9e2 fm4 (25.4±1.7 W.u.) for Ne21 and 205±14e2 fm4 (39.7±2.7 W.u.) for Na21. The fit to the present data and the known lifetimes determined E2/M1 mixing ratios and B(M1)↓ values of δ=(-)0.0767±0.0027 and 0.1274±0.0025μN2 and δ=(+)0.0832±0.0028 and 0.1513±0.0017μN2 for Ne21 and Na21, respectively (with Krane and Steffen sign convention). By using the effective charges ep=1.5e and en=0.5e, the B(E2) values produced by the p-sd shell model are 30.7 and 36.4 W.u. for Ne21 and Na21, respectively. This analysis resolves a significant discrepancy between a previous experimental result for Na21 and shell-model calculations.
The excitation mechanism of btp2 Ir(acac) in CBP host.

PubMed

Xiao-Bo, Zhang; Fu-Xiang, Wei

2017-05-01

Whether bis(2-(2'-benzo[4,5-α]thienyl)pyridinato-N,C3')iridium(acetylacetonate) (btp 2 Ir(acac)) emission comes from carrier trapping and/or energy transfer, when doped in the 4,4'-bis(N-carbazolyl)biphenyl (CBP) host in organic light-emitting devices, is not clear; therefore, the btp 2 Ir(acac) emission in CBP hosts was studied. In the red-doped device, both N,N'-bis(1-naphthyl)-N,N'-diphenyl-1.1'-bipheny1-4-4'-diamine (NPB) and (1,1'-biphenyl-4'-oxy)bis(8-hydroxy-2-methylquinolinato)-aluminum (BAlq) emission appeared, which illustrated that CBP excitons cannot be formed at two emissive layer (EML) interfaces in the device. In the co-doped devices, NPB and BAlq emissions disappear and 1,4-bis[2-(3-N-ethylcarbazoryl)vinyl]benzene (BCzVB) emission appears, illustrating the formation of CBP excitons at two EML interfaces in these devices. The reason for this difference was analyzed and it was found that holes in the NPB layer could be made directly into the CBP host in the EML interface of the red-doped device. In contrast, holes were injected into CBP host via the btp 2 Ir(acac)/BCzVB dopants in the co-doped devices, which facilitated hole injection from the NPB layer to the EML, leading to the formation of CBP excitons at two EML interfaces in the co-doped devices. Therefore, btp 2 Ir(acac) emission was caused by carrier trapping in the red-doped device, while, in the co-doped devices, it resulted from both carrier trapping and energy transfer from the CBP. Furthermore, it was revealed that the carrier trapping mechanism is less efficient than the energy transfer mechanism for btp 2 Ir(acac) excitation in co-doped devices. In summary, our results clarified the excitation mechanism of btp 2 Ir(acac) in the CBP host. Copyright © 2016 John Wiley & Sons, Ltd.
A Review of Parametric Oscillators and Mixers and an Evaluation of Materials for 2 - 6 micrometer Applications

DTIC Science & Technology

1974-07-01

44 ’a N -1 - ’ O𔃺 0 IU U O hl af f T o 8 N0 N 0!I .II . I N tD . N - -- N" N c00 0 ’~ 0 t4 .W 1 A 0 0 40 Q, Z.- 4 cc I n In m-" In w) ’n 41 N z0...Id 36 - 12 (Ref 39) Ref. 39,40 Id 14 I Id36 td Jsine (Type I) _____1 36__ _ _ _ _ __ _ _ _ _ _ _ 36 AgGaSe 2 T2m Negative Id 36 = 3 (Ref 41) Ref...4~~C’.-4.4 ’-tCl -40 (4C’J’J.l00 .-4.I.- 00 H. 04MrIrI"c) ý - 2- td Ln oo N o 0 NC 4’.OC4 V- N-: - C4 ~s ~~ NV.%D a 0t- 4 - n &nIfVl r cN O 1t N
Cholinergic Neurons Excite Cortically Projecting Basal Forebrain GABAergic Neurons

PubMed Central

Yang, Chun; McKenna, James T.; Zant, Janneke C.; Winston, Stuart; Basheer, Radhika

2014-01-01

The basal forebrain (BF) plays an important role in the control of cortical activation and attention. Understanding the modulation of BF neuronal activity is a prerequisite to treat disorders of cortical activation involving BF dysfunction, such as Alzheimer's disease. Here we reveal the interaction between cholinergic neurons and cortically projecting BF GABAergic neurons using immunohistochemistry and whole-cell recordings in vitro. In GAD67-GFP knock-in mice, BF cholinergic (choline acetyltransferase-positive) neurons were intermingled with GABAergic (GFP+) neurons. Immunohistochemistry for the vesicular acetylcholine transporter showed that cholinergic fibers apposed putative cortically projecting GABAergic neurons containing parvalbumin (PV). In coronal BF slices from GAD67-GFP knock-in or PV-tdTomato mice, pharmacological activation of cholinergic receptors with bath application of carbachol increased the firing rate of large (>20 μm diameter) BF GFP+ and PV (tdTomato+) neurons, which exhibited the intrinsic membrane properties of cortically projecting neurons. The excitatory effect of carbachol was blocked by antagonists of M1 and M3 muscarinic receptors in two subpopulations of BF GABAergic neurons [large hyperpolarization-activated cation current (Ih) and small Ih, respectively]. Ion substitution experiments and reversal potential measurements suggested that the carbachol-induced inward current was mediated mainly by sodium-permeable cation channels. Carbachol also increased the frequency of spontaneous excitatory and inhibitory synaptic currents. Furthermore, optogenetic stimulation of cholinergic neurons/fibers caused a mecamylamine- and atropine-sensitive inward current in putative GABAergic neurons. Thus, cortically projecting, BF GABAergic/PV neurons are excited by neighboring BF and/or brainstem cholinergic neurons. Loss of cholinergic neurons in Alzheimer's disease may impair cortical activation, in part, through disfacilitation of BF cortically
Perturbed soliton excitations of Rao-dust Alfvén waves in magnetized dusty plasmas

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

Kavitha, L., E-mail: louiskavitha@yahoo.co.in; The Abdus Salam International Centre for Theoretical Physics, Trieste; Lavanya, C.

We investigate the propagation dynamics of the perturbed soliton excitations in a three component fully ionized dusty magnetoplasma consisting of electrons, ions, and heavy charged dust particulates. We derive the governing equation of motion for the two dimensional Rao-dust magnetohydrodynamic (R-D-MHD) wave by employing the inertialess electron equation of motion, inertial ion equation of motion, the continuity equations in a plasma with immobile charged dust grains, together with the Maxwell's equations, by assuming quasi neutrality and neglecting the displacement current in Ampere's law. Furthermore, we assume the massive dust particles are practically immobile since we are interested in timescales muchmore » shorter than the dusty plasma period, thereby neglecting any damping of the modes due to the grain charge fluctuations. We invoke the reductive perturbation method to represent the governing dynamics by a perturbed cubic nonlinear Schrödinger (pCNLS) equation. We solve the pCNLS, along the lines of Kodama-Ablowitz multiple scale nonlinear perturbation technique and explored the R-D-MHD waves as solitary wave excitations in a magnetized dusty plasma. Since Alfvén waves play an important role in energy transport in driving field-aligned currents, particle acceleration and heating, solar flares, and the solar wind, this representation of R-D-MHD waves as soliton excitations may have extensive applications to study the lower part of the earth's ionosphere.« less
46 CFR 111.12-3 - Excitation.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 46 Shipping 4 2011-10-01 2011-10-01 false Excitation. 111.12-3 Section 111.12-3 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) ELECTRICAL ENGINEERING ELECTRIC SYSTEMS-GENERAL REQUIREMENTS Generator Construction and Circuits § 111.12-3 Excitation. In general, excitation must meet...
46 CFR 111.12-3 - Excitation.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 46 Shipping 4 2013-10-01 2013-10-01 false Excitation. 111.12-3 Section 111.12-3 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) ELECTRICAL ENGINEERING ELECTRIC SYSTEMS-GENERAL REQUIREMENTS Generator Construction and Circuits § 111.12-3 Excitation. In general, excitation must meet...
46 CFR 111.12-3 - Excitation.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 46 Shipping 4 2014-10-01 2014-10-01 false Excitation. 111.12-3 Section 111.12-3 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) ELECTRICAL ENGINEERING ELECTRIC SYSTEMS-GENERAL REQUIREMENTS Generator Construction and Circuits § 111.12-3 Excitation. In general, excitation must meet...

46 CFR 111.12-3 - Excitation.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 46 Shipping 4 2012-10-01 2012-10-01 false Excitation. 111.12-3 Section 111.12-3 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) ELECTRICAL ENGINEERING ELECTRIC SYSTEMS-GENERAL REQUIREMENTS Generator Construction and Circuits § 111.12-3 Excitation. In general, excitation must meet...
New foot remains from the Gran Dolina-TD6 Early Pleistocene site (Sierra de Atapuerca, Burgos, Spain).

PubMed

Pablos, Adrián; Lorenzo, Carlos; Martínez, Ignacio; Bermúdez de Castro, José María; Martinón-Torres, María; Carbonell, Eudald; Arsuaga, Juan Luis

2012-10-01

This paper presents and describes new foot fossils from the species Homo antecessor, found in level TD6 of the site of Gran Dolina (Sierra de Atapuerca, Burgos, Spain). These new fossils consist of an almost complete left talus (ATD6-95) and the proximal three-quarters of a right fourth metatarsal (ATD6-124). The talus ATD6-95 is tentatively assigned to Hominin 10 of the TD6 sample, an adult male specimen with which the second metatarsal ATD6-70+107 (already published) is also tentatively associated. Analysis of these fossils and other postcranial remains has made possible to estimate a stature similar to those of the specimens from the Middle Pleistocene site of Sima de los Huesos (Sierra de Atapuerca, Burgos, Spain). The morphology of the TD6 metatarsals does not differ significantly from that of modern humans, Neanderthals and the specimens from Sima de los Huesos. Talus ATD6-95, however, differs from the rest of the comparative samples in being long and high, having a long and wide trochlea, and displaying a proportionally short neck. Copyright © 2012 Elsevier Ltd. All rights reserved.
Replication of transformation-defective mutants of the Prague strain of Rous sarcoma virus and isolation of a td mutant from duck-adapted PR-RSV-C.

PubMed

Geryk, J; Mazo, A; Svoboda, J; Hlozánek, I

1980-01-01

The replication of transformation-defective mutants of the Prague strain of Rous sarcoma virus subgroup C was studied using roller cultures. Under such conditions, 10(5)--10(6) infectous units of virus per 0.2 ml were produced, as revealed in both the reverse transcriptase and 16Q complementation tests. A new td daPR-RSV-C mutant was isolated from duck-adapted PR-RSV-C. This mutant replicated in roller cultures with equal efficiency as the original td PR-RSV-C. It was verified that td daPR-RSV-C does not transform chicken fibroblasts, is not oncogenic for 3-week-old chickens and has subgroup C host-range specificity. Both td mutants replicate in duck cells and reach the same titres.
Higgs amplitude mode in the BCS superconductors Nb1-xTi(x)N induced by terahertz pulse excitation.

PubMed

Matsunaga, Ryusuke; Hamada, Yuki I; Makise, Kazumasa; Uzawa, Yoshinori; Terai, Hirotaka; Wang, Zhen; Shimano, Ryo

2013-08-02

Ultrafast responses of BCS superconductor Nb(1-x)Ti(x)N films in a nonadiabatic excitation regime were investigated by using terahertz (THz) pump-THz probe spectroscopy. After an instantaneous excitation with the monocycle THz pump pulse, a transient oscillation emerges in the electromagnetic response in the BCS gap energy region. The oscillation frequency coincides with the asymptotic value of the BCS gap energy, indicating the appearance of the theoretically anticipated collective amplitude mode of the order parameter, namely the Higgs amplitude mode. Our result opens a new pathway to the ultrafast manipulation of the superconducting order parameter by optical means.
Electron-impact excitation of the 1{sup 1}{ital S}{r_arrow}3{sup 1}{ital P} and 1{sup 1}{ital S}{r_arrow}4{sup 1}{ital P} transitions in helium

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

Khakoo, M.A.; Roundy, D.; Rugamas, F.

1996-11-01

The method of electron-photon coincidence is used to {open_quote}{open_quote}resolve{close_quote}{close_quote} the electron-impact excitation of the {ital n}{sup 1}{ital P} levels ({ital n}=3 and 4) from nearby levels. Experimentally determined ratios of the differential cross sections for the electron-impact excitation of 1{sup 1}{ital S}{r_arrow}2{sup 1}{ital P}, to 1{sup 1}{ital S}{r_arrow}3{sup 1}{ital P}, and 4{sup 1}{ital P} transitions are presented at 30-, 40-, and 80-eV incident electron energies. Differential cross sections for the 1{sup 1}{ital S}{r_arrow}3{sup 1}{ital P} and 1{sup 1}{ital S}{r_arrow}4{sup 1}{ital P} transitions are derived by normalizing these ratios to available experimental differential cross sections for the 1{sup 1}{ital S}{r_arrow}2{sup 1}{italmore » P} transition. The ratios and differential cross sections are compared to available theoretical and semiempirical data. {copyright} {ital 1996 The American Physical Society.}« less
Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes

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

Escudero, Daniel, E-mail: escudero@kofo.mpg.de, E-mail: thiel@kofo.mpg.de; Thiel, Walter, E-mail: escudero@kofo.mpg.de, E-mail: thiel@kofo.mpg.de

2014-05-21

We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF{sub 6} complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO{sub 4}{sup −}, Cr(CO){sub 6}, [Fe(CN){sub 6}]{sup 4−}, four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons withmore » results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.« less
RLV-TD Flight Measured Aeroacoustic Levels and its Comparison with Predictions

NASA Astrophysics Data System (ADS)

Manokaran, K.; Prasath, M.; Venkata Subrahmanyam, B.; Ganesan, V. R.; Ravindran, Archana; Babu, C.

2017-12-01

The Reusable Launch Vehicle-Technology Demonstrator (RLV-TD) is a wing body configuration successfully flight tested. One of the important flight measurements is the acoustic levels. There were five external microphones, mounted on the fuselage-forebody, wing, vertical tail, inter-stage (ITS) and core base shroud to measure the acoustic levels from lift-off to splash down. In the ascent phase, core base shroud recorded the overall maximum at both lift-off and transonic conditions. In-flight noise levels measured on the wing is second highest, followed by fuselage and vertical tail. Predictions for flight trajectory compare well at all locations except for vertical tail (4.5 dB). In the descent phase, maximum measured OASPL occurs at transonic condition for the wing, followed by vertical tail and fuselage. Predictions for flight trajectory compare well at all locations except for wing (- 6.0 dB). Spectrum comparison is good in the ascent phase compared to descent phase. Roll Reaction control system (RCS) thruster firing signature is seen in the acoustic measurements on the wing and vertical tail during lift-off.
Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

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

Huang, Wei; Jiang, Ning; Schwarz, W. H. Eugen

The geometric and electronic ground-state structures of six MS 4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS 4 species are compared to analogous MO 4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4, whereas low MOS=II appears in high- spin septet D 2d species Fe(S 2) 2 and (slightly excited) metastable Fe(O 2) 2. The ground states of all other moleculesmore » have intermediate MOS values, containing S 2-, S 2 2-, S2 1- (and resp. O 2--, O 1-, O 2 2-, O 2 1-) ligands, bonded by ionic, covalent and correlative contributions.« less
Use of DEAD-box polypeptide-4 (Ddx4) gene promoter-driven fluorescent reporter mice to identify mitotically active germ cells in post-natal mouse ovaries.

PubMed

Park, Eun-Sil; Tilly, Jonathan L

2015-01-01

Several laboratories have independently isolated mitotically active germ cells, termed female germline stem cells or oogonial stem cells (OSCs), from adult mouse ovaries. However, a recent study using Ddx4-Cre;Rosa26 reporter mice concluded that such germ cells do not exist. Given the disparity in conclusions drawn in this study compared with others, we felt it was important to re-assess the utility of Ddx4-Cre;Rosa26 reporter mice for identification of OSCs in adult mouse ovaries. Transgenic Ddx4-Cre mice were crossed with Rosa26(tdTm/tdTm) mice to drive restricted tomato red (tdTm) gene expression in cells in which the Ddx4 gene promoter has been activated. Crude dispersion of ovaries from recombined offspring generated cell fractions containing tdTm-positive immature oocytes, which are incapable of proliferation and thus probably represent the uncharacterized reporter-positive ovarian cells identified in the paper Zhang et al. (2012) as being mitotically inactive. Dispersed ovaries further subjected to fluorescence-activated cell sorting yielded a large population of non-germline tdTm-positive cells, indicative of promoter 'leakiness' in the Ddx4-Cre mouse line. Nonetheless, a small percentage of these tdTm-positive cells exhibited externalized (extracellular, ec) expression of Ddx4 protein (ecDdx4-positive), expressed markers of primitive germ cells but not of oocytes, and actively proliferated in culture, all of which are characteristic features of OSCs. Thus, crude dispersion of ovaries collected from Ddx4 gene promoter-driven reporter mice is not, by itself, a reliable approach to identify OSCs, whereas the same ovarian dispersates further subjected to cell sorting strategies yield purified OSCs that can be expanded in culture. © The Author 2014. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.
Excitation of atomic nitrogen by electron impact

NASA Technical Reports Server (NTRS)

Stone, E. J.; Zipf, E. C.

1972-01-01

Absolute cross sections were measured for the excitation of the N I(1134, 1164, 1168, 1200, 1243, and 1743 A) multiplets by electron impact on atomic nitrogen. The presence of vibrationally excited molecular nitrogen in the discharged gas was confirmed, and its effect on the measurements is discussed. The ratio of the oscillator strengths of the 1200 and 1134 A resonance transitions is presented, as well as the branching ratio for the N I(1311/1164 A) multiplets. Striking differences in the distribution of intensity between the spectra of atomic nitrogen and molecular nitrogen excited by energetic electrons suggest an optical method for measuring the density of atomic nitrogen in the upper atmosphere.
Dissociative Excitation of Thymine by Electron Impact

NASA Astrophysics Data System (ADS)

McConkey, William; Tiessen, Collin; Hein, Jeffrey; Trocchi, Joshuah; Kedzierski, Wladek

2014-05-01

A crossed electron-gas beam system coupled to a VUV spectrometer has been used to investigate the dissociation of thymine (C5H6N2O2) into excited atomic fragments in the electron-impact energy range from threshold to 375 eV. A special stainless steel oven is used to vaporize the thymine and form it into a beam where it is intersected by a magnetically collimated electron beam, typical current 50 μA. The main features in the spectrum are the H Lyman series lines. The probability of extracting excited C or N atoms from the ring is shown to be very small. In addition to spectral data, excitation probability curves as a function of electron energy will be presented for the main emission features. Possible dissociation channels and excitation mechanisms in the parent molecule will be discussed. The authors thank NSERC (Canada) for financial support.
0–0 Energies Using Hybrid Schemes: Benchmarks of TD-DFT, CIS(D), ADC(2), CC2, and BSE/GW formalisms for 80 Real-Life Compounds

PubMed Central

2015-01-01

The 0–0 energies of 80 medium and large molecules have been computed with a large panel of theoretical formalisms. We have used an approach computationally tractable for large molecules, that is, the structural and vibrational parameters are obtained with TD-DFT, the solvent effects are accounted for with the PCM model, whereas the total and transition energies have been determined with TD-DFT and with five wave function approaches accounting for contributions from double excitations, namely, CIS(D), ADC(2), CC2, SCS-CC2, and SOS-CC2, as well as Green’s function based BSE/GW approach. Atomic basis sets including diffuse functions have been systematically applied, and several variations of the PCM have been evaluated. Using solvent corrections obtained with corrected linear-response approach, we found that three schemes, namely, ADC(2), CC2, and BSE/GW allow one to reach a mean absolute deviation smaller than 0.15 eV compared to the measurements, the two former yielding slightly better correlation with experiments than the latter. CIS(D), SCS-CC2, and SOS-CC2 provide significantly larger deviations, though the latter approach delivers highly consistent transition energies. In addition, we show that (i) ADC(2) and CC2 values are extremely close to each other but for systems absorbing at low energies; (ii) the linear-response PCM scheme tends to overestimate solvation effects; and that (iii) the average impact of nonequilibrium correction on 0–0 energies is negligible. PMID:26574326
New Theoretical Developments in Exploring Electronically Excited States: Including Localized Configuration Interaction Singles and Application to Large Helium Clusters

NASA Astrophysics Data System (ADS)

Closser, Kristina Danielle

This thesis presents new developments in excited state electronic structure theory. Contrasted with the ground state, the electronically excited states of atoms and molecules often are unstable and have short lifetimes, exhibit a greater diversity of character and are generally less well understood. The very unusual excited states of helium clusters motivated much of this work. These clusters consist of large numbers of atoms (experimentally 103--109 atoms) and bands of nearly degenerate excited states. For an isolated atom the lowest energy excitation energies are from 1s → 2s and 1s → 2 p transitions, and in clusters describing the lowest energy band minimally requires four states per atom. In the ground state the clusters are weakly bound by van der Waals interactions, however in the excited state they can form well-defined covalent bonds. The computational cost of quantum chemical calculations rapidly becomes prohibitive as the size of the systems increase. Standard excited-state methods such as configuration interaction singles (CIS) and time-dependent density functional theory (TD-DFT) can be used with ≈100 atoms, and are optimized to treat only a few states. Thus, one of our primary aims is to develop a method which can treat these large systems with large numbers of nearly degenerate excited states. Additionally, excited states are generally formed far from their equilibrium structures. Vertical excitations from the ground state induce dynamics in the excited states. Thus, another focus of this work is to explore the results of these forces and the fate of the excited states. Very little was known about helium cluster excited states when this work began, thus we first investigated the excitations in small helium clusters consisting of 7 or 25 atoms using CIS. The character of these excited states was determined using attachment/detachment density analysis and we found that in the n = 2 manifold the excitations could generally be interpreted as
Adsorption and diffusion of Ga and N adatoms on GaN surfaces: Comparing the effects of Ga coverage and electronic excitation

NASA Astrophysics Data System (ADS)

Takeuchi, Noboru; Selloni, Annabella; Myers, T. H.; Doolittle, A.

2005-09-01

We present density-functional-theory calculations of the binding and diffusion of Ga and N adatoms on GaN (0001) and (000-1) surfaces under different conditions, including stoichiometric and Ga-rich surfaces, as well as in the presence of electron-hole (e-h) pairs induced by light- or electron-beam irradiation. We find that both Ga-rich conditions and electronic excitations cause a significant reduction of the adatom diffusion barriers, as required to improve the quality of the material. However, the two effects are nonadditive, as the influence of e-h pairs are found to be less important for the more metallic situations.
First principle study of a potential bioactive molecule with tetrahydroisoquinoline, carbothiomide and adamantane scaffolds

NASA Astrophysics Data System (ADS)

Al-Shehri, Mona M.; Al-Majed, Abdul-Rahman A.; Aljohar, Haya I.; El-Emam, Ali A.; Pathak, Shilendra K.; Sachan, Alok K.; Prasad, Onkar; Sinha, Leena

2017-09-01

The FT-Raman and FT-IR spectra of N-(adamantan-1-yl)-1,2,3,4-tetrahydroisoquinoline-2-carbothioamide were recorded and investigated. The DFT/M06-2X/6-311++G(d,p) method was used to compute the vibrational wavenumbers. The effect of solvents (water, carbon tetrachloride and chloroform) on the dipole moment and polarizability has been evaluated. UV-Vis spectrum of the title compound was recorded and compared with the theoretical spectrum calculated by TD-DFT approach. To investigate the movement of electrons within the system when excited, the difference of the excited and ground state densities has also been plotted. The molecular docking studies reveals that the investigated compound may exhibit HIV-1 Protease inhibitory activity.
Excitations in the Yang–Gaudin Bose gas

DOE PAGES

Robinson, Neil J.; Konik, Robert M.

2017-06-01

Here, we study the excitation spectrum of two-component delta-function interacting bosons confined to a single spatial dimension, the Yang–Gaudin Bose gas. We show that there are pronounced finite-size effects in the dispersion relations of excitations, perhaps best illustrated by the spinon single particle dispersion which exhibits a gap at 2k F and a finite-momentum roton-like minimum. Such features occur at energies far above the finite volume excitation gap, vanish slowly as 1/L for fixed spinon number, and can persist to the thermodynamic limit at fixed spinon density. Features such as the 2k F gap also persist to multi-particle excitation continua. Our results show that excitations in the finite system can behave in a qualitatively different manner to analogous excitations in the thermodynamic limit. The Yang–Gaudin Bose gas is also host to multi-spinon bound states, known asmore » $$\\Lambda$$ -strings. We study these excitations both in the thermodynamic limit under the string hypothesis and in finite size systems where string deviations are taken into account. In the zero-temperature limit we present a simple relation between the length n $$\\Lambda$$-string dressed energies $$\\epsilon_n(\\lambda)$$ and the dressed energy $$\\epsilon(k)$$. We solve the Yang–Yang–Takahashi equations numerically and compare to the analytical solution obtained under the strong couple expansion, revealing that the length n $$\\Lambda$$ -string dressed energy is Lorentzian over a wide range of real string centers λ in the vicinity of $$\\lambda = 0$$ . We then examine the finite size effects present in the dispersion of the two-spinon bound states by numerically solving the Bethe ansatz equations with string deviations.« less
Experimental ion mobility measurements in Xe-CH4

NASA Astrophysics Data System (ADS)

Perdigoto, J. M. C.; Cortez, A. F. V.; Veenhof, R.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Conde, C. A. N.

2017-09-01

Data on ion mobility is important to improve the performance of large volume gaseous detectors. In the present work, the method, experimental setup and results for the ion mobility measurements in Xe-CH4 mixtures are presented. The results for this mixture show the presence of two distinct groups of ions. The nature of the ions depend on the mixture ratio since they are originated by both Xe and CH4. The results here presented were obtained for low reduced electric fields, E/N, 10-25 Td (2.4-6.1 kV ṡ cm-1 ṡ bar-1), at low pressure (8 Torr) (10.6 mbar), and at room temperature.
The effect of rolling massage on the excitability of the corticospinal pathway.

PubMed

Aboodarda, Saied J; Greene, Rebecca M; Philpott, Devin T; Jaswal, Ramandeep S; Millet, Guillaume Y; Behm, David G

2018-04-01

The aim of the present study was to investigate the alterations of corticospinal excitability (motor evoked potential, MEP) and inhibition (silent period, SP) following rolling massage of the quadriceps muscles. Transcranial magnetic and femoral nerve electrical stimuli were used to elicit MEPs and compound muscle action potential (Mmax) in the vastus lateralis and vastus medialis muscles prior to and following either (i) 4 sets of 90-s rolling massage (ROLLING) or (ii) rest (CONTROL). One series of neuromuscular evaluations, performed after each set of ROLLING or CONTROL, included 3 MEPs and 1 Mmax elicited every 4 s during 15-s submaximal contractions at 10% (experiment 1, n = 16) and 50% (experiment 2, n = 10) of maximal voluntary knee extensions (MVC). The MEP/Mmax ratio and electromyographic activity recorded from vastus lateralis at 10% MVC demonstrated significantly lower values during ROLLING than CONTROL (P < 0.05). The ROLLING did not elicit any significant changes in muscle excitability (Mmax area) and duration of transcranial magnetic stimulation-induced SP recorded from any muscle or level of contraction (P > 0.05). The findings suggest that rolling massage can modulate the central excitability of the circuitries innervating the knee extensors; however, the observed effects are dependent on the background contraction intensity during which the neuromuscular measurements are recorded.
Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

NASA Astrophysics Data System (ADS)

Wang, Se; Wang, Zhuang; Hao, Ce

2016-01-01

The time-dependent density functional theory (TDDFT) method was performed to investigate the excited-state intramolecular double proton transfer (ESIDPT) reaction of calix[4] arene (C4A) and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S1, S2 and T1) were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S2 and T1 states compared to those in the ground state. Interestingly, upon excitation to the S1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1···O2 and O2-H2···O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.
Excitation energies of molecules within time-independent density functional theory

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

Hemanadhan, M., E-mail: hemanadh@iitk.ac.in; Harbola, Manoj K., E-mail: hemanadh@iitk.ac.in

2014-04-24

Recently proposed exchange energy functional for excited-states is tested for obtaining excitation energies of diatomic molecules. The functional is the ground-state counterpart of the local-density approximation, the modified local spin density (MLSD). The MLSD functional is tested for the N{sub 2} and CO diatomic molecules. The excitation energy obtained with the MLSD functional for the N{sub 2} molecule is in close vicinity to that obtained from the exact exchange orbital functional, Krieger, Li and Iafrate (KLI). For the CO molecule, the departure in excitation energy is observed and is due to the overcorrection of self-interaction.

Excitation energies of molecules within time-independent density functional theory

NASA Astrophysics Data System (ADS)

Hemanadhan, M.; Harbola, Manoj K.

2014-04-01

Recently proposed exchange energy functional for excited-states is tested for obtaining excitation energies of diatomic molecules. The functional is the ground-state counterpart of the local-density approximation, the modified local spin density (MLSD). The MLSD functional is tested for the N2 and CO diatomic molecules. The excitation energy obtained with the MLSD functional for the N2 molecule is in close vicinity to that obtained from the exact exchange orbital functional, Krieger, Li and Iafrate (KLI). For the CO molecule, the departure in excitation energy is observed and is due to the overcorrection of self-interaction.
Fluorescence excitation and excited state intramolecular relaxation dynamics of jet-cooled methyl-2-hydroxy-3-naphthoate

NASA Astrophysics Data System (ADS)

McCarthy, Annemarie; Ruth, Albert A.

2013-11-01

Two distinct S0 → S1 fluorescence excitation spectra of methyl-2-hydroxy-3-napthoate (MHN23) have been obtained by monitoring fluorescence separately in the short (˜410 nm) and long (˜650 nm) wavelength emission bands. The short wavelength fluorescence is assigned to two MHN23 conformers which do not undergo excited state intramolecular proton transfer (ESIPT). Analysis of the 'long wavelength' fluorescence excitation spectrum, which arises from the proton transfer tautomer of MHN23 indicates an average lifetime of τ ⩾ 18 ± 2 fs for the initially excited states. Invoking the results of Catalan et al. [J. Phys. Chem. A, 1999, 103, 10921], who determined the N tautomer to decay predominantly via a fast non-radiative process, the limit of the rate of intramolecular excited proton transfer in MHN23 is calculated as, kpt ⩽ 1 × 1012 s-1.
From N=4 Galilean superparticle to three-dimensional non-relativistic N=4 superfields

NASA Astrophysics Data System (ADS)

Fedoruk, Sergey; Ivanov, Evgeny; Lukierski, Jerzy

2018-05-01

We consider the general N=4 , d = 3 Galilean superalgebra with arbitrary central charges and study its dynamical realizations. Using the nonlinear realization techniques, we introduce a class of actions for N=4 three-dimensional non-relativistic superparticle, such that they are linear in the central charge Maurer-Cartan one-forms. As a prerequisite to the quantization, we analyze the phase space constraints structure of our model for various choices of the central charges. The first class constraints generate gauge transformations, involving fermionic κ-gauge transformations. The quantization of the model gives rise to the collection of free N=4 , d = 3 Galilean superfields, which can be further employed, e.g., for description of three-dimensional non-relativistic N=4 supersymmetric theories.
Collisional excitation of the highly excited hydrogen atoms in the dipole form of the semiclassical impact parameter and Born approximations

NASA Technical Reports Server (NTRS)

Omidvar, K.

1971-01-01

Expressions for the excitation cross section of the highly excited states of the hydrogenlike atoms by fast charged particles have been derived in the dipole approximation of the semiclassical impact parameter and the Born approximations, making use of a formula for the asymptotic expansion of the oscillator strength of the hydrogenlike atoms given by Menzel. When only the leading term in the asymptotic expansion is retained, the expression for the cross section becomes identical to the expression obtained by the method of the classical collision and correspondence principle given by Percival and Richards. Comparisons are made between the Bethe coefficients obtained here and the Bethe coefficients of the Born approximation for transitions where the Born calculation is available. Satisfactory agreement is obtained only for n yields n + 1 transitions, with n the principal quantum number of the excited state.
Magnetic excitations from an S=1/2 diamond-shaped tetramer compound Cu 2PO 4OH

DOE PAGES

Matsuda, Masaaki; Dissanayake, Sachith E.; Abernathy, Douglas L.; ...

2015-11-30

Inelastic neutron scattering experiments have been carried out on a powder sample of Cu 2PO 4OH, which consists of diamond-shaped tetramer spin units with S=1/2. We have observed two nearly dispersionless magnetic excitations at E 1 ~2 and E 2 ~0 meV, whose energy width are broader than the instrumental resolution. The simplest square tetramer model with one dominant interaction, which predicts two sharp excitation peaks at E 1 and E 2(=2E 1), does not explain the experimental result. We found that two diagonal intratetramer interactions compete with the main interaction and weak intertetramer interactions connect the tetramers. The mainmore » intratetramer interaction is found to split into two inequivalent ones due to a structural distortion below 160 K. Cu 2PO 4OH is considered to be a good material to study the S=1/2 Heisenberg tetramer system.« less
Adapted RF pulse design for SAR reduction in parallel excitation with experimental verification at 9.4 T.

PubMed

Wu, Xiaoping; Akgün, Can; Vaughan, J Thomas; Andersen, Peter; Strupp, John; Uğurbil, Kâmil; Van de Moortele, Pierre-François

2010-07-01

Parallel excitation holds strong promises to mitigate the impact of large transmit B1 (B+1) distortion at very high magnetic field. Accelerated RF pulses, however, inherently tend to require larger values in RF peak power which may result in substantial increase in Specific Absorption Rate (SAR) in tissues, which is a constant concern for patient safety at very high field. In this study, we demonstrate adapted rate RF pulse design allowing for SAR reduction while preserving excitation target accuracy. Compared with other proposed implementations of adapted rate RF pulses, our approach is compatible with any k-space trajectories, does not require an analytical expression of the gradient waveform and can be used for large flip angle excitation. We demonstrate our method with numerical simulations based on electromagnetic modeling and we include an experimental verification of transmit pattern accuracy on an 8 transmit channel 9.4 T system.
N-2-Hydroxy-4-methoxyacetophenone- N'-4-nitrobenzoyl hydrazine: Synthesis and structural characterization

NASA Astrophysics Data System (ADS)

Bessy Raj, B. N.; Kurup, M. R. Prathapachandra

2007-04-01

A new aroyl hydrazone, N-2-hydroxy-4-methoxyacetophenone- N'-4-nitrobenzoyl hydrazine was prepared by the condensation reaction of 2-hydroxy-4-methoxyacetophenone and 4-nitrobenzoyl hydrazine. Characterization of the compound was done by elemental analysis and electronic, infrared and NMR spectral analyses. The complete structural assignment of the compound was done by NMR studies by using COSY homonuclear and HSQC heteronuclear techniques. The crystal and molecular structure was determined by single crystal X-ray diffraction studies: crystallized in the monoclinic system, space group P2 1/ n, Z = 4, a = 7.3343(9) Å, b = 20.3517(9) Å, c = 10.1375(5) Å, α = 90.00°, β = 95.735(7)° and γ = 90.00°. From the crystal structure, it is concluded that the compound exists as the keto isomer in the solid state. There is a completely extended conformation in the central part of the molecule C5 sbnd C8 dbnd N1 sbnd N2 sbnd C10 dbnd O2 with an E configuration at the double bond of the hydrazinic bridge.
Constraining the excitation conditions of the molecular gas in the most distant submillimetre galaxy at z=4.76

NASA Astrophysics Data System (ADS)

Coppin, Kristen; Weiss, Axel; van der Werf, Paul; Menten, Karl; De Breuck, Carlos; Walter, Fabian; Loenen, Edo; Edge, Alastair; Emonts, Bjorn; Huynh, Minh; Swinbank, Mark; Smail, Ian; Schinnerer, Eva; Greve, Thomas; Chapman, Scott; Danielson, Alice; Knudsen, Kirsten; Dannerbauer, Helmut; Brandt, Niel; Berciano Alba, Alicia; Strom, Allison

2010-10-01

We propose to use ATCA to measure CO(5-4) emission in the currently highest redshift submm-selected galaxy (SMG) known: LESS J033229 at z=4.755. Combined with our previous successful ATCA observations of the CO(2-1) transition in this SMG, we will be able to start building up the CO SED excitation ladder and so gain new insight on the excitation conditions of the molecular gas which is fuelling a massive burst of star formation at a time when the Universe was only 1 Gyr old. ATCA is currently the only available facility that can provide these data, giving us a sneak-preview of the capabilities of ALMA for studying the youngest galaxies in the very distant Universe.
26 CFR 1.56A-4 - Certain taxpayers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... Applicable to Taxable Years Beginning in 1969 and Ending in 1970 § 1.56A-4 Certain taxpayers. For application of the minimum tax in the case of estates and trusts, electing small business corporations, common....58-2 through 1.58-6. [T.D. 7564, 43 FR 40468, Sept. 12, 1978. Redesignated by T.D. 8138, 52 FR 15309...
Predissociation in N2(C'4, 1 Sigma u +) and other N2 states and its importance in the atmospheres of Titan and Triton

NASA Technical Reports Server (NTRS)

Slanger, Tom G.; Copeland, Richard A.

1994-01-01

The objectives of this program are to further the understanding of the upper atmospheres of Titan, Triton, and the Earth in terms of the observed emissions of the 13-14 eV states of N2. These states are generated at quite high rates, yet very little emission is observed from them. The reasons are complex, involving resonance trapping and predissociation, and it is desired to quantify the effects of predissociation, particularly on the c(sub 4)' 1 Sigma(sub u),(sup +) state of N2. Earlier experiments had indicated that predissociation of the c(sub 4)' state was of little importance, yet over the last two years a growing body of evidence has shown that for levels above v = 2, predissociation is in fact a major process. It is the v = 0 level for which production by electron bombardment and photoexcitation is highest, and so it has been most important to evaluate the effects of predissociation on this particular level. The goal has been to target c(sub 4)' (v = 0) for a thorough analysis, in which both the extent of predissociation as a function of rotational level and the atomic product branching ratio, where the only possible products are N(4S) + N(4S) and N(2D) + N(4S), are determined. For the first year of funding, the intention was to demonstrate two-photon excitation of the intermediate N2(a(sup 1) Pi(sub g)) state, so that the gap to the 13 eV energy region could be bridged, and then use a second laser to reach the c(sub 4)' state itself.
Broadband excitation and indirect detection of nitrogen-14 in rotating solids using Delays Alternating with Nutation (DANTE)

NASA Astrophysics Data System (ADS)

Vitzthum, Veronika; Caporini, Marc A.; Ulzega, Simone; Bodenhausen, Geoffrey

2011-09-01

A train of short rotor-synchronized pulses in the manner of Delays Alternating with Nutations for Tailored Excitation (DANTE) applied to nitrogen-14 nuclei ( I = 1) in samples spinning at the magic angle at high frequencies (typically νrot = 62.5 kHz so that τrot = 16 μs) allows one to achieve uniform excitation of a great number of spinning sidebands that arise from large first-order quadrupole interactions, as occur for aromatic nitrogen-14 nuclei in histidine. With routine rf amplitudes ω1( 14N)/(2 π) = 60 kHz and very short pulses of a typical duration 0.5 < τp < 2 μs, efficient excitation can be achieved with 13 rotor-synchronized pulses in 13 τrot = 208 μs. Alternatively, with 'overtone' DANTE sequences using 2, 4, or 8 pulses per rotor period one can achieve efficient broadband excitation in fewer rotor periods, typically 2-4 τrot. These principles can be combined with the indirect detection of 14N nuclei via spy nuclei with S = ½ such as 1H or 13C in the manner of Dipolar Heteronuclear Multiple-Quantum Correlation (D-HMQC).
Photophysics of 4-dimethylamino-4'-cyanostilbene and 4-azetidinyl-4'-cyanostilbene. Time-resolved fluorescence and trans-cis photoisomerisation

NASA Astrophysics Data System (ADS)

Il'ichev, Yurii V.; Kühnle, Wolfgang; Zachariasse, Klaas A.

1996-11-01

The fluorescence decays of trans-4-dimethylamino-4'-cyanostilbene (DCS) and trans-4-azetidinyl-4'-cyanostilbene (ACS) in an unpolar (n-heptane) and a polar (acetonitrile) solvent are single exponential down to a time resolution of around 5 ps and dual fluorescence is not observed. The dipole moment increases in two steps: from 7 D in the ground state via 13 D (DCS) or 10 D (ACS) for the Franck-Condon excited state to 21 D (DCS) or 22 D (ACS) for the relaxed fluorescing CT state. This means that the intramolecular charge transfer (ICT) in the excited state at most involves an intermediate with a subpicosecond lifetime. The presence of the azetidinyl group in ACS does not slow down the ICT reaction, contrary to what has been found for the 4-aminobenzonitriles, showing that inversion of the amino group is not an important reaction coordinate here. The activation energy Etc for trans-cis photoisomerisation is determined from the fluorescence decays in n-heptane (14.0 kJ/mol, DCS) and in acetonitrile (22.7 kJ/mol, DCS and 22.5 kJ/mol, ACS). This increase of Etc with solvent polarity, opposite to what has been found for trans-stilbene, shows that the photoisomerisation transition state is less polar than the CT state.
AlN-based piezoelectric bimorph microgenerator utilizing low-level non-resonant excitation

NASA Astrophysics Data System (ADS)

Hampl, Stefan; Cimalla, Volker; Polster, Tobias; Hoffmann, Martin

2011-06-01

This work aims for utilizing human ocular motion for the self-sufficient power supply of a minimally invasive implantable monitoring system for intraocular pressure (IOP). With a proven piezoelectric functionality (d33>5 pm/V), nanocrystalline thin films of aluminum nitride (AlN) provide a good capability for micromechanical energy harvesting (EH) in medical applications. Many d31-mode microcantilever architectures are poorly suited for human-induced EH: Resonant mass-spring-damper systems are tested under high, narrow-band excitation frequencies. However, human motions, e.g. vibrations of eyeballs are marked by their low frequency, unpredictable, mainly aperiodic and time-varying signature. Different vibration types and directions are 3-dimensionally superimposed. Saccadic eye movements are favorable for inertial microgenerators because of their high dynamic loading (ω<=1000°/s). Our generator concept (symmetric active/active-parallel-bimorph cantilever) enables a high structural compliance by maximizing the piezoactive volume at very low cantilever thicknesses (<1 μm). An increased length and seismic mass enable an effective excitation by low-level aperiodic vibrations such as saccadic acceleration impulses. Analytic calculations and FEA-simulations investigate the potential distribution and transient response of different bimorph structures (length 200- 1000 μm, width 20-200 μm) on broadband vibrations. First released monomorph and bimorph structures show very low resonant frequencies and an adequate robustness.
Low-lying excited states by constrained DFT.

PubMed

Ramos, Pablo; Pavanello, Michele

2018-04-14

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, N c , in the virtual space of a reference set of occupied orbitals. By imposing this population to be N c = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H 3 ) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.
Comparative study of GaN-based ultraviolet LEDs grown on different-sized patterned sapphire substrates with sputtered AlN nucleation layer

NASA Astrophysics Data System (ADS)

Zhou, Shengjun; Hu, Hongpo; Liu, Xingtong; Liu, Mengling; Ding, Xinghuo; Gui, Chengqun; Liu, Sheng; Guo, L. Jay

2017-11-01

GaN-based ultraviolet-light-emitting diodes (UV LEDs) with 375 nm emission were grown on different-sized patterned sapphire substrates (PSSs) with ex situ 15-nm-thick sputtered AlN nucleation layers by metal-organic chemical vapor deposition (MOCVD). It was observed through in situ optical reflectance monitoring that the transition time from a three-dimensional (3D) island to a two-dimensional (2D) coalescence was prolonged when GaN was grown on a larger PSS, owing to a much longer lateral growth time of GaN. The full widths at half-maximum (FWHMs) of symmetric GaN(002) and asymmetric GaN(102) X-ray diffraction (XRD) rocking curves decreased as the PSS size increased. By cross-sectional transmission electron microscopy (TEM) analysis, it was found that the threading dislocation (TD) density in UV LEDs decreased with increasing pattern size and fill factor of the PSS, thereby resulting in a marked improvement in internal quantum efficiency (IQE). Finite-difference time-domain (FDTD) simulations quantitatively demonstrated a progressive decrease in light extraction efficiency (LEE) as the PSS size increased. However, owing to the significantly reduced TD density in InGaN/AlInGaN multiple quantum wells (MQWs) and thus improved IQE, the light output power of the UV LED grown on a large PSS with a fill factor of 0.71 was 131.8% higher than that of the UV LED grown on a small PSS with a fill factor of 0.4, albeit the UV LED grown on a large PSS exhibited a much lower LEE.
Unintentional indium incorporation into barriers of InGaN/GaN multiple quantum wells studied by photoreflectance and photoluminescence excitation spectroscopy

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

Freytag, Stefan, E-mail: stefan.freytag@ovgu.de; Feneberg, Martin; Berger, Christoph

2016-07-07

In{sub x}Ga{sub 1–x}N/GaN single and multi quantum well (MQW) structures with x ≈ 0.13 were investigated optically by photoreflectance, photoluminescence excitation spectroscopy, and luminescence. Clear evidence of unintentional indium incorporation into the nominal GaN barrier layers is found. The unintentional In content is found to be around 3%. Inhomogeneous distribution of In atoms occurs within the distinct quantum well (QW) layers, which is commonly described as statistical alloy fluctuation and leads to the characteristic S-shape temperature shift of emission energy. Furthermore, differences in emission energy between the first and the other QWs of a MQW stack are found experimentally. Thismore » effect is discussed with the help of model calculations and is assigned to differences in the confining potential due to unwanted indium incorporation for the upper QWs.« less
Accelerated ions and self-excited Alfvén waves at the Earth's bow shock

NASA Astrophysics Data System (ADS)

Berezhko, E. G.; Taneev, S. N.; Trattner, K. J.

2011-07-01

The diffuse energetic ion event and related Alfvén waves upstream of the Earth's bow shock, measured by AMPTE/IRM satellite on 29 September 1984, 06:42-07:22 UT, was studied using a self-consistent quasi-linear theory of ion diffusive shock acceleration and associated Alfvén wave generation. The wave energy density satisfies a wave kinetic equation, and the ion distribution function satisfies the diffusive transport equation. These coupled equations are solved numerically, and calculated ion and wave spectra are compared with observations. It is shown that calculated steady state ion and Alfvén wave spectra are established during the time period of about 1000 s. Alfvén waves excited by accelerated ions are confined within the frequency range (10-2 to 1) Hz, and their spectral peak with the wave amplitude δB ≈ B comparable to the interplanetary magnetic field value B corresponds to the frequency 2 × 10-2 Hz. The high-frequency part of the wave spectrum undergoes absorption by thermal protons. It is shown that the observed ion spectra and the associated Alfvén wave spectra are consistent with the theoretical prediction.
Direct excitation luminescence spectroscopy of Eu(III) complexes of 1,4,7-tris(carbamoylmethyl)-1,4,7,10- tetraazacyclododecane derivatives and kinetic studies of their catalytic cleavage of an RNA analog.

PubMed

Nwe, Kido; Richard, John P; Morrow, Janet R

2007-11-28

The macrocycles 1,4,7-tris(carbamoylmethyl)-1,4,7,10-tetrazacyclododecane (1), 1,4,7-tris[(N-ethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane (2), 1,4,7-tris[(N,N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane (3) and their Eu(III) complexes are prepared. Studies using direct Eu(III) excitation luminescence spectroscopy show that all three Eu(III) complexes exhibit only one predominant isomer with two bound waters under neutral to mildly basic conditions (Eu(X)(H(2)O)(2) for X = 1-3). There are no detectable ligand ionizations over the pH range 5.0-8.0 for Eu(3), 5.0-8.5 for Eu(2) or 5.0-9.5 for Eu(1). The three Eu(III) complexes show a linear dependence of second-order rate constants for the cleavage of 4-nitrophenyl-2-hydroxyethylphosphate (HpPNP) on pH in the range 6.5-8.0 for Eu(3), 7.0-8.5 for Eu(2) and 7.0-9.0 for Eu(1). This pH-rate profile is consistent with the Eu(III) complex-substrate complex being converted to the active form by loss of a proton and with Eu(III) water pK(a) values that are higher than 8.0 for Eu(3), 8.5 for Eu(2) and 9.0 for Eu(1). Inhibition studies show that Eu() binds strongly to the dianionic ligand methylphosphate (K(d) = 0.28 mM), and more weakly to diethylphosphate (K(d) = 7.5 mM), consistent with a catalytic role of the Eu(III) complexes in stabilizing the developing negative charge on the phosphorane transition state.
Excited-State Conformational/Electronic Responses of Saddle-Shaped N,N'-Disubstituted-Dihydrodibenzo[a,c]phenazines: Wide-Tuning Emission from Red to Deep Blue and White Light Combination.

PubMed

Zhang, Zhiyun; Wu, Yu-Sin; Tang, Kuo-Chun; Chen, Chi-Lin; Ho, Jr-Wei; Su, Jianhua; Tian, He; Chou, Pi-Tai

2015-07-08

A tailored strategy is utilized to modify 5,10-dimethylphenazine (DMP) to donor-acceptor type N,N'-disubstituted-dihydrodibenzo[a,c]phenazines. The representative compounds DMAC (N,N'-dimethyl), DPAC (N,N'-diphenyl), and FlPAC (N-phenyl-N'-fluorenyl) reveal significant nonplanar distortions (i.e., a saddle shape) and remarkably large Stokes-shifted emission independent of the solvent polarity. For DPAC and FlPAC with higher steric hindrance on the N,N'-substituents, normal Stokes-shifted emission also appears, for which the peak wavelength reveals solvent-polarity dependence. These unique photophysical behaviors are rationalized by electronic configuration coupled conformation changes en route to the geometry planarization in the excited state. This proposed mechanism is different from the symmetry rule imposed to explain the anomalously long-wavelength emission for DMP and is firmly supported by polarity-, viscosity-, and temperature-dependent steady-state and nanosecond time-resolved spectroscopy. Together with femtosecond early dynamics and computational simulation of the reaction energy surfaces, the results lead us to establish a sequential, three-step kinetics. Upon electronic excitation of N,N'-disubstituted-dihydrodibenzo[a,c]phenazines, intramolecular charge-transfer takes place, followed by the combination of polarization stabilization and skeletal motion toward the planarization, i.e., elongation of the π-delocalization over the benzo[a,c]phenazines moiety. Along the planarization, DPAC and FlPAC encounter steric hindrance raised by the N,N'-disubstitutes, resulting in a local minimum state, i.e., the intermediate. The combination of initial charge-transfer state, intermediate, and the final planarization state renders the full spectrum of interest and significance in their anomalous photophysics. Depending on rigidity, the N,N'-disubstituted-dihydrodibenzo[a,c]phenazines exhibit multiple emissions, which can be widely tuned from red to deep blue and
Comparison of exciplex generation under optical and X-ray excitation

NASA Astrophysics Data System (ADS)

Kipriyanov, A. A.; Melnikov, A. R.; Stass, D. V.; Doktorov, A. B.

2017-09-01

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

Comparison of exciplex generation under optical and X-ray excitation.

PubMed

Kipriyanov, A A; Melnikov, A R; Stass, D V; Doktorov, A B

2017-09-07

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.
Mechanistic insight into the enhanced photocatalytic activity of single-atom Pt, Pd or Au-embedded g-C3N4

NASA Astrophysics Data System (ADS)

Tong, Tong; Zhu, Bicheng; Jiang, Chuanjia; Cheng, Bei; Yu, Jiaguo

2018-03-01

Single atoms of platinum (Pt), palladium (Pd) or gold (Au) trapped by two-dimensional graphitic carbon nitride (g-C3N4) exhibit superior photocatalytic performance. However, the underlying mechanism of single-atom noble metal/g-C3N4 photocatalytic system is still unclear. Herein, the structural, electronic and optical properties of single-atom Pt, Pd and Au loaded on bilayer g-C3N4 (BL-g-C3N4) substrate were investigated by density functional theory (DFT) simulations. The results indicate that single-atom Pt/Pd/Au loading can significantly narrow the band gap of g-C3N4 and thus increase its light absorption in the visible-light region. Rather than being adsorbed on the surface, Pt and Pd atoms tend to be embedded into g-C3N4 interlayer and act as bridges to facilitate the interlayer charge carrier transfer due to the effects of conduction band offset. In particular, an internal electric field is generated in Pt/BL-g-C3N4, which is further beneficial for separating charge carrier of photoexcited g-C3N4. By contrast, Au can only be adsorbed on the g-C3N4 surface (in the six-fold cavity) and deliver a limited amount of charge carrier excited in the N-conjugated aromatic pore of g-C3N4 surface. Our finding is conducive to understanding the interactive relationship between single-atom noble metal co-catalysts and g-C3N4 and to the design of high-efficiency photocatalyst.
Selective vibrational excitation of the ethylene--fluorine reaction in a nitrogen matrix. II

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

Frei, H.

1983-07-15

The product branching between 1,2-difluoroethane and vinyl fluoride (plus HF) of the selective vibrationally stimulated reaction of molecular fluorine with C/sub 2/H/sub 4/ has been studied in a nitrogen matrix at 12 K and found to be the same for five different vibrational transitions of C/sub 2/H/sub 4/ between 1896 and 4209 cm/sup -1/. The HF/DF branching ratio of the reaction of F/sub 2/ with CH/sub 2/CD/sub 2/, trans-CHDCHD, and cis-CHDCHD was determined to be 1.1, independent of precursor C/sub 2/H/sub 2/D/sub 2/ isomer and particular mode which excited the reaction. These results, as well as the analysis of themore » mixtures of partially deuterated vinyl fluoride molecules produced by each C/sub 2/H/sub 2/D/sub 2/ isomer indicate that the product branching occurs by ..cap alpha beta.. elimination of HF(DF) from a vibrationally excited, electronic ground state 1,2-difluoroethane intermediate. Selective vibrational excitation of fluorine reactions in isotopically mixed matrices t-CHDCHD/C/sub 2/H/sub 4//F/sub 2//N/sub 2/ and CH/sub 2/CD/sub 2//C/sub 2/H/sub 4//F/sub 2//N/sub 2/, and in matrices C/sub 2/H/sub 2//C/sub 2/H/sub 4//F/sub 2//N/sub 2/ revealed a high degree of isotopic and molecular selectivity. The extent to which intermolecular energy transfer occurred is qualitatively explained in terms of dipole coupled vibrational energy transfer. A study of the loss of absorbance of the C/sub 2/H/sub 4/ x F/sub 2/ pairs in case of ..nu../sub 9/ as a function of both the laser irradiation frequency within the absorption profile, and the ethylene concentration showed that the C/sub 2/H/sub 4/ x F/sub 2/ absorption is inhomogeneously broadened. Substantial depletion of reactive pairs which did not absorb laser light is interpreted in terms of Forster transfer.« less
Effects of single bond-ion and single bond-diradical form on the stretching vibration of Cdbnd N bridging bond in 4,4‧-disubstituted benzylidene anilines

NASA Astrophysics Data System (ADS)

Cao, Chao-Tun; Bi, Yakun; Cao, Chenzhong

2016-06-01

Fifty-seven samples of model compounds, 4,4‧-disubstituted benzylidene anilines, p-X-ArCH = NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νCdbnd N of the Cdbnd N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νCdbnd N, that is there are mainly three modes in the stretching vibration of Cdbnd N bond: (I) polar double bond form Cdbnd N, (II) single bond-ion form C+-N- and (III) single bond-diradical form Crad -Nrad . The contributions of the forms (I) and (II) to the change of νCdbnd N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II).
Synthesis and functionalization of monodisperse near-ultraviolet and visible excitable multifunctional Eu3+, Bi3+:REVO4 nanophosphors for bioimaging and biosensing applications

NASA Astrophysics Data System (ADS)

Escudero, Alberto; Carrillo-Carrión, Carolina; Zyuzin, Mikhail V.; Ashraf, Sumaira; Hartmann, Raimo; Núñez, Nuria O.; Ocaña, Manuel; Parak, Wolfgang J.

2016-06-01

Near-ultraviolet and visible excitable Eu- and Bi-doped NPs based on rare earth vanadates (REVO4, RE = Y, Gd) have been synthesized by a facile route from appropriate RE precursors, europium and bismuth nitrate, and sodium orthovanadate, by homogeneous precipitation in an ethylene glycol/water mixture at 120 °C. The NPs can be functionalized either by a one-pot synthesis with polyacrylic acid (PAA) or by a Layer-by-Layer approach with poly(allylamine hydrochloride) (PAH) and PAA. In the first case, the particle size can also be tuned by adjusting the amount of PAA. The Eu- Bi-doped REVO4 based nanophosphors show the typical red luminescence of Eu(iii), which can be excited through an energy transfer process from the vanadate anions, resulting in a much higher luminescence intensity in comparison to the direct excitation of the europium cations. The incorporation of Bi into the REVO4 structure shifts the original absorption band of the vanadate anions towards longer wavelengths, giving rise to nanophosphors with an excitation maximum at 342 nm, which can also be excited in the visible range. The suitability of such nanophosphors for bioimaging and biosensing applications, as well as their colloidal stability in different buffer media of biological interest, their cytotoxicity, their degradability at low pH, and their uptake by HeLa cells have been evaluated. Their suitability for bioimaging and biosensing applications is also demonstrated.Near-ultraviolet and visible excitable Eu- and Bi-doped NPs based on rare earth vanadates (REVO4, RE = Y, Gd) have been synthesized by a facile route from appropriate RE precursors, europium and bismuth nitrate, and sodium orthovanadate, by homogeneous precipitation in an ethylene glycol/water mixture at 120 °C. The NPs can be functionalized either by a one-pot synthesis with polyacrylic acid (PAA) or by a Layer-by-Layer approach with poly(allylamine hydrochloride) (PAH) and PAA. In the first case, the particle size can also be
/B(E2) values from low-energy Coulomb excitation at an ISOL facility: the /N=80,82 Te isotopes

NASA Astrophysics Data System (ADS)

Barton, C. J.; Caprio, M. A.; Shapira, D.; Zamfir, N. V.; Brenner, D. S.; Gill, R. L.; Lewis, T. A.; Cooper, J. R.; Casten, R. F.; Beausang, C. W.; Krücken, R.; Novak, J. R.

2003-01-01

B(E2;0+1→2+1) values for the unstable, neutron-rich nuclei 132,134Te were determined through Coulomb excitation, in inverse kinematics, of accelerated beams of these nuclei. The systematics of measured B(E2) values from the ground state to the first excited state have been extended to the N=82 shell closure in the Te nuclei and have been compared with the predictions of different theories. The measurements were performed at the Holifield Radioactive Ion Beam Facility (HRIBF) using the GRAFIK detector. The success of this approach, which couples a 5.7% efficient through-well NaI(Tl) γ-ray detector with thin foil microchannel plate beam detectors, also demonstrates the feasibility for Coulomb excitation studies of neutron-rich nuclei even further from the valley of beta stability, both at present-generation ISOL facilities and at the proposed Rare Isotope Accelerator.
Spectroscopy and excitation dynamics of the trivalent lanthanides Tm(3+) and Ho(3+) in LiYF4

NASA Technical Reports Server (NTRS)

Walsh, Brian M.

1995-01-01

A detailed study of the spectroscopy and excitation dynamics Tm3+ and Ho3+ in yttrium lithium fluoride, LiYF4 (YLF), has been done. Absorption spectroscopy is utilized in the Judd-Ofelt theory to determine radiative transition rates of spontaneous emission. Luminescence spectroscopy is studied under cw diode laser excitation at 785nm. The effect of dopant ion concentration and excitation power on the observed luminescence are considered in these measurements. An analysis of these measurements have been used to determine channels of energy transfer between Tm3+ and Ho3+ ions. The temporal response of Tm and Ho in singly and co-doped YLF to pulsed laser excitation with a Ti:Al2O3 laser and a CoMgF2 laser turned to various wavelengths have also been studied. The energy transfer mechanisms of cross relaxation, upconversion, and resonant energy transfer between Tm3+ and Ho3+ ions have been modeled, and the model parameters extracted by a fitting procedure to the measured temporal response curves. Rate equation approaches to modeling are presented that result in predictions of rate constants for energy transfer processes, as well as more conventional approaches to modeling such as the Forster-Dexter models, which give the interaction strengths in terms of microscopic interaction parameters.
Determination of 2p Excitation Transfer Rate Coefficient in Neon Gas Discharges

NASA Astrophysics Data System (ADS)

Smith, D. J.; Stewart, R. S.

2001-10-01

We will discuss our theoretical modelling and application of an array of four complementary optical diagnostic techniques for low-temperature plasmas. These are cw laser collisionally-induced fluorescence (LCIF), cw optogalvanic effect (OGE), optical emission spectroscopy (OES) and optical absorption spectroscopy (OAS). We will briefly present an overview of our investigation of neon positive column plasmas for reduced axial electric fields ranging from 3x10-17 Vcm2 to 2x10-16 Vcm2 (3-20 Td), detailing our determination of five sets of important collisional rate coefficients involving the fifteen lowest levels, the 1S0 ground state and the 1s and 2p excited states (in Paschen notation), hence information on several energy regions of the electron distribution function (EDF). The discussion will be extended to show the new results obtained from analysis of the argon positive column over similar reduced fields. Future work includes application of our multi-diagnostic technique to more complex systems, including the addition of molecules for EDF determination. array of four complementary optical diagnostic techniques N7nWOhL9t3lRINw/abstract/ 0022-3727/33/7/318>OGE LCIF determination of five sets of important collisional rate coefficients
Electronic excited states and relaxation dynamics in polymer heterojunction systems

NASA Astrophysics Data System (ADS)

Ramon, John Glenn Santos

, we examine the effect of the nanoscale interfacial morphology and solvation on the electronic excited states of TFB/F8BT. Here, we employ time-dependent density functional theory (TD-DFT) to investigate the relevant excited states of two stacking configurations. We show that the calculated states agree with the excited states responsible for the experimentally observed emission peaks and that these states are blue shifted relative to those of the isolated chain. Furthermore, slight lateral shifts in the stacking orientation not only shift the excited state energies; more importantly, they alter the nature of these states altogether. Lastly, we see that solvation greatly stabilizes the charge-transfer states.
Nlgn4 knockout induces network hypo-excitability in juvenile mouse somatosensory cortex in vitro.

PubMed

Delattre, V; La Mendola, D; Meystre, J; Markram, H; Markram, K

2013-10-09

Neuroligins (Nlgns) are postsynaptic cell adhesion molecules that form transynaptic complexes with presynaptic neurexins and regulate synapse maturation and plasticity. We studied the impact of the loss of Nlgn4 on the excitatory and inhibitory circuits in somatosensory cortical slices of juvenile mice by electrically stimulating these circuits using a multi-electrode array and recording the synaptic input to single neurons using the patch-clamp technique. We detected a decreased network response to stimulation in both excitatory and inhibitory circuits of Nlgn4 knock-out animals as compared to wild-type controls, and a decreased excitation-inhibition ratio. These data indicate that Nlgn4 is involved in the regulation of excitatory and inhibitory circuits and contributes to a balanced circuit response to stimulation.
Nonlinear Analysis of Mechanical Systems Under Combined Harmonic and Stochastic Excitation

DTIC Science & Technology

1993-05-27

Namachchivaya and Naresh Malhotra Department of Aeronautical and Astronautical Engineering University of Illinois, Urbana-Champaign Urbana, Illinois...Aeronauticai and Astronautical Engineering, University of Illinois, 1991. 2. N. Sri Namachchivaya and N. Malhotra , Parametrically Excited Hopf Bifurcation...Namachchivaya and N. Malhotra , Parametrically Excited Hopf Bifurcation with Non-semisimple 1:1 Resonance, Nonlinear Vibrations, ASME-AMD, Vol. 114, 1992. 3
Determination of the Best Ground Penetrating Radar Source Signal Type for the Accurate Location of Underground Utilities

DTIC Science & Technology

1988-09-01

si2sna- loss was hige tra-e-: td A.R concluded that the- a~oroxim-at _’ns u-sed in heanalytical model may h-ave intrcou,_ce,, scom.e error :nothe...amplitudes f-om the Phase 2 measurements were in general significant1y 104 co cl -\\ Lnf C~’j tD .0n 1 -O21 w -- -L a u4 oCLa - I N -4 - n -7 c -4 > V) r...responses of the same device are uispla~ td . Tie Fr-equiency Domain refie~tion measuremient is a composite iesponise of* all of’ the discontinuities
Microcomputer Based Ship-Board Gun Control System.

DTIC Science & Technology

1981-03-01

to0 CD 04 5. 6D3. bi t0 U3 3 3. A - a U3 vi4 . * ~ ~ ~ 1 z.. n . 0 4 OR *4 AnS 94 C.) 0 3 * 04 td ) . cu 4. P* 0r * 3 6* 04 to 0 f 3. 4 6-4 "a I c *0...0I td ..M U o -Oq I Z ) OM Pm , N ou POO 0 -4 I h 4 * W33 SVil lot I 4- ad2 13 41 *f 0 44 ac ci 0 IH 4n 0= U 04 o3 0, 3a V). cav% n oft af 44 0 A4A... td ) -zl- ~ 6N 0 l 4 44L CdP 9 ~CI (n l 4 t3 0. .4 vi~ n - 4 U :A -. c 14 w i cn v - V", v- C) 4A " =- " cL c. Ni 0.4 (n Z m a -I 11) Cd E4 r a. a
Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions.

PubMed

Yamada, Michio; Slanina, Zdenek; Mizorogi, Naomi; Muranaka, Atsuya; Maeda, Yutaka; Nagase, Shigeru; Akasaka, Takeshi; Kobayashi, Nagao

2013-03-14

We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C(2v)-C(82), La(2)@I(h)-C(80), and Sc(3)N@I(h)-C(80) can be assigned using these techniques. Particularly, a difference in the electronic transitions between La(2)@I(h)-C(80) and Sc(3)N@I(h)-C(80), which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La(2)@I(h)-C(80) were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La(2)@I(h)-C(80), although no marked difference exists in their absorption spectra.
Alpha List of Prime Contract Awards. Oct 92-Sep 93. FY93. (Bt North America Inc. - Classified Location Domestic)

DTIC Science & Technology

1994-03-01

V4,(41, Or,.in cri nN c >1r- 0 10 f tao oinon0 40 M-4 -4 td n -w toce, of IC 𔃺 0 ca I1-&n UO0 - qtY(DC -04N I- . 30 C S-i Ur’L) . L-M4 U -4~ C...d 0o II Nca( 0 CI400W000 CD 10) Ny It 4. ev MNN.P.P rn If CIL I co00t I’l -4 co0 00000 -00 0 00C) 0 CV 4.4 Me V DCo tD H11 10 004D11 Nm Oin 000000...CO -4 0 11 -2c z .- Z 11 1 CO 0 fm 11 C z 2c z ed C z zx If I ca a 00 11 1- ed tv (d I td III 11 1 00000 11 00-t .- !`ý- W M It r- Ln Ln 0 tma N -4 -4
Theory of spin-conserving excitation of the N-V(-) center in diamond.

PubMed

Gali, Adam; Janzén, Erik; Deák, Péter; Kresse, Georg; Kaxiras, Efthimios

2009-10-30

The negatively charged nitrogen-vacancy defect in diamond is an important atomic-scale structure that can be used as a qubit in quantum computing and as a marker in biomedical applications. Its usefulness relies on the ability to optically excite electrons between well-defined gap states, which requires a clear and detailed understanding of the relevant states and excitation processes. Here we show that by using hybrid density-functional-theory calculations in a large supercell we can reproduce the zero-phonon line and the Stokes and anti-Stokes shifts, yielding a complete picture of the spin-conserving excitation of this defect.
Communication: Time-dependent optimized coupled-cluster method for multielectron dynamics

NASA Astrophysics Data System (ADS)

Sato, Takeshi; Pathak, Himadri; Orimo, Yuki; Ishikawa, Kenichi L.

2018-02-01

Time-dependent coupled-cluster method with time-varying orbital functions, called time-dependent optimized coupled-cluster (TD-OCC) method, is formulated for multielectron dynamics in an intense laser field. We have successfully derived the equations of motion for CC amplitudes and orthonormal orbital functions based on the real action functional, and implemented the method including double excitations (TD-OCCD) and double and triple excitations (TD-OCCDT) within the optimized active orbitals. The present method is size extensive and gauge invariant, a polynomial cost-scaling alternative to the time-dependent multiconfiguration self-consistent-field method. The first application of the TD-OCC method of intense-laser driven correlated electron dynamics in Ar atom is reported.
Communication: Time-dependent optimized coupled-cluster method for multielectron dynamics.

PubMed

Sato, Takeshi; Pathak, Himadri; Orimo, Yuki; Ishikawa, Kenichi L

2018-02-07

Time-dependent coupled-cluster method with time-varying orbital functions, called time-dependent optimized coupled-cluster (TD-OCC) method, is formulated for multielectron dynamics in an intense laser field. We have successfully derived the equations of motion for CC amplitudes and orthonormal orbital functions based on the real action functional, and implemented the method including double excitations (TD-OCCD) and double and triple excitations (TD-OCCDT) within the optimized active orbitals. The present method is size extensive and gauge invariant, a polynomial cost-scaling alternative to the time-dependent multiconfiguration self-consistent-field method. The first application of the TD-OCC method of intense-laser driven correlated electron dynamics in Ar atom is reported.
Drainage and tillage practices in the winter fallow season mitigate CH4 and N2O emissions from a double-rice field in China

NASA Astrophysics Data System (ADS)

Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Yang, Yuting; Ma, Jing; Xu, Hua

2016-09-01

Traditional land management (no tillage, no drainage, NTND) during the winter fallow season results in substantial CH4 and N2O emissions from double-rice fields in China. A field experiment was conducted to investigate the effects of drainage and tillage during the winter fallow season on CH4 and N2O emissions and to develop mitigation options. The experiment had four treatments: NTND, NTD (drainage but no tillage), TND (tillage but no drainage), and TD (both drainage and tillage). The study was conducted from 2010 to 2014 in a Chinese double-rice field. During winter, total precipitation and mean daily temperature significantly affected CH4 emission. Compared to NTND, drainage and tillage decreased annual CH4 emissions in early- and late-rice seasons by 54 and 33 kg CH4 ha-1 yr-1, respectively. Drainage and tillage increased N2O emissions in the winter fallow season but reduced it in early- and late-rice seasons, resulting in no annual change in N2O emission. Global warming potentials of CH4 and N2O emissions were decreased by 1.49 and 0.92 t CO2 eq. ha-1 yr-1, respectively, and were reduced more by combining drainage with tillage, providing a mitigation potential of 1.96 t CO2 eq. ha-1 yr-1. A low total C content and high C / N ratio in rice residues showed that tillage in the winter fallow season reduced CH4 and N2O emissions in both early- and late-rice seasons. Drainage and tillage significantly decreased the abundance of methanogens in paddy soil, and this may explain the decrease of CH4 emissions. Greenhouse gas intensity was significantly decreased by drainage and tillage separately, and the reduction was greater by combining drainage with tillage, resulting in a reduction of 0.17 t CO2 eq. t-1. The results indicate that drainage combined with tillage during the winter fallow season is an effective strategy for mitigating greenhouse gas releases from double-rice fields.
Characterization of a Unique Cell Population Marked by Transgene Expression in the Adult Cochlea of Nestin-CreERT2/tdTomato-Reporter Mice

PubMed Central

Chow, Cynthia L.; Guo, Weixiang; Trivedi, Parul; Zhao, Xinyu; Gubbels, Samuel P.

2015-01-01

Hair cells in the adult mammalian cochlea cannot spontaneously regenerate after damage resulting in the permanency of hearing loss. Stem cells have been found to be present in the cochlea of young rodents; however, there has been little evidence for their existence into adulthood. We used nestin-CreERT2/tdTomato-reporter mice to trace the lineage of putative nestin-expressing cells and their progeny in the cochleae of adult mice. Nestin, an intermediate filament found in neural progenitor cells during early development and adulthood, is regarded as a multi-potent and neural stem cell marker. Other investigators have reported its presence in postnatal and young adult rodents; however, there are discrepancies amongst these reports. Using lineage tracing, we documented a robust population of tdTomato-expressing cells and evaluated these cells at a series of adult time points. Upon activation of the nestin promoter, tdTomato was observed just below and medial to the inner hair cell layer. All cells co-localized with the stem cell and cochlear-supporting-cell marker Sox2 as well as the supporting cell and Schwann cell marker Sox10; however, they did not co-localize with the Schwann cell marker Krox20, spiral ganglion marker NF200, or GFAP-expressing supporting cell marker. The cellular identity of this unique population of tdTomato-expressing cells in the adult cochlea of nestin-CreERT2/tdTomato mice remains unclear however these cells may represent a type of supporting cell on the neural aspect of the inner hair cell layer. PMID:25611038

Bottom-up substitution assembly of AuF4-n0,-+nPO3 (n = 1-4): a theoretical study of novel oxyfluoride hyperhalogen molecules and anions AuF4-n(PO3)n0,-

NASA Astrophysics Data System (ADS)

Yang, Yi-fan; Cui, Zhong-hua; Ding, Yi-hong

2014-06-01

Compounds with high electron affinity, i.e. superhalogens, have continued to attract chemists' attention, due to their potential importance in fundamental chemistry and materials science. It has now proven very effective to build up novel superhalogens with multi-positively charged centres, which are usually called 'hyperhalogens'. Herein, using AuF4- and PO3 as the model building blocks, we made the first attempt to design the Au,P-based hyperhalogen anions AuF4-n(PO3)n- (n = 1-4) at the B3LYP/6-311+G(d)&SDD and CCSD(T)/6-311+G(d)&SDD (single-point) levels (6-311+G(d) for O, F, P and SDD for Au). Notably, for all the considered Au,P systems, the ground state bears a dioxo-bonded structure with n ≤ 3, which is significantly more stable than the usually presumed mono-oxo-bonded one. Moreover, the clustering of the -PO3 moieties becomes energetically favoured for n ≥ 3. The ground states of AuP4O120,- are the first reported cage-like oxide hyperhalogens. Thus, the -PO3 moiety cannot be retained during the 'bottom-up' assembly. The vertical detachment energy (VDE) value of the most stable AuF4-n(PO3)n- (n = 1-4) ranges from 7.16 to 8.20 eV, higher than the VDE values of the corresponding building blocks AuF4- (7.08 eV) and PO3- (4.69 eV). The adiabatic detachment energy values of these four hyperhalogens exceed 6.00 eV. Possible generation routes for AuF4-n(PO3)n- (n = 1-4) were discussed. The presently designed oxyfluorides not only enriches the family of hyperhalogens, but also demonstrates the great importance of considering the structural transformation during the superhalogen → hyperhalogen design such as for the present Au-P based systems.
Bathymetric Atlas of the Northcentral Pacific Ocean,

DTIC Science & Technology

1971-03-01

tD - fn O ) .4p coo 10~~ ob, o o -o 10- (0 00" 0% n ... .... x~ T’ CD ZD v aq *V)~ C’ 0O’ 0~ II tD C A 0 CD 7 -0 (CD 00., J...1I 2 I ~ N- * * * - I I I ~ I ci It * 2 At - ~* 0 I -1 o 0~ .................................... N- ’~ .~ __ 0 0 0 0 0 9 90 N - 0 - N 90 0 tD t4 C>C...9 . N- (D if) oo - - ’T~ / 0 7 ~ I ~’ ~.- -~ - j,~l ~ dz (0 I -d 2 09 ~-~-~--~ N -~ ~ JAJ 0 * (0 N ~ 0 -1 (0~ 0 𔃼~ ~q )A
Electron Excitation of High Dipole Moment Molecules

NASA Astrophysics Data System (ADS)

Goldsmith, Paul; Kauffmann, Jens

2018-01-01

Emission from high-dipole moment molecules such as HCN allows determination of the density in molecular clouds, and is often considered to trace the “dense” gas available for star formation. We assess the importance of electron excitation in various environments. The ratio of the rate coefficients for electrons and H2 molecules, ~10^5 for HCN, yields the requirements for electron excitation to be of practical importance if n(H2) < 10^{5.5} /cm3 and X(e-) > 10^{-5}, where the numerical factors reflect critical values n_c(H2) and X^*(e-). This indicates that in regions where a large fraction of carbon is ionized, X(e-) will be large enough to make electron excitation significant. The situation is in general similar for other “high density tracers”, including HCO+, CN, and CS. But there are significant differences in the critical electron fractional abundance, X^*(e-), defined by the value required for equal effect from collisions with H2 and e-. Electron excitation is, for example, unimportant for CO and C+. Electron excitation may be responsible for the surprisingly large spatial extent of the emission from dense gas tracers in some molecular clouds (Pety et al. 2017, Kauffmann, Goldsmith et al. 2017, A&A, submitted). The enhanced estimates for HCN abundances and HCN/CO and HCN/HCO+ ratios observed in the nuclear regions of luminous galaxies may be in part a result of electron excitation of high dipole moment tracers. The importance of electron excitation will depend on detailed models of the chemistry, which may well be non-steady state and non--static.
Hot corrosion of four superalloys - HA-188, S-57, IN-617, and TD-NiCrAl

NASA Technical Reports Server (NTRS)

Santoro, G. J.

1979-01-01

Cyclic oxidation and hot corrosion tests of two cobalt-base and two nickel-base alloys are reported. The alloys were exposed to maximum temperatures of 900 and 1000 C in a Mach 0.3 burner rig whose flame was doped with various concentrations of sea salt and sodium sulfate for hot corrosion tests. The test data were subjected to a regression analysis for the development of model equations relating corrosion to temperature and for the effects of salt concentration and composition on corrosion. The corrosion resistance varied with temperature, sea salt concentration, and salt composition, concluding that the S-57 cobalt-base alloy was the most hot corrosion-resistant alloy, and the TD-NiCrAl nickel-base alloy was the least resistant. However, under straight oxidation conditions, the TD-NiCrAl was most resistant, while S-57 was the least resistant alloy.
A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule

NASA Astrophysics Data System (ADS)

Egidi, Franco; Segado, Mireia; Koch, Henrik; Cappelli, Chiara; Barone, Vincenzo

2014-12-01

In this work, we report a comparative study of computed excitation energies, oscillator strengths, and excited-state energy gradients of (S)-nicotine, chosen as a test case, using multireference methods, coupled cluster singles and doubles, and methods based on time-dependent density functional theory. This system was chosen because its apparent simplicity hides a complex electronic structure, as several different types of valence excitations are possible, including n-π*, π-π*, and charge-transfer states, and in order to simulate its spectrum it is necessary to describe all of them consistently well by the chosen method.
A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule

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

Egidi, Franco, E-mail: franco.egidi@sns.it; Segado, Mireia; Barone, Vincenzo, E-mail: vincenzo.barone@sns.it

In this work, we report a comparative study of computed excitation energies, oscillator strengths, and excited-state energy gradients of (S)-nicotine, chosen as a test case, using multireference methods, coupled cluster singles and doubles, and methods based on time-dependent density functional theory. This system was chosen because its apparent simplicity hides a complex electronic structure, as several different types of valence excitations are possible, including n-π{sup *}, π-π{sup *}, and charge-transfer states, and in order to simulate its spectrum it is necessary to describe all of them consistently well by the chosen method.
Calculations of Excitation Functions of Some Structural Fusion Materials for ( n, t) Reactions up to 50 MeV Energy

NASA Astrophysics Data System (ADS)

Tel, E.; Durgu, C.; Aktı, N. N.; Okuducu, Ş.

2010-06-01

Fusion serves an inexhaustible energy for humankind. Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, the working out the systematics of ( n, t) reaction cross sections is of great importance for the definition of the excitation function character for the given reaction taking place on various nuclei at different energies. In this study, ( n, t) reactions for some structural fusion materials such as 27Al, 51V, 52Cr, 55Mn, and 56Fe have been investigated. The new calculations on the excitation functions of 27Al( n, t)25Mg, 51V( n, t)49Ti, 52Cr( n, t)50V, 55Mn( n, t)53Cr and 56Fe( n, t)54Mn reactions have been carried out up to 50 MeV incident neutron energy. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve the new evaluated the geometry dependent hybrid model, hybrid model and the cascade exciton model. Equilibrium effects are calculated according to the Weisskopf-Ewing model. Also in the present work, we have calculated ( n, t) reaction cross-sections by using new evaluated semi-empirical formulas developed by Tel et al. at 14-15 MeV energy. The calculated results are discussed and compared with the experimental data taken from the literature.
Evaluating excited state atomic polarizabilities of chromophores† †Electronic supplementary information (ESI) available: Basis set dependence, definition of bond charges, Romberg differentiation, python script to calculate atomic polarizabilities, influence of the cavity radius, atomic polarizabilities of coumarin 153, all tables in atomic units. See DOI: 10.1039/c7cp08549d

PubMed Central

Heid, Esther

2018-01-01

Ground and excited state dipoles and polarizabilities of the chromophores N-methyl-6-oxyquinolinium betaine (MQ) and coumarin 153 (C153) in solution have been evaluated using time-dependent density functional theory (TD-DFT). A method for determining the atomic polarizabilities has been developed; the molecular dipole has been decomposed into atomic charge transfer and polarizability terms, and variation in the presence of an electric field has been used to evaluate atomic polarizabilities. On excitation, MQ undergoes very site-specific changes in polarizability while C153 shows significantly less variation. We also conclude that MQ cannot be adequately described by standard atomic polarizabilities based on atomic number and hybridization state. Changes in the molecular polarizability of MQ (on excitation) are not representative of the local site-specific changes in atomic polarizability, thus the overall molecular polarizability ratio does not provide a good approximation for local atom-specific polarizability changes on excitation. Accurate excited state force fields are needed for computer simulation of solvation dynamics. The chromophores considered in this study are often used as molecular probes. The methods and data reported here can be used for the construction of polarizable ground and excited state force fields. Atomic and molecular polarizabilities (ground and excited states) have been evaluated over a range of functionals and basis sets. Different mechanisms for including solvation effects have been examined; using a polarizable continuum model, explicit solvation and via sampling of clusters extracted from a MD simulation. A range of different solvents have also been considered. PMID:29542743
40 CFR 721.285 - Acetamide, N-[4-(pentyloxy)phenyl]-, acetamide, N-[2-nitro-4-(pentyloxy)phenyl]-, and acetamide...

Code of Federal Regulations, 2010 CFR

2010-07-01

... § 721.90 (a)(4), (b)(4), and (c)(4) (where N = 90 ppb for PMNs P-92-31 and P-92-32, and N = 30 ppb for P... reporting. (1) The chemical substances identified as acetamide, N-[4-(pentyloxy)phenyl]- (PMN P-92-31), acetamide, N-[2-nitro-4-(pentyloxy)phenyl]- (PMN P-92-32), and acetamide, N-[2-amino-4-(pentyloxy)phenyl...
40 CFR 721.285 - Acetamide, N-[4-(pentyloxy)phenyl]-, acetamide, N-[2-nitro-4-(pentyloxy)phenyl]-, and acetamide...

Code of Federal Regulations, 2011 CFR

2011-07-01

... § 721.90 (a)(4), (b)(4), and (c)(4) (where N = 90 ppb for PMNs P-92-31 and P-92-32, and N = 30 ppb for P... reporting. (1) The chemical substances identified as acetamide, N-[4-(pentyloxy)phenyl]- (PMN P-92-31), acetamide, N-[2-nitro-4-(pentyloxy)phenyl]- (PMN P-92-32), and acetamide, N-[2-amino-4-(pentyloxy)phenyl...
Dollar Summary of Prime Contract Awards by Contractor, State or Country, and Place. Part 5 (Matthew Electric Supply Co-Quantum Research Inc

DTIC Science & Technology

1990-01-01

t4Ie~ r-)6 f- 016240 C c 6-) 0. N. ’)M 40 0 - < qt U..6 ON’)t V- Mw iS.m MM m M w N M v v n I 6- 06.- I wI td -. -N 6 ma toC’ (G. 0- 0g 00 Z-6- o...Into 064 - WI ’a OW)C’IC 00 CO 0 (0( 0- > ’ 0 4 0 td 00 6 4 00 0-4 0 N-N0 0-L) 6-46 4Z ,L- V6 U. 4 I I- 06 so6 00 00 M0 a( 00 E 6-4~1 >- I-- (0- ow...0L L. 0eC) - ) ~ U 0 1- 09 0) .- 4 N (C-0 U) m<t~ (3 4 ans U 06 LL. c I 4 -4 C’). -4 00- 4a 0L to I.L 4 C - w Co- LL a) C 0 > 4 5r~ 5 >O td - - .. >Ci
Hot N2 in Titan's upper atmosphere

NASA Astrophysics Data System (ADS)

Lavvas, P.; Yelle, R. V.; Heays, A.; Campbell, L.; Brunger, M. J.; Galand, M.; Vuitton, V.

2015-10-01

We present a detailed model for the vibrational population of all non pre-dissociating excited electronic states of N2, as well as for the ground and ionic states,in Titan's atmosphere. Our model includes the detailed energy deposition calculations presented in the past [1] as well as the more recent developments in the high resolution N2 photo-absorption cross sections that allow us to calculate photo-excitation rates for different vibrational levels of singlet nitrogen states, and provide information for their pre-dissociation yields.In addition, we consider the effect of collisions and chemical reactions in the population of the different states. Our results demonstrate that a significant population of vibrationally excited ground state N2 survives in Titan's upper atmosphere. This hot N2population can improve the agreement between models and observations for the emission of the c'4 state that is significantly affected by resonant scattering. Moreover we discuss the potential implications of the vibrationally excited population on the ionospheric densities.
Crystal structure of di-μ-chlorido-bis-(chlorido-{N1,N1-diethyl-N4-[(pyridin-2-yl-κN)methyl-idene]benzene-1,4-di-amine-κN4}mercury(II)).

PubMed

Faizi, Md Serajul Haque; Dege, Necmi; Goleva, Kateryna

2017-06-01

The title dinuclear mercury(II) complex, [Hg 2 Cl 4 (C 16 H 19 N 3 ) 2 ], synthesized from the pyridine-derived Schiff base ( E )- N 1 , N 1 -diethyl- N 4 -[(pyridin-2-yl)methyl-idene]benzene-1,4-di-amine (DPMBD), has inversion symmetry. The five-coordinated Hg II atoms have distorted square-pyramidal stereochemistry comprising two N-atom donors from bidentate chelate BPMBD ligands and three Cl-atom donors, two bridging and one monodentate. The dihedral angle between the benzene and the pyridine rings in the BPMBD ligand is 7.55 (4)°. In the crystal, the dinuclear mol-ecules are linked by weak C-H⋯Cl hydrogen bonds, forming zigzag ribbons lying parallel to [001]. Also present in the structure are π-π inter-actions between benzene and pyridine rings [minimum ring-centroid separation = 3.698 (8) Å].
Systematic study of fission barriers of excited superheavy nuclei

NASA Astrophysics Data System (ADS)

Sheikh, J. A.; Nazarewicz, W.; Pei, J. C.

2009-07-01

A systematic study of fission-barrier dependence on excitation energy has been performed using the self-consistent finite-temperature Hartree-Fock + BCS (FT-HF + BCS) formalism with the SkM* Skyrme energy density functional. The calculations have been carried out for even-even superheavy nuclei with Z ranging between 110 and 124. For an accurate description of fission pathways, the effects of triaxial and reflection-asymmetric degrees of freedom have been fully incorporated. Our survey demonstrates that the dependence of isentropic fission barriers on excitation energy changes rapidly with particle number, pointing to the importance of shell effects even at large excitation energies characteristic of compound nuclei. The fastest decrease of fission barriers with excitation energy is predicted for deformed nuclei around N=164 and spherical nuclei around N=184 that are strongly stabilized by ground-state shell effects. For the nuclei Pu240 and Fm256, which exhibit asymmetric spontaneous fission, our calculations predict a transition to symmetric fission at high excitation energies owing to the thermal quenching of static reflection asymmetric deformations.
Tuning optical properties of magic number cluster (SiO2)4O2H4 by substitutional bonding with gold atoms.

PubMed

Cai, Xiulong; Zhang, Peng; Ma, Liuxue; Zhang, Wenxian; Ning, Xijing; Zhao, Li; Zhuang, Jun

2009-04-30

By bonding gold atoms to the magic number cluster (SiO(2))(4)O(2)H(4), two groups of Au-adsorbed shell-like clusters Au(n)(SiO(2))(4)O(2)H(4-n) (n = 1-4) and Au(n)(SiO(2))(4)O(2) (n = 5-8) were obtained, and their spectral properties were studied. The ground-state structures of these clusters were optimized by density functional theory, and the results show that in despite of the different numbers and types of the adsorbed Au atoms, the cluster core (SiO(2))(4)O(2) of T(d) point-group symmetry keeps almost unchanged. The absorption spectra were obtained by time-dependent density functional theory. From one group to the other, an extension of absorption wavelength from the UV-visible to the NIR region was observed, and in each group the absorption strengths vary linearly with the number of Au atoms. These features indicate their advantages for exploring novel materials with easily controlled tunable optical properties. Furthermore, due to the weak electronic charge transfer between the Au atoms, the clusters containing Au(2) dimers, especially Au(8)(SiO(2))(4)O(2), absorb strongly NIR light at 900 approximately 1200 nm. Such strong absorption suggests potential applications of these shell-like clusters in tumor cells thermal therapy, like the gold-coated silica nanoshells with larger sizes.
Synthesis and functionalization of monodisperse near-ultraviolet and visible excitable multifunctional Eu(3+), Bi(3+):REVO4 nanophosphors for bioimaging and biosensing applications.

PubMed

Escudero, Alberto; Carrillo-Carrión, Carolina; Zyuzin, Mikhail V; Ashraf, Sumaira; Hartmann, Raimo; Núñez, Nuria O; Ocaña, Manuel; Parak, Wolfgang J

2016-06-16

Near-ultraviolet and visible excitable Eu- and Bi-doped NPs based on rare earth vanadates (REVO4, RE = Y, Gd) have been synthesized by a facile route from appropriate RE precursors, europium and bismuth nitrate, and sodium orthovanadate, by homogeneous precipitation in an ethylene glycol/water mixture at 120 °C. The NPs can be functionalized either by a one-pot synthesis with polyacrylic acid (PAA) or by a Layer-by-Layer approach with poly(allylamine hydrochloride) (PAH) and PAA. In the first case, the particle size can also be tuned by adjusting the amount of PAA. The Eu- Bi-doped REVO4 based nanophosphors show the typical red luminescence of Eu(iii), which can be excited through an energy transfer process from the vanadate anions, resulting in a much higher luminescence intensity in comparison to the direct excitation of the europium cations. The incorporation of Bi into the REVO4 structure shifts the original absorption band of the vanadate anions towards longer wavelengths, giving rise to nanophosphors with an excitation maximum at 342 nm, which can also be excited in the visible range. The suitability of such nanophosphors for bioimaging and biosensing applications, as well as their colloidal stability in different buffer media of biological interest, their cytotoxicity, their degradability at low pH, and their uptake by HeLa cells have been evaluated. Their suitability for bioimaging and biosensing applications is also demonstrated.
Crystal structures of 4-meth-oxy-N-(4-methyl-phenyl)benzene-sulfonamide and N-(4-fluoro-phenyl)-4-meth-oxy-benzene-sulfonamide.

PubMed

Rodrigues, Vinola Z; Preema, C P; Naveen, S; Lokanath, N K; Suchetan, P A

2015-11-01

Crystal structures of two N-(ar-yl)aryl-sulfonamides, namely, 4-meth-oxy-N-(4-methyl-phen-yl)benzene-sulfonamide, C14H15NO3S, (I), and N-(4-fluoro-phen-yl)-4-meth-oxy-benzene-sulfonamide, C13H12FNO3S, (II), were determined and analyzed. In (I), the benzene-sulfonamide ring is disordered over two orientations, in a 0.516 (7):0.484 (7) ratio, which are inclined to each other at 28.0 (1)°. In (I), the major component of the sulfonyl benzene ring and the aniline ring form a dihedral angle of 63.36 (19)°, while in (II), the planes of the two benzene rings form a dihedral angle of 44.26 (13)°. In the crystal structure of (I), N-H⋯O hydrogen bonds form infinite C(4) chains extended in [010], and inter-molecular C-H⋯πar-yl inter-actions link these chains into layers parallel to the ab plane. The crystal structure of (II) features N-H⋯O hydrogen bonds forming infinite one dimensional C(4) chains along [001]. Further, a pair of C-H⋯O inter-molecular inter-actions consolidate the crystal packing of (II) into a three-dimensional supra-molecular architecture.
Dollar Summary of Prime Contract Awards over $25,000 by Contractor, State or Country, and Place. Part 1 (102 Construction Inc, Oklahoma City, Oklahoma -- Bay Cities Refuse Co, Sunnyvale AFS, California), FY1991

DTIC Science & Technology

1991-01-01

L I-m 0d 0 td 4 10.1-4 4L o ) 0-40 # 2 I XI i( iC c u :W ( W .1 1- Ie ix W0- cc -4- (00 0 0-0 CO I E 00N0 00((0 UU) 0 0 0 3 00 o *zz a txa...43 td 00 0N -4 t - ) CZ IS WI - IL < (M I. 1.- (0 (0 z -- 0 0N f 1 Ii Iu -4 --4z L 0 I CI D- = 0- x I- c ow ( I- I I e 0 I.I. w 0 1Q4 0 0- I0.- C )C...LU 05 01t- 0 00 -4-4 o~c cc I- I c P:M 0 4e 1 C1 cl-4 -4 44 N I c 00 td E(0 c0 10 00 w 4 4- N N < 4-0 -4-4 - 0 c I 44 - 9 -I M IA- I 00 E >I (,C. 14
Second-Nearest-Neighbor Effects upon N NMR Shieldings in Models for Solid Si 3N 4and C 3N 4

NASA Astrophysics Data System (ADS)

Tossell, J. A.

1997-07-01

NMR shifts are generally determined mainly by the nearest-neighbor environment of an atom, with fairly small changes in the shift arising from differences in the second-nearest-neighbor environment. Previous calculations on the (SiH3)3N molecule used as a model for the local environment of N in crystalline α- and β-Si3N4gave N NMR shieldings much larger than those measured in the solids and gave the wrong order for the shifts of the inequivalent N sites (e.g., N1 and N2 in β-Si3N4). We have now calculated the N NMR shieldings in larger molecular models for the N2 site of β-Si3N4and have found that the N2 shielding is greatly reduced when additional N1 atoms (second-nearest-neighbors to the central N2) are included. The calculated N2 shieldings (using the GIAO method with the 6-31G* basis set and 6-31G* SCF optimized geometries) are 288.1, 244.7, and 206.0 ppm for the molecules (SiH3)3N, Si6N5H15, and Si9N9H21(central N2), respectively, while the experimental shielding of N2 in β-Si3N4is about 155 ppm. Second-nearest-neighbor effects of only slightly smaller magnitude are calculated for the analog C molecules. At the same time, the effects of molecule size upon Si NMR shieldings and N electric field gradients are small. The local geometries at the N2-like Ns in C6N5H15and C9N9H21are calculated to be planar, consistent with the planar local geometry recently calculated for N in crystalline C3N4using density functional theory.
Excitation energies, radiative and autoionization rates, dielectronic satellite lines, and dielectronic recombination rates for excited states of Na-like W from Ne-like W

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

Safronova, U.I.; Safronova, A.S.; Beiersdorfer, P.

Energy levels, radiative transition probabilities, and autoionization rates for 1s{sup 2}2s{sup 2}2p{sup 5}3l{sup '}nl,1s{sup 2}2s2p{sup 6}3l{sup '}nl(n=3-7,l{<=}n-1) and 1s{sup 2}2s{sup 2}2p{sup 5}4l{sup '}nl,1s{sup 2}2s2p{sup 6}4l{sup '}nl(n=4-6,l{<=}n-1) states in Na-like tungsten (W{sup 63+}) are calculated. Cowan's relativistic Hartree-Fock method, the relativistic multiconfiguration method implemented in the Hebrew University Lawrence Livermore Atomic Code, and the relativistic many-body perturbation theory method, are used. Autoionizing levels above the threshold 1s{sup 2}2s{sup 2}2p{sup 6} are considered. It is found that configuration mixing [3sns+3pnp+3dnd],[3snp+3pns+3pnd+3dnp] plays an important role for all atomic characteristics. Also strong mixing between states with 2s and 2p holes (1s{sup 2}2s{sup 2}2p{sup 5}3l{submore » 1}nl{sub 2}+1s{sup 2}2s2p{sup 6}3l{sub 3}nl{sub 4}) occurs. Branching ratios relative to the first threshold and intensity factors are calculated for satellite lines, and dielectronic recombination (DR) rate coefficients are determined for the excited 1s{sup 2}2s{sup 2}2p{sup 6}nl(n=3-7,l{<=}n-1) states. It is shown that the contribution of the highly excited states is very important for calculation of total DR rates. Contributions from the autoionizing states 1s{sup 2}2s{sup 2}2p{sup 5}3l{sup '}nl,1s{sup 2}2s2p{sup 6}3l{sup '}nl(n{>=}8) and 1s{sup 2}2s{sup 2}2p{sup 5}4l{sup '}nl,1s{sup 2}2s2p{sup 6}4l{sup '}nl(n{>=}7) to the DR rate coefficients are estimated by extrapolation of all atomic parameters. The orbital angular momentum (l) distribution of the rate coefficients shows a peak at l=2. The total DR rate coefficient is derived as a function of electron temperature. The dielectronic satellite spectra of W{sup 63+} are important for L-shell diagnostics of very high-temperature laboratory plasmas such as future ITER fusion plasmas.« less

Early Pleistocene hominin deciduous teeth from the Homo antecessor Gran Dolina-TD6 bearing level (Sierra de Atapuerca, Spain).

PubMed

Bermúdez de Castro, José María; Martinón-Torres, María; Martín-Francés, Laura; Martínez de Pinillos, Marina; Modesto-Mata, Mario; García-Campos, Cecilia; Wu, Xiujie; Xing, Song; Liu, Wu

2017-07-01

During the last 13 years, the late Early Pleistocene Gran Dolina-TD6-2 level (Sierra de Atapuerca, northern Spain) has yielded an additional sample of 26 dental specimens attributed to Homo antecessor. In this report, we present a descriptive and comparative study of the six deciduous teeth. We provide external and internal morphological descriptions following classical terminology, as well as the mesiodistal and buccolingual measurements of the teeth. The internal morphology was described by means of micro-CT technique. The TD6 deciduous teeth preserve primitive features regarding the Homo clade, such as the presence of styles in lower and upper canines and developed anterior and posterior foveae in the dm 2 . However, other features related to the complexity of the crown morphology (e.g., cingulum) are not present in this sample. Furthermore, the great reduction of the talonid of the dm 1 s is also noteworthy. Despite the limited comparative evidence, the presence of a remarkably well-developed tuberculum molare in the dm 1 and dm 1 s from TD6 can be also considered a derived feature in the genus Homo. The TD6 hominins exhibit dental dimensions similar to those of other Pleistocene hominins. The dm 1 s are buccolingually elongated and the buccolingual diameter of ATD6-93 is the largest recorded so far in the Homo fossil record. This study expands the list of plesiomorphic features of H. antecessor, and provides some information on the evolutionary status of this species. However, the identification of some advanced traits evinces a step towards the derived morphology of European Pleistocene teeth. The study of the deciduous dentition confirms the mosaic pattern of H. antecessor morphology revealed in previous studies of this hominin sample. © 2017 Wiley Periodicals, Inc.
Fresno Air Terminal, California. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F

DTIC Science & Technology

1981-01-15

34 *,"- *< " + "-o:"- I *13 C. -"-d+J °0 ’ A4 *+ *" - "~ ._______+: .+ ..G+ ., .2+ .- + tD .: rrgC 67 .. .+ .- -- T C’ TRAC 690 l1ei1. -+ _ *d ef . 5 .t CU L...3;M’d4 JitrET&: SURFACE WINDS 11 Z TD ,T-.[ 5IVIIE/A: PERCENTAGE FREQUENCY OF WIND DIRECTION AND SPEED (FROM HOURLY OBSEVATIONS) STATIO1N V"AT O NAM...041.5 (OL.A) PNvICUs contom1co tins JooN om ossouiti A I - - - - - -- - - - - - - - - - - -__ _ _ _ _ _ _ _ _ _ -_ _ _ _ U : LI4& TD ...3SY 3RA4𔃾 -211
Terminal Area Forecasts, FY 1993-2005

DTIC Science & Technology

1993-07-01

0 td U) ~ 4-) 4.J.4 0 J~ :s 0- -"C4 4o U ).4CO ) 0 u *Wý44 o 41C kdQ(n v 00 UrC~ 4) -4 0 M 0~ 4j > (D M kca 41 Ř b bO CA -A~ ..O 0 .0 Cd~ bl ~ - k...o tD ~ Hr- Nr,- `4v oH f n% oM 0( ON %D ~H w H LnODH (1 O O D DO ODG OD 00 OhOh(T ma % m %0 HC4.Ch h %Ch( i % )d% HN 4J H 1-0 %D- O M (NWN DU VO D...I ~ J)I C1 F "H OD ,- V 1 D ( -r r -4 Ch’. ON 00 -4 c,4 mu) n( (n A;1 m tD b r-4 rJ’q~~ I Nr-W L o 0 ( O HM N~ - I- IV N- M M O ’ rI % NN . OD U NCh0
Scalar Casimir energies in M4>=N for even N

NASA Astrophysics Data System (ADS)

Kantowski, R.; Milton, Kimball A.

1987-01-01

We construct a Green's-function formalism for computing vacuum-fluctuation energies of scalar fields in 4+N dimensions, where the extra N dimensions are compactified into a hypersphere SN of radius a. In all cases a leading cosmological energy term ucosmo~aN/b4+N results. Here b is an ultraviolet cutoff at the Planck scale. In all cases an unambiguous Casimir energy is computed. For odd N these energies agree with those calculated by Candelas and Weinberg. For even N, the Casimir energy is logarithmically divergent: uCasimir~(αN/a4)ln(a/b). The coefficients αN are computed in terms of Bernoulli numbers.
A novel N-terminal motif of dipeptidyl peptidase-like proteins produces rapid inactivation of KV4.2 channels by a pore-blocking mechanism.

PubMed

Jerng, Henry H; Dougherty, Kevin; Covarrubias, Manuel; Pfaffinger, Paul J

2009-11-01

The somatodendritic subthreshold A-type K(+) current in neurons (I(SA)) depends on its kinetic and voltage-dependent properties to regulate membrane excitability, action potential repetitive firing, and signal integration. Key functional properties of the K(V)4 channel complex underlying I(SA) are determined by dipeptidyl peptidase-like proteins known as dipeptidyl peptidase 6 (DPP6) and dipeptidyl peptidase 10 (DPP10). Among the multiple known DPP10 isoforms with alternative N-terminal sequences, DPP10a confers exceptionally fast inactivation to K(V)4.2 channels. To elucidate the molecular basis of this fast inactivation, we investigated the structure-function relationship of the DPP10a N-terminal region and its interaction with the K(V)4.2 channel. Here, we show that DPP10a shares a conserved N-terminal sequence (MNQTA) with DPP6a (aka DPP6-E), which also induces fast inactivation. Deletion of the NQTA sequence in DPP10a eliminates this dramatic fast inactivation, and perfusion of MNQTA peptide to the cytoplasmic face of inside-out patches inhibits the K(V)4.2 current. DPP10a-induced fast inactivation exhibits competitive interactions with internally applied tetraethylammonium (TEA), and elevating the external K(+) concentration accelerates recovery from DPP10a-mediated fast inactivation. These results suggest that fast inactivation induced by DPP10a or DPP6a is mediated by a common N-terminal inactivation motif via a pore-blocking mechanism. This mechanism may offer an attractive target for novel pharmacological interventions directed at impairing I(SA) inactivation and reducing neuronal excitability.
Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline

NASA Astrophysics Data System (ADS)

Hernández-Paredes, Javier; Hernández-Negrete, Ofelia; Carrillo-Torres, Roberto C.; Sánchez-Zeferino, Raúl; Duarte-Moller, Alberto; Alvarez-Ramos, Mario E.

2015-10-01

2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good β values. However, the β values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline.
Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline.

PubMed

Hernández-Paredes, Javier; Hernández-Negrete, Ofelia; Carrillo-Torres, Roberto C; Sánchez-Zeferino, Raúl; Duarte-Moller, Alberto; Alvarez-Ramos, Mario E

2015-10-05

2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good β values. However, the β values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline. Copyright © 2015 Elsevier B.V. All rights reserved.
Decoherence at constant excitation

NASA Astrophysics Data System (ADS)

Torres, J. M.; Sadurní, E.; Seligman, T. H.

2012-02-01

We present a simple exactly solvable extension of the Jaynes-Cummings model by adding dissipation. This is done such that the total number of excitations is conserved. The Liouville operator in the resulting master equation can be reduced to blocks of 4×4 matrices.
State-of-technology for joining TD-NiCr sheet

NASA Technical Reports Server (NTRS)

Holko, K. H.; Moore, T. J.; Gyorgak, C. A.

1972-01-01

At the current state-of-technology there are many joining processes that can be used to make sound welds in TD-NiCr sheet. Some of these that are described in this report are electron beam welding, gas-tungsten arc welding, diffusion welding, resistance spot welding, resistance seam welding, and brazing. The strengths of the welds made by the various processes show considerable variation, especially at elevated temperatures. Most of the fusion welding processes tend to give weak welds at elevated temperatures (with the exception of fusion-type resistance spotwelds). However, solid-state welds have been made with parent metal properties. The process used for a specific application will be dictated by the specific joint requirements. In highly stressed joints at elevated temperatures, one of the solid-state processes, such as DFW, RSW (solid-state or fusion), and RSEW, offer the most promise.
REVIEWS OF TOPICAL PROBLEMS: Gas lasers with solar excitation

NASA Astrophysics Data System (ADS)

Gordiets, B. F.; Panchenko, Vladislav Ya

1986-07-01

CONTENTS 1. Introduction 703 2. General requirements for laser media using solar excitation 704 3. Lasers with direct excitation by solar light 705 3.1. Basic characteristics of laser media. 3.2. Photodissociation Br2-CO2 lasers. 3.3. Interhalogen molecule lasers. 3.4. Iodine lasers. 3.5. Alkali metal vapor lasers. 4. Lasers with thermal conversion of solar pumping 709 4.1. General considerations. 4.2. CO2 laser with excitation in a black body cavity and with gas flow. 4.3. cw CO2 laser without gas flow. 5. Space laser media with solar excitation 713 5.1. Population inversion of molecular levels in the outer atmosphere of the Earth. 5.2. Laser effect in the atmospheres of Venus and Mars. 5.3. Terrestrial experimental technique for observing infrared emission in the atmospheres of planets. 5.4. Designs for laser systems in the atmospheres of Venus and Mars. 6. Conclusions 717 References 717
Stress in (Al, Ga)N heterostructures grown on 6H-SiC and Si substrates byplasma-assisted molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Koshelev, O. A.; Nechaev, D. V.; Sitnikova, A. A.; Ratnikov, V. V.; Ivanov, S. V.; Jmerik, V. N.

2017-11-01

The paper describes experimental results on low temperature plasma-assisted molecular beam epitaxy of GaN/AlN heterostructures on both 6H-SiC and Si(111) substrates. We demonstrate that application of migration enhanced epitaxy and metal-modulated epitaxy for growth of AlN nucleation and buffer layers lowers the screw and edge(total)threading dislocation (TD) densities down to 1.7·108 and 2·109 cm-2, respectively, in a 2.8-μm-thick GaN buffer layer grown atop of AlN/6H-SiC. The screw and total TD densities of 1.2·109 and 7.4·109 cm-2, respectively, were achieved in a 1-μm-thickGaN/AlNheterostructure on Si(111). Stress generation and relaxation in GaN/AlN heterostructures were investigated by using multi-beam optical stress sensor (MOSS) to achieve zero substrate curvature at room temperature. It is demonstrated that a 1-μm-thick GaN/AlN buffer layer grown by PA MBE provides planar substrate morphology in the case of growth on Si substrates whereas 5-μm-thick GaN buffer layers have to be used to achieve the same when growing on 6H-SiC substrates.
Role of core excitation in ( d , p ) transfer reactions

DOE PAGES

Deltuva, A.; Ross, A.; Norvaišas, E.; ...

2016-10-24

In our recent work we found that core excitations can be important in extracting structure information from (d,p) reactions. Our objective is to systematically explore the role of core excitation in (d,p) reactions and to understand the origin of the dynamical effects. Based on the particle-rotor model of n+Be 10, we generate a number of models with a range of separation energies (S n=0.1–5.0 MeV), while maintaining a significant core excited component. We then apply the latest extension of the momentum-space-based Faddeev method, including dynamical core excitation in the reaction mechanism to all orders, to the Be 10(d,p)Be 11-like reactions,more » and study the excitation effects for beam energies E d=15–90 MeV. We study the resulting angular distributions and the differences between the spectroscopic factor that would be extracted from the cross sections, when including dynamical core excitation in the reaction, and that of the original structure model. We also explore how different partial waves affect the final cross section. Our results show a strong beam-energy dependence of the extracted spectroscopic factors that become smaller for intermediate beam energies. Finally, this dependence increases for loosely bound systems.« less
Momentum Dependence of Charge Excitations in YBa2Cu3O7-δ and Nd2-xCexCuO4

NASA Astrophysics Data System (ADS)

Ishii, Kenji

2006-03-01

Resonant inelastic x-ray scattering (RIXS) studies at Cu K-edge on high-Tc superconducting cuprates, YBa2Cu3O7-δ and Nd2-xCexCuO4 are presented. The superconductivity occurs in the vicinity of the Mott insulating state and it is important to clarify the nature of the Mott gap and its doping dependence. Because RIXS has an advantage that we can measure charge excitation in a wide energy-momentum space, it gives a unique opportunity to study the electronic structure of materials. We apply this technique to high-Tc superconducting cuprates. In particular the electronic structure of strongly correlated metals is in the focus of our RIXS study. The experiments were performed at BL11XU of SPring-8, Japan, where a specially designed spectrometer for inelastic x-ray scattering is installed. In optimally doped YBa2Cu3O7-δ, anisotropic spectra are observed in the ab plane of a twin-free crystal. The Mott gap excitation from the one-dimensional CuO chain is enhanced at 2 eV near the zone boundary of the chain direction, while the excitation from the CuO2 plane is broad at 1.5-4 eV and almost independent of momentum. Theoretical calculation based on the one-dimensional and two-dimensional Hubbard model reproduces the observed features in the RIXS spectra when smaller values of the on-site Coulomb energy of the chain than that of the plane are assumed. This means that the charge transfer gap of the chain is smaller than that of the plane. On the other hand, both interband excitation across the Mott gap and intraband excitation in the upper Hubbard band are observed in the electron-doped Nd2-xCexCuO4. The intensity of the interband excitation is concentrated at ˜ 2 eV near the zone boundary while a dispersion relation with a momentum-dependent width emerges in the intraband excitation. The author would like to acknowledge to his collaborators, K. Tsutsui, Y. Endoh, T. Tohyama, K. Kuzushita, T. Inami, K. Ohwada, M. Hoesch, M. Tsubota, Y. Murakami, J. Mizuki, S. Maekawa, T
Characterization of a potentially axially symmetric europium(III) complex of a tetraacetate,tetraaza, macrocyclic ligand by luminescence excitation, emission and lifetime spectroscopy

NASA Astrophysics Data System (ADS)

Albin, Michael; de, William; Horrocks, W., Jr.; Liotta, Frank J.

1982-01-01

The Eu(III) complex of the octadentate macrocyclic ligand, 1,4,7,10-tetraazacyclododecane-N,N',N'',N''' -tetraacetate, DOTA, has been examined by luminescence excitation, emission, and lifetime spectroscopy using pulsed dye laser techniques. The results confirm the expected axially symmetric nature of the major component in solution and reveal that 1.2 ± 0.4 water molecules arc coordinatcd to the Eu(III) ion in the complex.
Spectroscopic (FT-IR, FT-Raman and UV-Visible) investigations, NMR chemical shielding anisotropy (CSA) parameters of 2,6-Diamino-4-chloropyrimidine for dye sensitized solar cells using density functional theory.

PubMed

Gladis Anitha, E; Joseph Vedhagiri, S; Parimala, K

2015-02-05

The molecular structure, geometry optimization, vibrational frequencies of organic dye sensitizer 2,6-Diamino-4-chloropyrimidine (DACP) were studied based on Hartree-Fock (HF) and density functional theory (DFT) using B3LYP methods with 6-311++G(d,p) basis set. Ultraviolet-Visible (UV-Vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the UV-Visible regions were assigned based on TD-DFT calculation. The absorption bands are assigned to transitions. The interfacial electron transfer between semiconductor TiO2 electrode and dye sensitizer DACP is due to an electron injection process from excited dye to the semiconductor's conduction band. The observed and the calculated frequencies are found to be in good agreement. The energies of the frontier molecular orbitals (FMOS) have also been determined. The chemical shielding anisotropic (CSA) parameters are calculated from the NMR analysis, Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Copyright © 2014 Elsevier B.V. All rights reserved.
A direct evidence of allocating yellow luminescence band in undoped GaN by two-wavelength excited photoluminescence

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

Julkarnain, M., E-mail: s13ds053@mail.saitama-u.ac.jp, E-mail: jnain.apee@ru.ac.bd; Department of Applied Physics and Electronic Engineering, University of Rajshahi, Rajshahi 6205; Fukuda, T.

2015-11-23

The behavior of below-gap luminescence of undoped GaN grown by MOCVD has been studied by the scheme of two-wavelength-excited photoluminescence. The emission intensity of shallow donor to valence band transition (I{sub OX}) increased while intensities of donor-acceptor pair transition and the Yellow Luminescence band (YLB) decreased after the irradiation of a below-gap excitation source of 1.17 eV. The conventional energy schemes and recombination models have been considered to explain our experimental result but only one model in which YLB is the transition of a shallow donor to a deep state placed at ∼1 eV above the valence band maximum satisfies our result.more » The defect related parameters that give a qualitative insight in the samples have been evaluated by systematically solving the rate equations and fitting the result with the experiment.« less
On the calculation of charge transfer transitions with standard density functionals using constrained variational density functional theory.

PubMed

Ziegler, Tom; Krykunov, Mykhaylo

2010-08-21

It is well known that time-dependent density functional theory (TD-DFT) based on standard gradient corrected functionals affords both a quantitative and qualitative incorrect picture of charge transfer transitions between two spatially separated regions. It is shown here that the well known failure can be traced back to the use of linear response theory. Further, it is demonstrated that the inclusion of higher order terms readily affords a qualitatively correct picture even for simple functionals based on the local density approximation. The inclusion of these terms is done within the framework of a newly developed variational approach to excitation energies called constrained variational density functional theory (CV-DFT). To second order [CV(2)-DFT] this theory is identical to adiabatic TD-DFT within the Tamm-Dancoff approximation. With inclusion of fourth order corrections [CV(4)-DFT] it affords a qualitative correct description of charge transfer transitions. It is finally demonstrated that the relaxation of the ground state Kohn-Sham orbitals to first order in response to the change in density on excitation together with CV(4)-DFT affords charge transfer excitations in good agreement with experiment. The new relaxed theory is termed R-CV(4)-DFT. The relaxed scheme represents an effective way in which to introduce double replacements into the description of single electron excitations, something that would otherwise require a frequency dependent kernel.
Using single top rapidity to measure V{sub td}, V{sub ts}, V{sub tb} at hadron colliders

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

Aguilar-Saavedra, J. A.; Onofre, A.; Departamento de Fisica, Universidade do Minho, P-4710-057 Braga

2011-04-01

Single top production processes are usually regarded as the ones in which V{sub tb} can be directly measured at hadron colliders. We show that the analysis of the single top rapidity distribution in t-channel and tW production can also set direct limits on V{sub td}. At LHC with 10 fb{sup -1} at 14 TeV, the combined limits on V{sub td} may be reduced by almost a factor of 2 when the top rapidity distribution is used. This also implies that the limits on V{sub tb} can also be reduced by 15%, since both parameters, as well as V{sub ts}, mustmore » be simultaneously obtained from a global fit to data. At Tevatron, the exploitation of this distribution would require very high statistics.« less
New fluorescent probes for visual proteins. Part II. 5-(Oxo)penta-2,4-dienyl-p-(N,N-dimethylamino)benzoate.

PubMed

Papper, Vladislav; Kharlanov, Vladimir; Schädel, Sandra; Maretzki, Dieter; Rettig, Wolfgang

2003-12-01

A new dual-fluorescent compound, 5-(oxo)penta-2,4-dienyl-p-(N,N-dimethylamino)benzoate (1), a derivative of dimethylaminobenzoic acid, has been synthesised and studied photophysically. This compound continues the series of potential fluorescent probes for visual and proton-pumping opsin proteins. The photophysical behaviour of this molecule, including charge-transfer interaction in the ground state and dual-fluorescence emission, is similar to that of the previously studied analogue cis-3-(oxo)propenyl-p-(N,N-dimethylamino)benzoate (cis-2). The presence of several theoretically calculated conformers of compound 2 was suggested to be responsible for the observed strongly red-shifted absorption and excitation wavelength dependence. These photophysical anomalies were also observed for molecule 1, though the models put forward to explain them in the cases of 1 and 2 are rather different. Based on theoretical calculations and experimental results, we propose that some of the stable conformers might be connected with either a charge-transfer complex or mesomeric interactions in the ground state. Upon changing the electronic nature of the oxo-pentadienyl acceptor moiety, e.g. protonation, chemical or biochemical reaction, the charge-transfer absorption disappears, which leads to a dramatic increase in the fluorescence quantum yield.
Excitation cross sections for the ns 2S yields np 2P resonance transitions in Mg(+) (n = 3) and Zn(+) (n = 4) using electron-energy-loss and merged-beams methods

NASA Technical Reports Server (NTRS)

Smith, Steven J.; Chutjian, A.; Mitroy, J.; Tayal, S. S.; Henry, Ronald J. W.; Man, K.-F.; Mawhorter, R. J.; Williams, I. D.

1993-01-01

Electron-excitation cross sections are reported for the 3s 2S yields 3p 2P(h, k) resonance transition in Mg(+) at energies from threshold (4.43 eV) to approximately 9 times threshold (40.0 eV). The electron-energy-loss merged-beams technique used in these measurements is described in detail. In addition, the method of separating contributions of the elastically scattered (Coulomb) and the inelastically scattered electrons in the present Mg(+) case and previously reported Zn(+) results is described. Comparisons in the experimental energy range are made for Mg(+) with the two five-state close-coupling theoretical calculations carried out herein, and with other published close-coupling, distorted-wave, and semiempirical calculations. The present Mg(+) cross sections and Zn(+) cross sections from earlier measurements are tabulated.

Exploring the binding of 4-thiothymidine with human serum albumin by spectroscopy, atomic force microscopy, and molecular modeling methods.

PubMed

Zhang, Juling; Gu, Huaimin; Zhang, Xiaohui

2014-01-30

The interaction of 4-thiothymidine (S(4)TdR) with human serum albumin (HSA) was studied by equilibrium dialysis under normal physiological conditions. In this work, the mechanism of the interaction between S(4)TdR and human serum albumin (HSA) was exploited by fluorescence, UV, CD circular, and SERS spectroscopic. Fluorescence and UV spectroscopy suggest that HSA intensities are significantly decreased when adding S(4)TdR to HAS, and the quenching mechanism of the fluorescence is static. Also, the ΔG, ΔH, and ΔS values across temperature indicated that hydrophobic interaction was the predominant binding force. The CD circular results show that there is little change in the secondary structure of HSA except the environment of amino acid changes when adding S(4)TdR to HSA. The surface-enhanced Raman scattering (SERS) shows that the interaction between S(4)TdR and HSA can be achieved through different binding sites which are probably located in the II A and III A hydrophobic pockets of HSA which correspond to Sudlow's I and II binding sites. In addition, the molecular modeling displays that S(4)TdR-HSA complex is stabilized by hydrophobic forces, which result from amino acid residues. The atomic force microscopy results revealed that the single HSA molecular dimensions were larger after interaction of 4-thiothymidine. This work would be useful to understand the state of the transportation, distribution, and metabolism of the anticancer drugs in the human body, and it could provide a useful biochemistry parameter for the development of new anti-cancer drugs and research of pharmacology mechanisms. Copyright © 2013 Elsevier Ltd. All rights reserved.
Entanglement entropy for (3+1)-dimensional topological order with excitations

NASA Astrophysics Data System (ADS)

Wen, Xueda; He, Huan; Tiwari, Apoorv; Zheng, Yunqin; Ye, Peng

2018-02-01

Excitations in (3+1)-dimensional [(3+1)D] topologically ordered phases have very rich structures. (3+1)D topological phases support both pointlike and stringlike excitations, and in particular the loop (closed string) excitations may admit knotted and linked structures. In this work, we ask the following question: How do different types of topological excitations contribute to the entanglement entropy or, alternatively, can we use the entanglement entropy to detect the structure of excitations, and further obtain the information of the underlying topological order? We are mainly interested in (3+1)D topological order that can be realized in Dijkgraaf-Witten (DW) gauge theories, which are labeled by a finite group G and its group 4-cocycle ω ∈H4[G ;U(1 ) ] up to group automorphisms. We find that each topological excitation contributes a universal constant lndi to the entanglement entropy, where di is the quantum dimension that depends on both the structure of the excitation and the data (G ,ω ) . The entanglement entropy of the excitations of the linked/unlinked topology can capture different information of the DW theory (G ,ω ) . In particular, the entanglement entropy introduced by Hopf-link loop excitations can distinguish certain group 4-cocycles ω from the others.
Preparation and luminescence properties of Ce3+ and Ce3+/Tb(3+)-activated Y4Si2O7N2 phosphors.

PubMed

Xia, Zhiguo; Wu, Weiwei

2013-09-28

Ce(3+) and Ce(3+)/Tb(3+)-activated Y4Si2O7N2 phosphors are synthesized by the solid-state method, which can be efficiently excited by near ultraviolet (UV) light emitting diode (LED) chips. The PL spectrum of Y4Si2O7N2:Ce(3+) shows a broad hump between 380 and 650 nm, assigned to the electron transition from the 4f energy level to different 5d sub levels of the Ce(3+) ions at different Y(3+) sites. The color of the Y4Si2O7N2:Ce(3+) phosphor can shift from blue to green by introducing Tb(3+). In addition, the energy transfer process from Ce(3+) to Tb(3+) in the Y4Si2O7N2 host was investigated and discussed in terms of both the luminescence spectra and decay curves. The energy transfer critical distance has been calculated and evaluated by the concentration quenching method. Therefore, the Ce(3+) and Ce(3+)/Tb(3+)-activated Y4Si2O7N2 phosphors can serve as key materials for phosphor-converted white-light UV-LEDs.
FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule

NASA Astrophysics Data System (ADS)

Muthu, S.; Elamurugu Porchelvi, E.

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed.
FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule.

PubMed

Muthu, S; Elamurugu Porchelvi, E

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed. Copyright © 2013 Elsevier B
Electron-impact excitation of diatomic hydride cations II: OH+ and SH+

NASA Astrophysics Data System (ADS)

Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

2018-05-01

R-matrix calculations combined with the adiabatic-nuclei-rotation and Coulomb-Born approximations are used to compute electron-impact rotational rate coefficients for two open-shell diatomic cations of astrophysical interest: the hydoxyl and sulphanyl ions, OH+ and SH+. Hyperfine resolved rate coefficients are deduced using the infinite-order-sudden approximation. The propensity rule ΔF = Δj = ΔN = ±1 is observed, as is expected for cations with a large dipole moment. A model for OH+ excitation in the Orion Bar photon-dominated region is presented which nicely reproduces Herschel observations for an electron fraction xe = 10-4 and an OH+ column density of 3 × 1013 cm-2. Electron-impact electronic excitation cross-sections and rate coefficients for the ions are also presented.
Vibrational excitation of triatomic molecules near the shape resonance region

NASA Astrophysics Data System (ADS)

Ishijima, Y.; Ohkawa, M.; Hoshino, M.; Campbell, L.; Brunger, M. J.; Tanaka, H.

2012-11-01

In this study we have measured angular distributions of differential cross sections (DCS) for vibrational excitation and superelastic scattering from vibrationally excited N2O. The results are analyzed and interpreted using the angular correlation theory by Read.
Excited State Atom-Ion Charge-Exchange

NASA Astrophysics Data System (ADS)

Li, Ming; Makrides, Constantinos; Petrov, Alexander; Kotochigova, Svetlana

2017-04-01

We theoretically investigate the exothermic charge-exchange reaction between an excited atom and a ground-state positive ion. In particular, we focus on MOT-excited Ca*(4s4p 1P) atoms colliding with ground-state Yb+ ions, which are under active study by the experimental group of E. Hudson at UCLA. Collisions between an excited atom and an ion are guided by two major contributions to the long-range interaction potentials, the induction C4 /R4 and charge-quadrupole C3 /R3 potentials, and their coupling by the electron-exchange interaction. Our model of these forces leads to close-coupling equations for multiple reaction channels. We find several avoided crossings between the potentials that couple to the nearby asymptotic limits of Yb*+Ca+, some of which can possibly provide large charge exchange rate coefficients above 10-10 cm3 / s. We acknowledge support from the US Army Research Office, MURI Grants W911NF-14-1-0378 and the US National Science Foundation, Grant PHY-1619788.
Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

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

Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.

Resonance Raman and electronic absorption spectra are reported for the S/sub 0/ and T/sub 1/ states of the carotenoids ..beta..-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C/sub 50/)-..beta..-carotene, ..beta..-apo-8'-carotenal, and ethyl ..beta..-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S/sub 0/ and T/sub 1/, regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S/sub 0/ and T/sub 1/ reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited statemore » which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T/sub 1/ states of carotenoids and in the S/sub 1/ states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S/sub 1/ lifetime (of the /sup 1/B/sub u/ and/or the /sup 1/A/sub g/* states) of ..beta..-carotene in benzene is less than 1 ps.« less
Polarization, excited states, trans-cis properties and anisotropy of thermal and electrical conductivity of the 4-(phenyldiazenyl)aniline in PVA matrix

NASA Astrophysics Data System (ADS)

Shahab, Siyamak; Filippovich, Liudmila; Sheikhi, Masoome; Kumar, Rakesh; Dikusar, Evgenij; Yahyaei, Hooriye; Muravsky, Alexander

2017-08-01

In the present work, Polarization, Excited States, Trans-Cis (E → Z) Isomerization Properties and Anisotropy of Thermal and Electrical Conductivity of the 4-(phenyldiazenyl)aniline in the presence of polyvinyl alcohol (PVA) matrix were studied. DFT, UV/Vis, IR-Spectroscopies and Indicator Method were used for Determination of Thermal Conductivity of polymer films. The absorption spectra of the 4-(phenyldiazenyl)aniline in dimethylformamide (DMF) solvent and in aqueous medium were calculated. The nature of absorption peaks of the 4-(phenyldiazenyl)aniline in the UV/Vis spectral regions were interpreted. The solvent effect on the absorption spectrum of the 4-(phenyldiazenyl)aniline has established. The molecular HOMO-LUMO, excitation energies and oscillator strengths for E and Z isomers of the 4-(phenyldiazenyl)aniline have also been calculated and presented. Optical Properties of the PVA-films containing 4-(phenyldiazenyl)aniline have been also investigated. Polarizing Efficiency (PE) of obtained PVA-film is 98-99% at Stretching Degree (Rs) 3.5. Anisotropy of thermal and electrical conductivity of PVA-films containing E and Z isomers of the 4-(phenyldiazenyl)aniline was also measured and discussed.
Synthesis and structure of the extended phosphazane ligand [(1,4-C6H4){N(μ-PN(t)Bu)2N(t)Bu}2](4).

PubMed

Sevilla, Raquel; Less, Robert J; García-Rodríguez, Raúl; Bond, Andrew D; Wright, Dominic S

2016-02-07

The reaction of the phenylene-bridged precursor (1,4-C6H4)[N(PCl2)2]2 with (t)BuNH2 in the presence of Et3N gives the new ligand precursor (1,4-C6H4)[N(μ-N(t)Bu)2(PNH(t)Bu)2]2, deprotonation of which with Bu2Mg gives the novel tetraanion [(1,4-C6H4){N(μ-N(t)Bu)2(PN(t)Bu)2}2](4-).
Cryogenic exciter

DOEpatents

Bray, James William [Niskayuna, NY; Garces, Luis Jose [Niskayuna, NY

2012-03-13

The disclosed technology is a cryogenic static exciter. The cryogenic static exciter is connected to a synchronous electric machine that has a field winding. The synchronous electric machine is cooled via a refrigerator or cryogen like liquid nitrogen. The static exciter is in communication with the field winding and is operating at ambient temperature. The static exciter receives cooling from a refrigerator or cryogen source, which may also service the synchronous machine, to selected areas of the static exciter and the cooling selectively reduces the operating temperature of the selected areas of the static exciter.
Icariin Ameliorate Thiram-Induced Tibial Dyschondroplasia via Regulation of WNT4 and VEGF Expression in Broiler Chickens

PubMed Central

Zhang, Hui; Mehmood, Khalid; Li, Kun; Rehman, Mujeeb U.; Jiang, Xiong; Huang, Shucheng; Wang, Lei; Zhang, Lihong; Tong, Xiaole; Nabi, Fazul; Yao, Wangyuan; Iqbal, Muhammad K.; Shahzad, Muhammad; Li, Jiakui

2018-01-01

Tibial dyschondroplasia (TD) is main bone problem in fast growing poultry birds that effect proximal growth plate (GP) of tibia bone. TD is broadly defined as non-vascularized and non-mineralized, and enlarged GP with tibia bone deformation and lameness. Icariin (Epimedium sagittatum) is a traditional Chinese medicine, which is commonly practiced in the treatment of various bone diseases. Recently, many researcher reports about the beneficial effects of icariin in relation to various types of bone conditions but no report is available about promoting effect of icariin against TD. Therefore, current study was conducted to explore the ameliorating effect of icariin in thiram-induced TD chickens. A total of 180 broiler chicks were equally distributed in three groups; control, TD induced by thiram (50 mg/kg), and icariin group (treated with icariin @10 mg/kg). All groups were administered with normal standard diet ad libitum regularly until the end of experiment. The wingless-type member 4 (WNT4) and vascular endothelial growth factor (VEGF) genes and proteins expression were analyzed by quantitative real-time polymerase chain reaction and western blot analysis respectively. Tibial bone parameters, physiological changes in serum, antioxidant enzymes, and chicken growth performance were determined to assess advantage and protective effect of the medicine in broiler chicken. The expression of WNT4 was decreased while VEGF increased significantly (P < 0.05) in TD affected chicks. TD enhanced the GP, lameness, and irregular chondrocytes, while reduced the liver function, antioxidant enzymes in liver, and performance of chickens. Icariin treatment up-regulated WNT4 and down-regulated VEGF gene and protein expressions significantly (P < 0.05), restored the GP width, increased growth performance, corrected liver functions and antioxidant enzymes levels in liver, and mitigated the lameness in broiler chickens. In conclusion, icariin administration recovered GP size, normalized
Photoluminescence and Energy Transfer Properties with Y+SiO4 Substituting Ba+PO4 in Ba3Y(PO4)3:Ce(3+)/Tb(3+), Tb(3+)/Eu(3+) Phosphors for w-LEDs.

PubMed

Li, Kai; Liang, Sisi; Shang, Mengmeng; Lian, Hongzhou; Lin, Jun

2016-08-01

A series of Ce(3+), Tb(3+), Eu(3+) doped Ba2Y2(PO4)2(SiO4) (BYSPO) phosphors were synthesized via the high-temperature solid-state reaction route. X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared, solid-state NMR, photoluminescence (PL) including temperature-dependent PL, and fluorescent decay measurements were conducted to characterize and analyze as-prepared samples. BYSPO was obtained by the substitution of Y+SiO4 for Ba+PO4 in Ba3Y(PO4)3 (BYPO). The red shift of PL emission from 375 to 401 nm occurs by comparing BYSPO:0.14Ce(3+) with BYPO:0.14Ce(3+) under 323 nm UV excitation. More importantly, the excitation edge can be extended from 350 to 400 nm, which makes it be excited by UV/n-UV chips (330-410 nm). Tunable emission color from blue to green can be observed under 365 nm UV excitation based on the energy transfer from Ce(3+) to Tb(3+) ions after codoping Tb(3+) into BYSPO:0.14Ce(3+). Moreover, energy transfer from Tb(3+) to Eu(3+) ions also can be found in BYSPO:Tb(3+),Eu(3+) phosphors, resulting in the tunable color from green to orange red upon 377 nm UV excitation. Energy transfer properties were demonstrated by overlap of excitation spectra, variations of emission spectra, and decay times. In addition, energy transfer mechanisms from Ce(3+) to Tb(3+) and Tb(3+) to Eu(3+) in BYSPO were also discussed in detail. Quantum yields and CIE chromatic coordinates were also presented. Generally, the results suggest their potential applications in UV/n-UV pumped LEDs.
Fixed node diffusion Monte Carlo using a genetic algorithm: a study of the CO-(4)He(N) complex, N = 1…10.

PubMed

Ramilowski, Jordan A; Farrelly, David

2012-06-14

The diffusion Monte Carlo (DMC) method is a widely used algorithm for computing both ground and excited states of many-particle systems; for states without nodes the algorithm is numerically exact. In the presence of nodes approximations must be introduced, for example, the fixed-node approximation. Recently we have developed a genetic algorithm (GA) based approach which allows the computation of nodal surfaces on-the-fly [Ramilowski and Farrelly, Phys. Chem. Chem. Phys., 2010, 12, 12450]. Here GA-DMC is applied to the computation of rovibrational states of CO-(4)He(N) complexes with N≤ 10. These complexes have been the subject of recent high resolution microwave and millimeter-wave studies which traced the onset of microscopic superfluidity in a doped (4)He droplet, one atom at a time, up to N = 10 [Surin et al., Phys. Rev. Lett., 2008, 101, 233401; Raston et al., Phys. Chem. Chem. Phys., 2010, 12, 8260]. The frequencies of the a-type (microwave) series, which correlate with end-over-end rotation in the CO-(4)He dimer, decrease from N = 1 to 3 and then smoothly increase. This signifies the transition from a molecular complex to a quantum solvated system. The frequencies of the b-type (millimeter-wave) series, which evolves from free rotation of the rigid CO molecule, initially increase from N = 0 to N∼ 6 before starting to decrease with increasing N. An interesting feature of the b-type series, originally observed in the high resolution infra-red (IR) experiments of Tang and McKellar [J. Chem. Phys., 2003, 119, 754] is that, for N = 7, two lines are observed. The GA-DMC algorithm is found to be in good agreement with experimental results and possibly detects the small (∼0.7 cm(-1)) splitting in the b-series line at N = 7. Advantages and disadvantages of GA-DMC are discussed.
A novel yellow-emitting SrAlSi{sub 4}N{sub 7}:Ce{sup 3+} phosphor for solid state lighting: Synthesis, electronic structure and photoluminescence properties

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

Ruan, Jian; Laboratory of Glasses and Nanostructured Functional Materials, 122 Luoshi Road, Wuhan, Hubei 430070; Xie, Rong-Jun, E-mail: Xie.Rong-Jun@nims.go.jp

2013-12-15

Ce{sup 3+}-doped and Ce{sup 3+}/Li{sup +}-codoped SrAlSi{sub 4}N{sub 7} phosphors were synthesized by gas pressure sintering of powder mixtures of Sr{sub 3}N{sub 2}, AlN, α-Si{sub 3}N{sub 4}, CeN and Li{sub 3}N. The phase purity, electronic crystal structure, photoluminescence properties of SrAlSi{sub 4}N{sub 7}:Ce{sup 3+}(Ce{sup 3+}/Li{sup +}) were investigated in this work. The band structure calculated by the DMol{sup 3} code shows that SrAlSi{sub 4}N{sub 7} has a direct band gap of 3.87 eV. The single crystal analysis of Ce{sup 3+}-doped SrAlSi{sub 4}N{sub 7} indicates a disordered Si/Al distribution and nitrogen vacnacy defects. SrAlSi{sub 4}N{sub 7} was identified as a majormore » phase of the fired powders, and Sr{sub 5}Al{sub 5}Si{sub 21}N{sub 35}O{sub 2} and AlN as minor phases. Both Ce{sup 3+} and Ce{sup 3+}/Li{sup +} doped SrAlSi{sub 4}N{sub 7} phosphors can be efficiently excited by near-UV or blue light and show a broadband yellow emission peaking around 565 nm. A highest external quantum efficiency of 38.3% under the 450 nm excitation was observed for the Ce{sup 3+}/Li{sup +}-doped SrAlSi{sub 4}N{sub 7} (5 mol%). A white light LED lamp with color temperature of 6300 K and color rendering index of Ra=78 was achieved by combining Sr{sub 0.97}Al{sub 1.03}Si{sub 3.997}N/94/maccounttest14=t0005{sub 1}8193 {sub 7}:Ce{sup 3+}{sub 0.03} with a commercial blue InGaN chip. It indicates that SrAlSi{sub 4}N{sub 7}:Ce{sup 3+} is a promising yellow emitting down-conversion phosphor for white LEDs. - Graphical abstract: One-phosphor converted white light-emitting diode (LED) was fabricated by combining a blue LED chip and a yellow-emitting SrAlSi4N7:Ce{sup 3+} phosphor (see inset), which has the color rendering index of 78 and color temperature of 6300 K. - Highlights: • We reported a new yellow nitride phosphor suitable for solid state lighting. • We solved the crystal structure and evidenced a disordered Si/Al distribution. • We fabricated a high color
Crystal structure of (4-cyanopyridine-κN){5,10,15,20-tetrakis[4-(benzoyloxy)phenyl]porphyrinato-κ4 N}zinc–4-cyanopyridine (1/1)

PubMed Central

Nasri, Soumaya; Amiri, Nesrine; Turowska-Tyrk, Ilona; Daran, Jean-Claude; Nasri, Habib

2016-01-01

In the title compound, [Zn(C72H44N4O8)(C6H4N2)]·C6H4N2 or [Zn(TPBP)(4-CNpy]·(4-CNpy) [where TPBP and 4-CNpy are 5,10,15,20-(tetraphenylbenzoate)porphyrinate and 4-cyanopyridine, respectively], the ZnII cation is chelated by four pyrrole-N atoms of the porphyrinate anion and coordinated by a pyridyl-N atom of the 4-CNpy axial ligand in a distorted square-pyramidal geometry. The average Zn—N(pyrrole) bond length is 2.060 (6) Å and the Zn—N(4-CNpy) bond length is 2.159 (2) Å. The zinc cation is displaced by 0.319 (1) Å from the N4C20 mean plane of the porphyrinate anion toward the 4-cyanopyridine axial ligand. This porphyrinate macrocycle exhibits major saddle and moderate ruffling and doming deformations. In the crystal, the [Zn(TPBP)(4-CNpy)] complex molecules are linked together via weak C—H⋯N, C—H⋯O and C—H⋯π interactions, forming supramolecular channels parallel to the c axis. The non-coordinating 4-cyanopyridine molecules are located in the channels and linked with the complex molecules, via weak C—H⋯N interactions and π-π stacking or via weak C—H⋯O and C—H⋯π interactions. The non-coordinating 4-cyanopyridine molecule is disordered over two positions with an occupancy ratio of 0.666 (4):0.334 (4). PMID:26958379
DFT and TD-DFT calculations of metallotetraphenylporphyrin and metallotetraphenylporphyrin fullerene complexes as potential dye sensitizers for solar cells

NASA Astrophysics Data System (ADS)

El Mahdy, A. M.; Halim, Shimaa Abdel; Taha, H. O.

2018-05-01

Density functional theory (DFT) and time-dependent DFT calculations have been employed to model metallotetraphenylporphyrin dyes and metallotetraphenylporphyrin -fullerene complexes in order to investigate the geometries, electronic structures, the density of states, non-linear optical properties (NLO), IR-vis spectra, molecular electrostatic potential contours, and electrophilicity. To calculate the excited states of the tetraphenyl porphyrin analogs, time-dependent density functional theory (TD-DFT) are used. Their UV-vis spectra were also obtained and a comparison with available experimental and theoretical results is included. The results reveal that the metal and the tertiary butyl groups of the dyes are electron donors, and the tetraphenylporphyrin rings are electron acceptors. The HOMOs of the dyes fall within the (TiO2)60 and Ti38O76 band gaps and support the issue of typical interfacial electron transfer reaction. The resulting potential drop of Mn-TPP-C60 increased by ca. 3.50% under the effect of the tertiary butyl groups. The increase in the potential drop indicates that the tertiary butyl complexes could be a better choice for the strong operation of the molecular rectifiers. The introduction of metal atom and tertiary butyl groups to the tetraphenyl porphyrin moiety leads to a stronger response to the external electric field and induces higher photo-to-current conversion efficiency. This also shifts the absorption in the dyes and makes them potential candidates for harvesting light in the entire visible and near IR region for photovoltaic applications.
An efficient approach to CI: General matrix element formulas for spin-coupled particle-hole excitations

NASA Astrophysics Data System (ADS)

Tavan, Paul; Schulten, Klaus

1980-03-01

A new, efficient algorithm for the evaluation of the matrix elements of the CI Hamiltonian in the basis of spin-coupled ν-fold excitations (over orthonormal orbitals) is developed for even electron systems. For this purpose we construct an orthonormal, spin-adapted CI basis in the framework of second quantization. As a prerequisite, spin and space parts of the fermion operators have to be separated; this makes it possible to introduce the representation theory of the permutation group. The ν-fold excitation operators are Serber spin-coupled products of particle-hole excitations. This construction is also designed for CI calculations from multireference (open-shell) states. The 2N-electron Hamiltonian is expanded in terms of spin-coupled particle-hole operators which map any ν-fold excitation on ν-, and ν±1-, and ν±2-fold excitations. For the calculation of the CI matrix this leaves one with only the evaluation of overlap matrix elements between spin-coupled excitations. This leads to a set of ten general matrix element formulas which contain Serber representation matrices of the permutation group Sν×Sν as parameters. Because of the Serber structure of the CI basis these group-theoretical parameters are kept to a minimum such that they can be stored readily in the central memory of a computer for ν?4 and even for higher excitations. As the computational effort required to obtain the CI matrix elements from the general formulas is very small, the algorithm presented appears to constitute for even electron systems a promising alternative to existing CI methods for multiply excited configurations, e.g., the unitary group approach. Our method makes possible the adaptation of spatial symmetries and the selection of any subset of configurations. The algorithm has been implemented in a computer program and tested extensively for ν?4 and singlet ground and excited states.
Syntheses and structures of [UO2( L)5](ClO4)2 and [U( L')4(H2O)4](ClO4)4 ( L is dimethylformamide, L' is N,N-dimethylcarbamide)

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Vologzhanina, A. V.; Pushkin, D. V.; Astashkina, D. A.; Savchenkov, A. V.; Serezhkina, L. B.

2017-09-01

The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [UVIO2(C3H7NO)5](ClO4)2 ( I) and [UIV(C3H8N2O)4(H2O)4](ClO4)4 ( II), where C3H7NO is N,N-dimethylformamide ( Dmfa) and C3H8N2O is N,N-dimethylcarbamide ( a-Dmur), were studied by X-ray diffraction. Complex II and the complex UIV( s-Dmur)4(H2O)4(ClO4)4 ( III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO2( Dmfa)5]2+ and [U( Dmur)4(H2O)4]4+ groups as uranium-containing structural units belonging to the crystal-chemical groups AM 7 1 ( A = UVI, M 1 = O2- and Dmfa) and AM 8 1 ( A = UIV, M 1 = Dmur and H2O) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

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