A first-principles study of carbon-related energy levels in GaN. I. Complexes formed by substitutional/interstitial carbons and gallium/nitrogen vacancies

NASA Astrophysics Data System (ADS)

Matsubara, Masahiko; Bellotti, Enrico

2017-05-01

Various forms of carbon based complexes in GaN are studied with first-principles calculations employing Heyd-Scuseria-Ernzerhof hybrid functionals within the framework of the density functional theory. We consider carbon complexes made of the combinations of single impurities, i.e., CN-CGa, CI-CN , and CI-CGa , where CN, CGa , and CI denote C substituting nitrogen, C substituting gallium, and interstitial C, respectively, and of neighboring gallium/nitrogen vacancies ( VGa / VN ), i.e., CN-VGa and CGa-VN . Formation energies are computed for all these configurations with different charge states after full geometry optimizations. From our calculated formation energies, thermodynamic transition levels are evaluated, which are related to the thermal activation energies observed in experimental techniques such as deep level transient spectroscopy. Furthermore, the lattice relaxation energies (Franck-Condon shift) are computed to obtain optical activation energies, which are observed in experimental techniques such as deep level optical spectroscopy. We compare our calculated values of activation energies with the energies of experimentally observed C-related trap levels and identify the physical origins of these traps, which were unknown before.

Full-dimensional quantum mechanics calculations for the spectroscopic characterization of the isomerization transition states of HOCO/DOCO systems.

PubMed

Ma, Dandan; Ren, Haisheng; Ma, Jianyi

2018-02-14

Full-dimensional quantum mechanics calculations were performed to determine the vibrational energy levels of HOCO and DOCO based on an accurate potential energy surface. Almost all of the vibrational energy levels up to 3500 cm -1 from the vibrational ground state were assigned, and the calculated energy levels in this work are well in agreement with the reported results by Bowman. The corresponding full dimensional wavefunctions present some special features. When the energy level approaches the barrier height, the trans-HOCO and cis-HOCO states strongly couple through tunneling interactions, and the tunneling interaction and Fermi resonance were observed in the DOCO system. The energy level patterns of trans-HOCO, cis-HOCO and trans-DOCO provide a reasonable fitted barrier height using the fitting formula of Field et al., however, a discrepancy exists for the cis-DOCO species which is considered as a random event. Our full-dimensional calculations give positive evidence for the accuracy of the spectroscopic characterization model of the isomerization transition state reported by Field et al., which was developed from one-dimensional model systems. Furthermore, the special case of cis-DOCO in this work means that the isotopic substitution can solve the problem of the accidental failure of Field's spectroscopic characterization model.

A Simple Approach for the Calculation of Energy Levels of Light Atoms

ERIC Educational Resources Information Center

Woodyard, Jack R., Sr.

1972-01-01

Describes a method for direct calculation of energy levels by using elementary techniques. Describes the limitations of the approach but also claims that with a minimum amount of labor a student can get greater understanding of atomic physics problems. (PS)

Novel Δ J =1 Sequence in 78Ge: Possible Evidence for Triaxiality

NASA Astrophysics Data System (ADS)

Forney, A. M.; Walters, W. B.; Chiara, C. J.; Janssens, R. V. F.; Ayangeakaa, A. D.; Sethi, J.; Harker, J.; Alcorta, M.; Carpenter, M. P.; Gürdal, G.; Hoffman, C. R.; Kay, B. P.; Kondev, F. G.; Lauritsen, T.; Lister, C. J.; McCutchan, E. A.; Rogers, A. M.; Seweryniak, D.; Stefanescu, I.; Zhu, S.

2018-05-01

A sequence of low-energy levels in Ge783246 has been identified with spins and parity of 2+, 3+, 4+, 5+, and 6+. Decays within this band proceed strictly through Δ J =1 transitions, unlike similar sequences in neighboring Ge and Se nuclei. Above the 2+ level, members of this sequence do not decay into the ground-state band. Moreover, the energy staggering of this sequence has the phase that would be expected for a γ -rigid structure. The energies and branching ratios of many of the levels are described well by shell-model calculations. However, the calculated reduced transition probabilities for the Δ J =2 in-band transitions imply that they should have been observed, in contradiction with the experiment. Within the calculations of Davydov, Filippov, and Rostovsky for rigid-triaxial rotors with γ =3 0 ° , there are sequences of higher-spin levels connected by strong Δ J =1 transitions which decay in the same manner as those observed experimentally, yet are calculated at too high an excitation energy.

Hybrid Density Functional Study of the Local Structures and Energy Levels of CaAl2O4:Ce3.

PubMed

Lou, Bibo; Jing, Weiguo; Lou, Liren; Zhang, Yongfan; Yin, Min; Duan, Chang-Kui

2018-05-03

First-principles calculations were carried out for the electronic structures of Ce 3+ in calcium aluminate phosphors, CaAl 2 O 4 , and their effects on luminescence properties. Hybrid density functional approaches were used to overcome the well-known underestimation of band gaps of conventional density functional approaches and to calculate the energy levels of Ce 3+ ions more accurately. The obtained 4f-5d excitation and emission energies show good consistency with measured values. A detailed energy diagram of all three sites is obtained, which explains qualitatively all of the luminescent phenomena. With the results of energy levels calculated by combining the hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE06) and the constraint occupancy approach, we are able to construct a configurational coordinate diagram to analyze the processes of capture of a hole or an electron and luminescence. This approach can be applied for systematic high-throughput calculations in predicting Ce 3+ activated luminescent materials with a moderate computing requirement.

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

Abou El-Maaref, A., E-mail: aahmh@hotmail.com; Allam, S.H.; El-Sherbini, Th.M.

The energy levels, oscillator strengths, line strengths, and transition probabilities for transitions among the terms belonging to the 3s{sup 2}3p{sup 2}, 3s3p{sup 3}, 3s{sup 2}3p3d, 3s{sup 2}3p4s, 3s{sup 2}3p4p and 3s{sup 2}3p4d configurations of silicon-like ions (Zn XVII, Ga XVIII, Ge XIX, and As XX) have been calculated using the configuration-interaction code CIV3. The calculations have been carried out in the intermediate coupling scheme using the Breit–Pauli Hamiltonian. The present calculations have been compared with the available experimental data and other theoretical calculations. Most of our calculations of energy levels and oscillator strengths (in length form) show good agreement withmore » both experimental and theoretical data. Lifetimes of the excited levels have also been calculated. -- Highlights: •We have calculated the fine-structure energy levels of Si-like Zn, Ga, Ge and As. •The calculations are performed using the configuration interaction method (CIV3). •We have calculated the oscillator strengths, line strengths and transition rates. •The wavelengths of the transitions are listed in this article. •We also have made comparisons between our data and other calculations.« less

Full-Dimensional Quantum Calculations of Vibrational Levels of NH4(+) and Isotopomers on An Accurate Ab Initio Potential Energy Surface.

PubMed

Yu, Hua-Gen; Han, Huixian; Guo, Hua

2016-04-14

Vibrational energy levels of the ammonium cation (NH4(+)) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4(+) and ND4(+) exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. The low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm(-1).

Electronic Characterization of Defects in Narrow Gap Semiconductors-Comparison of Electronic Energy Levels and Formation Energies in Mercury Cadmium Telluride, Mercury Zinc Telluride, and Mercury Zinc Selenide

NASA Technical Reports Server (NTRS)

Patterson, James D.

1996-01-01

We have used a Green's function technique to calculate the energy levels and formation energy of deep defects in the narrow gap semiconductors mercury cadmium telluride (MCT), mercury zinc telluride (MZT) and mercury zinc selenide (MZS). The formation energy is calculated from the difference between the total energy with an impurity cluster and the total energy for the perfect crystal. Substitutional (including antisite), interstitial (self and foreign), and vacancy deep defects are considered. Relaxation effects are calculated (with molecular dynamics). By use of a pseudopotential, we generalize the ideal vacancy model so as to be able to consider relaxation for vacancies. Different charge states are considered and the charged state energy shift (as computed by a modified Haldane-Anderson model) can be twice that due to relaxation. Different charged states for vacancies were not calculated to have much effect on the formation energy. For all cases we find deep defects in the energy gap only for cation site s-like orbitals or anion site p-like orbitals, and for the substitutional case only the latter are appreciably effected by relaxation. For most cases for MCT, MZT, MZS, we consider x (the concentration of Cd or Zn) in the range appropriate for a band gap of 0.1 eV. For defect energy levels, the absolute accuracy of our results is limited, but the precision is good, and hence chemical trends are accurately predicted. For the same reason, defect formation energies are more accurately predicted than energy level position. We attempt, in Appendix B, to calculate vacancy formation energies using relatively simple chemical bonding ideas due to Harrison. However, these results are only marginally accurate for estimating vacancy binding energies. Appendix C lists all written reports and publications produced for the grant. We include abstracts and a complete paper that summarizes our work which is not yet available.

Energy Levels and Oscillator Strengths for Allowed Transitions in S III

NASA Technical Reports Server (NTRS)

Tayal, S. S.

1995-01-01

We have calculated energy levels and oscillator strengths for dipole-allowed transitions between the terms belonging to the 3s(sup 2)3p(sup 2), 3s3p(sup 3), 3S(sup 2)3p3d, 3S(sup 2)3p4s, 3S(sup 2)3p4p and 3s(sup 2)3p4d configurations of S iii in the LS-coupling scheme. We used flexible radial functions and included a large number of configurations in the configuration-interaction expansions to ensure convergence. The calculated energy levels are in close agreement with the recent laboratory measurement. The present oscillator strengths are compared with other calculations and experiments and most of the existing discrepancies between the available calculations are resolved.

The Kπ Interaction in Finite Volume

NASA Astrophysics Data System (ADS)

Zhou, Dan; Cui, Er-Liang; Chen, Hua-Xing; Geng, Li-Sheng; Zhu, Li-Hua

We calculate energy levels of the Kπ scattering in the K∗ channel in finite volume using chiral unitary theory. We use these energy levels to obtain the Kπ phase shifts and the K∗ meson properties. We also investigate their dependence on the pion mass and compare this with Lattice QCD calculations.

Calculation of Quasi-Particle Energies of Aromatic Self-Assembled Monolayers on Au(111).

PubMed

Li, Yan; Lu, Deyu; Galli, Giulia

2009-04-14

We present many-body perturbation theory calculations of the electronic properties of phenylene diisocyanide self-assembled monolayers (SAMs) on a gold surface. Using structural models obtained within density functional theory (DFT), we have investigated how the SAM molecular energies are modified by self-energy corrections and how they are affected by the presence of the surface. We have employed a combination of GW (G = Green's function; W = screened Coulomb interaction) calculations of the SAM quasi-particle energies and a semiclassical image potential model to account for surface polarization effects. We find that it is essential to include both quasi-particle corrections and surface screening in order to provide a reasonable estimate of the energy level alignment at a SAM-metal interface. In particular, our results show that within the GW approximation the energy distance between phenylene diisocyanide SAM energy levels and the gold surface Fermi level is much larger than that found within DFT, e.g., more than double in the case of low packing densities of the SAM.

The Calculation of Accurate Metal-Ligand Bond Energies

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W.; Partridge, Harry, III; Ricca, Alessandra; Arnold, James O. (Technical Monitor)

1997-01-01

The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

Energy levels and optical properties of neodymium-doped barium fluorapatite

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

Stefanos, Sennay M.; Bonner, Carl E. Jr.; Meegoda, Chandana

Energy levels of the 4f{sup 3} electronic configuration of Nd{sup 3+} in barium fluorapatite, Ba{sub 5}(PO{sub 4}){sub 3}F(B-FAP) have been determined from polarized absorption and fluorescence spectra using crystals at 8 K. Experimental energy-level assignments were made initially by comparing the crystal spectra energy levels with those obtained from those previously reported for Nd{sup 3+} in strontium fluorapatite and fluorapatite. The initial crystal-field parameters were calculated by using lattice summation techniques. The crystal-field parameters were varied to obtain a best fit between experimental and theoretical energies and the final values give a root-mean-square deviation of 7.1 cm-1. The odd-fold crystal-fieldmore » components are used to calculate the emission intensities and lifetimes of the Nd{sup 3+} ions in B-FAP. These calculations yield results in good agreement with the experimental measurements of the absorption and emission cross sections and lifetimes. (c) 2000 American Institute of Physics.« less

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.

FT-Raman, FT-IR spectra and total energy distribution of 3-pentyl-2,6-diphenylpiperidin-4-one: DFT method.

PubMed

Subashchandrabose, S; Saleem, H; Erdogdu, Y; Rajarajan, G; Thanikachalam, V

2011-11-01

FT-Raman and FT-IR spectra were recorded for 3-pentyl-2,6-diphenylpiperidin-4-one (PDPO) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, infrared and the Raman scattering intensities were computed using DFT/6-31G(d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the infrared and Raman spectra, based on the total energy distribution (TED) of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated and compared with X-ray diffraction data. This comparison was good agreement. The intra-molecular charge transfer was calculated by means of natural bond orbital analysis (NBO). Hyperconjugative interaction energy was more during the π-π* transition. Energy gap of the molecule was found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. Atomic charges of the carbon, nitrogen and oxygen were calculated using same level of calculation. Copyright © 2011 Elsevier B.V. All rights reserved.

Novel Δ J = 1 Sequence in Ge 78 : Possible Evidence for Triaxiality

DOE PAGES

Forney, A. M.; Walters, W. B.; Chiara, C. J.; ...

2018-05-22

Here, a sequence of low-energy levels in 78 32Ge 46 has been identified with spins and parity of 2 +, 3 +, 4 +, 5 +, and 6 +. Decays within this band proceed strictly through ΔJ=1 transitions, unlike similar sequences in neighboring Ge and Se nuclei. Above the 2+ level, members of this sequence do not decay into the ground-state band. Moreover, the energy staggering of this sequence has the phase that would be expected for a γ-rigid structure. The energies and branching ratios of many of the levels are described well by shell-model calculations. However, the calculated reducedmore » transition probabilities for the ΔJ=2 in-band transitions imply that they should have been observed, in contradiction with the experiment. Within the calculations of Davydov, Filippov, and Rostovsky for rigid-triaxial rotors with γ=30°, there are sequences of higher-spin levels connected by strong ΔJ=1 transitions which decay in the same manner as those observed experimentally, yet are calculated at too high an excitation energy.« less

A novel ΔJ = 1 sequence in 78Ge: possible evidence for triaxiality

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

Forney, A. M.; Walters, W. B.; Chiara, C. J.

2018-02-20

A sequence of low-energy levels inmore » $$78\\atop{32}$$Ge 46 has been identi ed with spins and parity of 2 +, 3 +, 4 +, 5 +, and 6 +. Decays within this band proceed strictly through ΔJ = 1 transitions, unlike similar sequences in neighboring Ge and Se nuclei. Above the 2 + level, members of this sequence do not decay into the ground-state band. Moreover, the energy staggering of this sequence has the phase that would be expected for a γ-rigid structure. The energies and branching ratios of many of the levels are described well by shell-model calculations. However, the calculated reduced transition probabilities for the ΔJ = 2 in-band transitions imply that they should have been observed, in contradiction with the experiment. Lastly, within the calculations of Davydov, Filippov, and Rostovsky for rigid-triaxial rotors with γ = 30°, there are sequences of higher-spin levels connected by strong ΔJ = 1 transitions which decay in the same manner as those observed experimentally, yet calculated at too high an excitation energy.« less

Novel Δ J = 1 Sequence in Ge 78 : Possible Evidence for Triaxiality

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

Forney, A. M.; Walters, W. B.; Chiara, C. J.

Here, a sequence of low-energy levels in 78 32Ge 46 has been identified with spins and parity of 2 +, 3 +, 4 +, 5 +, and 6 +. Decays within this band proceed strictly through ΔJ=1 transitions, unlike similar sequences in neighboring Ge and Se nuclei. Above the 2+ level, members of this sequence do not decay into the ground-state band. Moreover, the energy staggering of this sequence has the phase that would be expected for a γ-rigid structure. The energies and branching ratios of many of the levels are described well by shell-model calculations. However, the calculated reducedmore » transition probabilities for the ΔJ=2 in-band transitions imply that they should have been observed, in contradiction with the experiment. Within the calculations of Davydov, Filippov, and Rostovsky for rigid-triaxial rotors with γ=30°, there are sequences of higher-spin levels connected by strong ΔJ=1 transitions which decay in the same manner as those observed experimentally, yet are calculated at too high an excitation energy.« less

Full-dimensional quantum calculations of vibrational levels of NH 4 + and isotopomers on an accurate ab initio potential energy surface

DOE PAGES

Hua -Gen Yu; Han, Huixian; Guo, Hua

2016-03-29

Vibrational energy levels of the ammonium cation (NH 4 +) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH 4 + and ND 4 + exhibit a polyad structure, characterized by a collective quantum number P = 2(v 1 + v 3) + v 2 + v 4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data ismore » better than 1 cm –1.« less

Level Energies, Oscillator Strengths and Lifetimes for Transitions in Pb IV

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

Colon, C.; Alonso-Medina, A.; Zanon, A.

2008-10-22

Oscillator strengths for several lines of astrophysical interest arising from some configurations and some levels radiative lifetimes of Pb IV have been calculated. These values were obtained in intermediate coupling (IC) and using ab initio relativistic Hartree-Fock calculations. We use for the IC calculations the standard method of least square fitting of experimental energy levels by means of computer codes from Cowan. Transition Probabilities and oscillator strengths obtained, although in general agreement with the rare experimental data, do present some noticeable discrepancies that are studied in the text.

Electron impact collision strengths in Ne VII

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

Di, L.; Shi, J.R.; Zhao, G., E-mail: gzhao@bao.ac.cn

2012-07-15

The lines of Ne VII have been observed in many astronomical objects, and some transitions from high energy levels were observed both in Seyfert galaxies and stellar coronae. Thus, the atomic data for these transitions are important for modeling. Using the code FAC we calculated the collision strengths based on the distorted-wave method with large configuration interactions included. The Maxwellian averaged effective collision strengths covering the typical temperature range of astronomical and laboratory hot plasmas are presented. We extend the calculation of the energy levels to n=4 and 5. The energy levels, wavelengths, spontaneous transition rates, weighted oscillator strengths, andmore » effective collision strengths were reported. Compared with the results from experiment or previous theoretical calculations a general agreement is found. It is found that the resonance effects are important in calculating the effective collision strengths.« less

Dirac-Fock-Breit-Gaunt calculations for tungsten hexacarbonyl W(CO)6.

PubMed

Malli, Gulzari L

2016-05-21

The first all-electron fully relativistic Dirac-Fock-Breit-Gaunt (DFBG), Dirac-Fock (DF), and nonrelativistic (NR) Hartree-Fock (HF) calculations are reported for octahedral (Oh) tungsten hexacarbonyl W(CO)6. Our DF and NR HF calculations predict atomization energy of 73.76 and 70.33 eV, respectively. The relativistic contribution of ∼3.4 eV to the atomization energy of W(CO)6 is fairly significant. The DF and NR energy for the reaction W + 6CO → W(CO)6 is calculated as -7.90 and -8.86 eV, respectively. The mean bond energy predicted by our NR and DF calculations is 142.5 kJ/mol and 177.5 kJ/mol, respectively, and our predicted DF mean bond energy is in excellent agreement with the experimental value of 179 kJ/mol quoted in the literature. The relativistic effects contribute ∼35 kJ/mol to the mean bond energy and the calculated BSSE is 1.6 kcal/mol, which indicates that the triple zeta basis set used here is fairly good. The mean bond energy and the atomization energy calculated in our DFBG SCF calculations, which include variationally both the relativistic and magnetic Breit effects, is 157.4 kJ/mol and 68.84 eV, respectively. The magnetic Breit effects lead to a decrease of ∼20 kJ/mol and ∼4.9 eV for the mean bond energy and atomization energy, respectively, for W(CO)6. Our calculated magnetic Breit interaction energy of -9.79 eV for the energy of reaction (ΔE) for W + 6CO → W(CO)6 is lower by ∼1.90 eV as compared to the corresponding DF value (ΔE) and contributes significantly to the ΔE. A detailed discussion is presented of electronic structure, bonding, and molecular energy levels at various levels of theory for W(CO)6.

Spectrum and Energy Levels of Five-Times Ionized Zirconium (Zr VI)

PubMed Central

Lindsay, Mark D.

2016-01-01

We carried out a new analysis of the spectrum of five-times-ionized zirconium Zr VI. For this we used sliding-spark discharges together with normal- and grazing-incidence spectrographs to observe the spectrum from 160 to 2000 Å. These observations showed that the analysis of this spectrum by Khan Z. A. et al. 1985 Phys. Scr. 31 837 contained a significant number of incorrect energy levels. We have now classified ∼420 lines as transitions between 23 even-parity levels 73 odd-parity levels. The 4s24p5, 4s4p6, 4s24p44d, 5s, 5d, 6s configurations are now complete, although a few levels of 4s24p45d are tentative. We determined Ritz-type wavelengths for ∼135 lines from the optimized energy levels. The uncertainties range from 0.0003 to 0.0020 Å. Hartree-Fock calculations and least-squares fits of the energy parameters to the observed levels were used to interpret the observed configurations. Oscillator strengths for all classified lines were calculated with the fitted parameters. The results are compared with values for the level energies, percentage compositions, and transition probabilities from recent ab initio theoretical calculations. The ionization energy was revised to 777380±300 cm-1 (96.38±0.04 eV). PMID:27325903

Spectrum and Energy Levels of Five-Times Ionized Zirconium (Zr VI).

PubMed

Reader, Joseph; Lindsay, Mark D

2016-02-01

We carried out a new analysis of the spectrum of five-times-ionized zirconium Zr VI. For this we used sliding-spark discharges together with normal- and grazing-incidence spectrographs to observe the spectrum from 160 to 2000 Å. These observations showed that the analysis of this spectrum by Khan Z. A. et al. 1985 Phys. Scr. 31 837 contained a significant number of incorrect energy levels. We have now classified ∼420 lines as transitions between 23 even-parity levels 73 odd-parity levels. The 4s 2 4p 5 , 4s4p 6 , 4s 2 4p 4 4d, 5s, 5d, 6s configurations are now complete, although a few levels of 4s 2 4p 4 5d are tentative. We determined Ritz-type wavelengths for ∼135 lines from the optimized energy levels. The uncertainties range from 0.0003 to 0.0020 Å. Hartree-Fock calculations and least-squares fits of the energy parameters to the observed levels were used to interpret the observed configurations. Oscillator strengths for all classified lines were calculated with the fitted parameters. The results are compared with values for the level energies, percentage compositions, and transition probabilities from recent ab initio theoretical calculations. The ionization energy was revised to 777380±300 cm -1 (96.38±0.04 eV).

Spectrum and energy levels of five-times ionized zirconium (Zr VI)

NASA Astrophysics Data System (ADS)

Reader, Joseph; Lindsay, Mark D.

2016-02-01

We carried out a new analysis of the spectrum of five-times-ionized zirconium Zr VI. For this we used sliding-spark discharges together with normal- and grazing-incidence spectrographs to observe the spectrum from 160 to 2000 Å. These observations showed that the analysis of this spectrum by Khan et al (1985 Phys. Scr. 31 837) contained a significant number of incorrect energy levels. We have now classified ˜420 lines as transitions between 23 even-parity levels 73 odd-parity levels. The 4s24p5, 4s4p6, 4s24p44d, 5s, 5d, 6s configurations are now complete, although a few levels of 4s24p45d are tentative. We determined Ritz-type wavelengths for ˜135 lines from the optimized energy levels. The uncertainties range from 0.0003 to 0.0020 Å. Hartree-Fock calculations and least-squares fits of the energy parameters to the observed levels were used to interpret the observed configurations. Oscillator strengths for all classified lines were calculated with the fitted parameters. The results are compared with values for the level energies, percentage compositions, and transition probabilities from recent ab initio theoretical calculations. The ionization energy was revised to 777 380 ± 300 cm-1 (96.38 ± 0.04 eV).

Using ‘particle in a box’ models to calculate energy levels in semiconductor quantum well structures

NASA Astrophysics Data System (ADS)

Ebbens, A. T.

2018-07-01

Although infinite potential ‘particle in a box’ models are widely used to introduce quantised energy levels their predictions cannot be quantitatively compared with atomic emission spectra. Here, this problem is overcome by describing how both infinite and finite potential well models can be used to calculate the confined energy levels of semiconductor quantum wells. This is done by using physics and mathematics concepts that are accessible to pre-university students. The results of the models are compared with experimental data and their accuracy discussed.

Absorption spectra of ammonia near 1 μm

NASA Astrophysics Data System (ADS)

Barton, Emma J.; Polyansky, Oleg L.; Yurchenko, Sergei. N.; Tennyson, Jonathan; Civiš, S.; Ferus, M.; Hargreaves, R.; Ovsyannikov, R. I.; Kyuberis, A. A.; Zobov, N. F.; Béguier, S.; Campargue, A.

2017-12-01

An ammonia absorption spectrum recorded at room temperature in the region 8800-10,400 cm-1 is analysed using a variational line list, BYTe, and ground state energies determined using the MARVEL procedure. BYTe is used as a starting point to initialise assignments by combination differences and the method of branches. Assignments are presented for the region 9400-9850 cm-1. 642 lines are assigned to 6 previously unobserved vibrational bands, (2v1 + 2 v42) ±, (2v1 + v31) ± and (v1 + v31 + 2 v42) ±, leading to 428 new energy levels with 208 confirmed by combination differences. A recently calculated purely ab initio NH3 PES is also used to calculate rovibrational energy levels. Comparison with assigned levels shows better agreement between observed and calculated levels than for BYTe for higher vibrational bands.

Energy levels and radiative rates for transitions in Cr-like Co IV and Ni V

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Bogdanovich, P.; Karpuškienė, R.; Keenan, F. P.; Kisielius, R.; Stancalie, V.

2016-01-01

We report calculations of energy levels and radiative rates (A-values) for transitions in Cr-like Co IV and Ni V. The quasi-relativistic Hartree-Fock (QRHF) code is adopted for calculating the data although GRASP (general-purpose relativistic atomic structure package) and flexible atomic code (FAC) have also been employed for comparison purposes. No radiative rates are available in the literature to compare with our results, but our calculated energies are in close agreement with those compiled by NIST for a majority of the levels. However, there are discrepancies for a few levels of up to 3%. The A-values are listed for all significantly contributing E1, E2 and M1 transitions, and the corresponding lifetimes reported, although unfortunately no previous theoretical or experimental results exist to compare with our data.

Extended calculations of energies, transition rates, and lifetimes for F-like Kr XXVIII

NASA Astrophysics Data System (ADS)

Zhang, C. Y.; Si, R.; Yao, K.; Gu, M. F.; Wang, K.; Chen, C. Y.

2018-02-01

The excitation energies, lifetimes, wavelengths and E1, E2, M1 and M2 transition rates for the lowest 389 levels of the 2l7, 2l63l‧, 2l64l‧, and 2l65l‧ configurations from second-order many-body perturbation theory (MBPT) calculations, and the results for the lowest 200 states of the 2l7, 2l63l‧, and 2l64l‧ configurations from multi-configuration Dirac-Hartree-Fock (MCDHF) calculations in F-like Kr XXVIII are presented in this work. The relative differences between our two sets of level energies are mostly within 0.005% for the lowest 200 levels. Comparisons are made with experimental and other available theoretical results to assess the reliability and accuracy of the present calculations. We believe them to be the most complete and accurate results for Kr XXVIII at present.

Theoretical study of the crystal-field energy levels and two-photon absorption intensities of Tb3+ in cubic host lattices.

PubMed

Duan, Chang-Kui; Tanner, Peter A

2011-03-17

Published two photon excitation (TPE) intensities for the cubic elpasolite systems Cs(2)NaTbX(6) (X = Cl, F) have been simulated by a calculation of two photon absorption (TPA) intensities which takes into account electric dipole transitions involving the detailed crystal-field structure of 4f(7)5d intermediate states, as well as the interactions of the 4f(7) core with the d-electron. The intensity calculation employed parameters from an energy level calculation which not only presented an accurate fit, but also yielded parameters consistent with those from other lanthanide ions. The calculated intensities were used to confirm or adjust the previous assignments of energy levels, resulting in some minor revisions. Generally, the TPA intensity simulations were in better agreement with experimental data for the fluoride, rather than the chloride, system and possible reasons for this are given.

24 CFR 990.185 - Utilities expense level: Incentives for energy conservation/rate reduction.

Code of Federal Regulations, 2012 CFR

2012-04-01

... the energy conservation measures and other direct costs related to the energy project under the... for energy conservation/rate reduction. 990.185 Section 990.185 Housing and Urban Development... Calculating Formula Expenses § 990.185 Utilities expense level: Incentives for energy conservation/rate...

24 CFR 990.185 - Utilities expense level: Incentives for energy conservation/rate reduction.

Code of Federal Regulations, 2013 CFR

2013-04-01

... the energy conservation measures and other direct costs related to the energy project under the... for energy conservation/rate reduction. 990.185 Section 990.185 Housing and Urban Development... Calculating Formula Expenses § 990.185 Utilities expense level: Incentives for energy conservation/rate...

24 CFR 990.185 - Utilities expense level: Incentives for energy conservation/rate reduction.

Code of Federal Regulations, 2014 CFR

2014-04-01

... the energy conservation measures and other direct costs related to the energy project under the... for energy conservation/rate reduction. 990.185 Section 990.185 Housing and Urban Development... Calculating Formula Expenses § 990.185 Utilities expense level: Incentives for energy conservation/rate...

Observations of the high vibrational levels of the B ' ' B ¯ 1 Σu + state of H2

NASA Astrophysics Data System (ADS)

Chartrand, A. M.; Duan, W.; Ekey, R. C.; McCormack, E. F.

2016-01-01

Double-resonance laser spectroscopy via the E F 1 Σg + , v ' = 6 , J ' = 0 -2 state was used to probe the high vibrational levels of the B ' ' B ¯ 1 Σu + state of molecular hydrogen. Resonantly enhanced multiphoton ionization spectra were recorded by detecting ion production as a function of energy using a time of flight mass spectrometer. New measurements of energies for the v = 51-66 levels for the B ' ' B ¯ state of H2 are reported, which, taken with previous results, span the v = 46-69 vibrational levels. Results for energy levels are compared to theoretical close-coupled calculations [L. Wolniewicz, T. Orlikowski, and G. Staszewska, J. Mol. Spectrosc. 238, 118-126 (2006)]. The average difference between the 84 measured energies and calculated energies is -3.8 cm-1 with a standard deviation of 5.3 cm-1. This level of agreement showcases the success of the theoretical calculations in accounting for the strong rovibronic mixing of the 1 Σu + and 1 Πu + states. Due to the ion-pair character of the outer well, the observed energies of the vibrational levels below the third dissociation limit smoothly connect with previously observed energies of ion-pair states above this limit. The results provide an opportunity for testing a heavy Rydberg multi-channel quantum defect analysis of the high vibrational states below the third dissociation limit.

Calculations of the energy levels and oscillator strengths of the Ne-like Fe Ion (Fe XVII)

NASA Astrophysics Data System (ADS)

Zhong, Jia-yong; Zhang, Jie; Zhao, Gang; Lu, Xin

Energy levels and oscillator strengths among the 27 fine-structure levels belonging to the (ls 22s 2)2p 6, 2p 53s, 2p 53p and 2p 53d configurations of the neon-like iron ion have been calculated using three atomic structure codes RCN/RCG, AUTOSTRUCTURE (AS) and GRASP. Relativistic corrections of the wave functions are taken into account in the RCN/RCG calculation. The results agree well with the available experimental and theoretical data. The accuracy of the three codes is analysed.

Energy Levels and Radiative Rates for Transitions in F-like Sc XIII and Ne-like Sc XII and Y XXX

NASA Astrophysics Data System (ADS)

Aggarwal, Kanti

2018-05-01

Energy levels, radiative rates and lifetimes are reported for F-like Sc~XIII and Ne-like Sc~XII and Y~XXX for which the general-purpose relativistic atomic structure package ({\\sc grasp}) has been adopted. For all three ions limited data exist in the literature but comparisons have been made wherever possible to assess the accuracy of the calculations. In the present work the lowest 102, 125 and 139 levels have been considered for the respective ions. Additionally, calculations have also been performed with the flexible atomic code ({\\sc fac}) to (particularly) confirm the accuracy of energy levels.

Inversion of chalcogen defect levels in silicon - An MNDO study. [modified neglect of diatomic overlap

NASA Technical Reports Server (NTRS)

Singh, R. K.; Sahu, S. N.; Singh, V. A.; Corbett, J. W.

1985-01-01

MNDO (modified neglect of diatomic overlap) calculations have been carried out for substitutional oxygen and sulfur impurities in silicon. The calculations of the gap levels reveal a reversal of trend with atomic ionization energies in agreement with self-consistent Green function results, and analysis of the MNDO charge distribution supports the view that the electronegativity difference between oxygen and sulfur gives rise to this shallower energy level.

EXCITATION OF LEVELS IN Li$sup 7$ BY INELASTIC ELECTRON SCATTERING

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

Bernheim, M; Bishop, G R

1963-07-15

Cross sections for the excitation of some levels in Li/sup 7/ up to 8- Mev excitation energy were measured by the iiielastic scattering of electrons for a variety of incident electron energies and scatiering angles. The cross section calculated in first Dorn approximation is expected to be valid for this nucleus. The calculated angular distribution is given for different spin and parity and for different levels of excitation. (R.E.U.)

Importance of semicore states in GW calculations for simulating accurately the photoemission spectra of metal phthalocyanine molecules.

PubMed

Umari, P; Fabris, S

2012-05-07

The quasi-particle energy levels of the Zn-Phthalocyanine (ZnPc) molecule calculated with the GW approximation are shown to depend sensitively on the explicit description of the metal-center semicore states. We find that the calculated GW energy levels are in good agreement with the measured experimental photoemission spectra only when explicitly including the Zn 3s and 3p semicore states in the valence. The main origin of this effect is traced back to the exchange term in the self-energy GW approximation. Based on this finding, we propose a simplified approach for correcting GW calculations of metal phthalocyanine molecules that avoids the time-consuming explicit treatment of the metal semicore states. Our method allows for speeding up the calculations without compromising the accuracy of the computed spectra.

Atomic Data and Spectral Line Intensities for NI XVII

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Landi, E.

2011-01-01

Electron impact collision strengths, energy levels, oscillator strengths, and spontaneous radiative decay rates are calculated for Ni XVII. We include in the calculations the 23 lowest configurations, corresponding to 159 fine-structure levels: 3l3l', 3l4l0'' , and 3s5l0''' , with l,l' = s,p,d, l'' = s,p,d, f, and l''' = s,p,d. Collision strengths are calculated at five incident energies for all transitions at varying energies above the threshold of each transition. One additional energy, very close to the threshold of each transition, has also been included. Calculations have been carried out using the Flexible Atomic Code in the distorted wave approximation. Additional calculations have been performed with the University College London suite of codes for comparison. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates of the present work, statistical equilibrium equations for level populations are solved at electron densities covering the range of 10(exp 8) - 10(exp 14) / cubic cm and at an electron temperature of logT(sub e)e(K) = 6.5, corresponding to the maximum abundance of Ni XVII. Spectral line intensities are calculated, and their diagnostic relevance is discussed. This dataset will be made available in the next version of the CHIANTI database

Rovibrational bound states of SO2 isotopologues. I: Total angular momentum J = 0-10

NASA Astrophysics Data System (ADS)

Kumar, Praveen; Ellis, Joseph; Poirier, Bill

2015-04-01

Isotopic variation of the rovibrational bound states of SO2 for the four stable sulfur isotopes 32-34,36S is investigated in comprehensive detail. In a two-part series, we compute the low-lying energy levels for all values of total angular momentum in the range J = 0-20. All rovibrational levels are computed, to an extremely high level of numerical convergence. The calculations have been carried out using the ScalIT suite of parallel codes. The present study (Paper I) examines the J = 0-10 rovibrational levels, providing unambiguous symmetry and rovibrational label assignments for each computed state. The calculated vibrational energy levels exhibit very good agreement with previously reported experimental and theoretical data. Rovibrational energy levels, calculated without any Coriolis approximations, are reported here for the first time. Among other potential ramifications, this data will facilitate understanding of the origin of mass-independent fractionation of sulfur isotopes in the Archean rock record-of great relevance for understanding the "oxygen revolution".

The problem of hole localization in inner-shell states of N2 and CO2 revisited with complete active space self-consistent field approach.

PubMed

Rocha, Alexandre B; de Moura, Carlos E V

2011-12-14

Potential energy curves for inner-shell states of nitrogen and carbon dioxide molecules are calculated by inner-shell complete active space self-consistent field (CASSCF) method, which is a protocol, recently proposed, to obtain specifically converged inner-shell states at multiconfigurational level. This is possible since the collapse of the wave function to a low-lying state is avoided by a sequence of constrained optimization in the orbital mixing step. The problem of localization of K-shell states is revisited by calculating their energies at CASSCF level based on both localized and delocalized orbitals. The localized basis presents the best results at this level of calculation. Transition energies are also calculated by perturbation theory, by taking the above mentioned MCSCF function as zeroth order wave function. Values for transition energy are in fairly good agreement with experimental ones. Bond dissociation energies for N(2) are considerably high, which means that these states are strongly bound. Potential curves along ground state normal modes of CO(2) indicate the occurrence of Renner-Teller effect in inner-shell states. © 2011 American Institute of Physics

Refined energetic ordering for sulphate-water (n = 3-6) clusters using high-level electronic structure calculations

NASA Astrophysics Data System (ADS)

Lambrecht, Daniel S.; McCaslin, Laura; Xantheas, Sotiris S.; Epifanovsky, Evgeny; Head-Gordon, Martin

2012-10-01

This work reports refinements of the energetic ordering of the known low-energy structures of sulphate-water clusters ? (n = 3-6) using high-level electronic structure methods. Coupled cluster singles and doubles with perturbative triples (CCSD(T)) is used in combination with an estimate of basis set effects up to the complete basis set limit using second-order Møller-Plesset theory. Harmonic zero-point energy (ZPE), included at the B3LYP/6-311 + + G(3df,3pd) level, was found to have a significant effect on the energetic ordering. In fact, we show that the energetic ordering is a result of a delicate balance between the electronic and vibrational energies. Limitations of the ZPE calculations, both due to electronic structure errors, and use of the harmonic approximation, probably constitute the largest remaining errors. Due to the often small energy differences between cluster isomers, and the significant role of ZPE, deuteration can alter the relative energies of low-lying structures, and, when it is applied in conjunction with calculated harmonic ZPEs, even alters the global minimum for n = 5. Experiments on deuterated clusters, as well as more sophisticated vibrational calculations, may therefore be quite interesting.

Accurate anharmonic zero-point energies for some combustion-related species from diffusion Monte Carlo

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

Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.

Full dimensional analytic potential energy surfaces based on CCSD(T)/cc-pVTZ calculations have been determined for 48 small combustion related molecules. The analytic surfaces have been used in Diffusion Monte Carlo calculations of the anharmonic, zero point energies. Here, the resulting anharmonicity corrections are compared to vibrational perturbation theory results based both on the same level of electronic structure theory and on lower level electronic structure methods (B3LYP and MP2).

Accurate Anharmonic Zero-Point Energies for Some Combustion-Related Species from Diffusion Monte Carlo.

PubMed

Harding, Lawrence B; Georgievskii, Yuri; Klippenstein, Stephen J

2017-06-08

Full-dimensional analytic potential energy surfaces based on CCSD(T)/cc-pVTZ calculations have been determined for 48 small combustion-related molecules. The analytic surfaces have been used in Diffusion Monte Carlo calculations of the anharmonic zero-point energies. The resulting anharmonicity corrections are compared to vibrational perturbation theory results based both on the same level of electronic structure theory and on lower-level electronic structure methods (B3LYP and MP2).

Accurate anharmonic zero-point energies for some combustion-related species from diffusion Monte Carlo

DOE PAGES

Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.

2017-05-17

Full dimensional analytic potential energy surfaces based on CCSD(T)/cc-pVTZ calculations have been determined for 48 small combustion related molecules. The analytic surfaces have been used in Diffusion Monte Carlo calculations of the anharmonic, zero point energies. Here, the resulting anharmonicity corrections are compared to vibrational perturbation theory results based both on the same level of electronic structure theory and on lower level electronic structure methods (B3LYP and MP2).

Energy levels of one-dimensional systems satisfying the minimal length uncertainty relation

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

Bernardo, Reginald Christian S., E-mail: rcbernardo@nip.upd.edu.ph; Esguerra, Jose Perico H., E-mail: jesguerra@nip.upd.edu.ph

2016-10-15

The standard approach to calculating the energy levels for quantum systems satisfying the minimal length uncertainty relation is to solve an eigenvalue problem involving a fourth- or higher-order differential equation in quasiposition space. It is shown that the problem can be reformulated so that the energy levels of these systems can be obtained by solving only a second-order quasiposition eigenvalue equation. Through this formulation the energy levels are calculated for the following potentials: particle in a box, harmonic oscillator, Pöschl–Teller well, Gaussian well, and double-Gaussian well. For the particle in a box, the second-order quasiposition eigenvalue equation is a second-ordermore » differential equation with constant coefficients. For the harmonic oscillator, Pöschl–Teller well, Gaussian well, and double-Gaussian well, a method that involves using Wronskians has been used to solve the second-order quasiposition eigenvalue equation. It is observed for all of these quantum systems that the introduction of a nonzero minimal length uncertainty induces a positive shift in the energy levels. It is shown that the calculation of energy levels in systems satisfying the minimal length uncertainty relation is not limited to a small number of problems like particle in a box and the harmonic oscillator but can be extended to a wider class of problems involving potentials such as the Pöschl–Teller and Gaussian wells.« less

The excitation of electronic transverse energy levels in an intense magnetic field

NASA Technical Reports Server (NTRS)

Bussard, R. W.

1978-01-01

Observations of the X-ray pulsar Hercules X-1 show a line emission feature at about 60 keV, which has been interpreted as the fundamental electron cyclotron line in a magnetic field of around six trillion gauss. In this interpretation, the line radiation results from transitions between transverse energy levels, which are quantized by the field. The expected line luminosity from the excitation of these levels by protons which are falling into the polar cap of a neutron star are calculated. They are assumed to attain kinetic energies up to around 200 MeV, the gravitational potential energy at the surface. The cross sections for high energy Coulomb encounters between small pitch angle protons and electrons in a strong field are measured and used to calculate the energy loss rate of the infalling protons. This rate, together with the rate of elastic nuclear proton collisions, is then used to calculate the number of line photons an infalling proton can be expected to produce, directly or indirectly. The results are applied to Hercules X-1.

A Recursive Method for Calculating Certain Partition Functions.

ERIC Educational Resources Information Center

Woodrum, Luther; And Others

1978-01-01

Describes a simple recursive method for calculating the partition function and average energy of a system consisting of N electrons and L energy levels. Also, presents an efficient APL computer program to utilize the recursion relation. (Author/GA)

Atomic Data and Spectral Line Intensities for CA XVII

NASA Technical Reports Server (NTRS)

Bhatia, A.K.; Landi, E.

2007-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ca XVII. The configurations used are 2s(sup 2), 2s2p, 2p(sup 2), 2l3l', 214l' and 2s5l', with l = s,p and l' = s,p, d giving rise to 92 fine-structure levels in intermediate coupling. Collision strengths are calculated at seven incident energies (15, 30, 75, 112.5, 150, 187.5 and 225 Ry) for the transitions within the three lowest configurations corresponding to the 10 lowest energy levels, and five incident energies (75, 112.5, 150, 187.5 and 225 Ry) for transitions between the lowest five levels and the n = 3,4,5 configurations. Calculations have been carried out using the distorted wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates of the present work, and R-Matrix results for the 2s2, 2s2p, 2p2 configurations available in the literature, statistical equilibrium equations for level populations are solved at electron densities covering the range of 10(exp 8)-10(exp 14)/cu cm at an electron temperature of log Te(K)=6.7, corresponding to the maximum abundance of Ca XVII. Spectral line intensities are calculated, and their diagnostic relevance L; discussed. This dataset will be made available in the next version of the CHIANTI database.

Quantum chemical calculations of glycine glutaric acid

NASA Astrophysics Data System (ADS)

Arioǧlu, ćaǧla; Tamer, Ömer; Avci, Davut; Atalay, Yusuf

2017-02-01

Density functional theory (DFT) calculations of glycine glutaric acid were performed by using B3LYP levels with 6-311++G(d,p) basis set. The theoretical structural parameters such as bond lengths and bond angles are in a good agreement with the experimental values of the title compound. HOMO and LUMO energies were calculated, and the obtained energy gap shows that charge transfer occurs in the title compound. Vibrational frequencies were calculated and compare with experimental ones. 3D molecular surfaces of the title compound were simulated using the same level and basis set. Finally, the 13C and 1H NMR chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method.

Calculations with spectroscopic accuracy for energies, transition rates, hyperfine interaction constants, and Landé gJ-factors in nitrogen-like Kr XXX

NASA Astrophysics Data System (ADS)

Wang, K.; Li, S.; Jönsson, P.; Fu, N.; Dang, W.; Guo, X. L.; Chen, C. Y.; Yan, J.; Chen, Z. B.; Si, R.

2017-01-01

Extensive self-consistent multi-configuration Dirac-Fock (MCDF) calculations and second-order many-body perturbation theory (MBPT) calculations are performed for the lowest 272 states belonging to the 2s22p3, 2s2p4, 2p5, 2s22p23l, and 2s2p33l (l=s, p, d) configurations of N-like Kr XXX. Complete and consistent data sets of level energies, wavelengths, line strengths, oscillator strengths, lifetimes, AJ, BJ hyperfine interaction constants, Landé gJ-factors, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), magnetic quadrupole (M2) transition rates among all these levels are given. The present MCDF and MBPT results are compared with each other and with other available experimental and theoretical results. The mean relative difference between our two sets of level energies is only about 0.003% for these 272 levels. The accuracy of the present calculations are high enough to facilitate identification of many observed spectral lines. These accurate data can be served as benchmark for other calculations and can be useful for fusion plasma research and astrophysical applications.

High-temperature partition functions, specific heats and spectral radiative properties of diatomic molecules with an improved calculation of energy levels

NASA Astrophysics Data System (ADS)

Qin, Z.; Zhao, J. M.; Liu, L. H.

2018-05-01

The level energies of diatomic molecules calculated by the frequently used Dunham expansion will become less accurate for high-lying vibrational and rotational levels. In this paper, the potential curves for the lower-lying electronic states with accurate spectroscopic constants are reconstructed using the Rydberg-Klein-Rees (RKR) method, which are extrapolated to the dissociation limits by fitting of the theoretical potentials, and the rest of the potential curves are obtained from the ab-initio results in the literature. Solving the rotational dependence of the radial Schrödinger equation over the obtained potential curves, we determine the rovibrational level energies, which are then used to calculate the equilibrium and non-equilibrium thermodynamic properties of N2, N2+, NO, O2, CN, C2, CO and CO+. The partition functions and the specific heats are systematically validated by available data in the literature. Finally, we calculate the radiative source strengths of diatomic molecules in thermodynamic equilibrium, which agree well with the available values in the literature. The spectral radiative intensities for some diatomic molecules in thermodynamic non-equilibrium are calculated and validated by available experimental data.

First-Principles Approach to Energy Level Alignment at Aqueous Semiconductor Interfaces

NASA Astrophysics Data System (ADS)

Hybertsen, Mark

2015-03-01

We have developed a first principles method to calculate the energy level alignment between semiconductor band edges and reference energy levels at aqueous interfaces. This alignment is fundamental to understand the electrochemical characteristics of any semiconductor electrode in general and the potential for photocatalytic activity in particular. For example, in the search for new photo-catalytic materials, viable candidates must demonstrate both efficient absorption of the solar spectrum and an appropriate alignment of the band edge levels in the semiconductor to the redox levels for the target reactions. In our approach, the interface-specific contribution to the electrostatic step across the interface is evaluated using density functional theory (DFT) based molecular dynamics to sample the physical interface structure and the corresponding change in the electrostatic potential at the interface. The reference electronic levels in the semiconductor and in the water are calculated using the GW approach, which naturally corrects for errors inherent in the use of Kohn-Sham energy eigenvalues to approximate the electronic excitation energies in each material. Taken together, our calculations provide the alignment of the semiconductor valence band edge to the centroid of the highest occupied 1b1 level in water. The known relationship of the 1b1 level to the normal hydrogen electrode completes the connection to electrochemical levels. We discuss specific results for GaN, ZnO, and TiO2. The effect of interface structural motifs, such as different degrees of water dissociation, and of dynamical characteristics, will be presented together with available experimental data. Work supported by the US Department of Energy, Office of Basic Energy Sciences under Contract No. DE-AC02-98CH10886.

Atomic Data and Spectral Line Intensities for Ca IX

NASA Technical Reports Server (NTRS)

Landi, E.; Bhatia, A. K.

2012-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ca IX. We include in the calculations the 33 lowest configurations in the n = 3, 4, 5 complexes, corresponding to 283 fine structure levels in the 3l3l ', 3l4l'' and 3l4l''' configurations, where l,l' = s, p, d, l '' = s, p, d, f and l''' = s, p, d, f, g. Collision strengths are calculated at five incident energies for all transitions: 5.8, 13.6, 24.2, 38.6 and 57.9 Ry above the threshold of each transition. An additional energy, very close to the transition threshold, has been added, whose value is between 0.0055 Ry and 0.23 Ry depending on the levels involved. Calculations have been carried out using the Flexible Atomic Code and the distorted wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates calculated in the present work, statistical equilibrium equations for level populations are solved at electron densities covering the 10(exp 8)-10(exp 14)/cubic cm range and at an electron temperature of log T(sub e)(K)=5.8, corresponding to the maximum abundance of Ca IX. Spectral line intensities are calculated, and their diagnostic relevance is discussed.

Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach

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

Duchemin, Ivan, E-mail: ivan.duchemin@cea.fr; Jacquemin, Denis; Institut Universitaire de France, 1 rue Descartes, 75005 Paris Cedex 5

We have implemented the polarizable continuum model within the framework of the many-body Green’s function GW formalism for the calculation of electron addition and removal energies in solution. The present formalism includes both ground-state and non-equilibrium polarization effects. In addition, the polarization energies are state-specific, allowing to obtain the bath-induced renormalisation energy of all occupied and virtual energy levels. Our implementation is validated by comparisons with ΔSCF calculations performed at both the density functional theory and coupled-cluster single and double levels for solvated nucleobases. The present study opens the way to GW and Bethe-Salpeter calculations in disordered condensed phases ofmore » interest in organic optoelectronics, wet chemistry, and biology.« less

Molecular structure and vibrational assignments of 2,4-dichlorophenoxyacetic acid herbicide

NASA Astrophysics Data System (ADS)

Badawi, Hassan M.

2010-09-01

The structural stability of 2,4-dichlorophenoxyacetic acid was investigated by the DFT-B3LYP and the ab initio MP2 calculations with the 6-311G** basis set. From the calculations at both levels of theory the Cgcpp structure was predicted to be the lowest energy minimum for the acid. The DFT and the MP2 levels disagreed about the nature of the second stable structure of 2,4-dichlorophenoxyacetic acid. At the DFT-B3LYP level of calculation the planar Tttp ( transoid O dbnd C sbnd O sbnd H) and the non-planar Tgcpp ( cisoid O dbnd C sbnd O sbnd H) forms were predicted to be 0.7 and 1.5 kcal/mol, respectively higher in energy than the Cgcpp conformation. At the MP2 level the two high energy Tttp and Tgcpp forms were predicted to be 2.7 and 1.4 kcal/mol, respectively higher in energy than the ground state Cgcpp structure. The Tgcpp form was adopted as the second possible structure of 2,4-dichlorophenoxyacetic acid on the basis of the fact that the Møller-Plesset calculations account better than the DFT ones for the non-bonding O⋯H interactions. The vibrational frequencies of the lowest energy Cgcpp conformer were computed at the B3LYP level of theory and tentative vibrational assignments were provided on the basis of normal coordinate analysis and experimental infrared and Raman data.

Calculated gadolinium atomic electron energy levels and Auger electron emission probability as a function of atomic number Z

NASA Astrophysics Data System (ADS)

Miloshevsky, G. V.; Tolkach, V. I.; Shani, Gad; Rozin, Semion

2002-06-01

Auger electron interaction with matter is gaining importance in particular in medical application of radiation. The production probability and energy spectrum is therefore of great importance. A good source of Auger electrons is the 157Gd(n,γ) 158Gd reaction. The present article describes calculations of electron levels in Gd atoms and provides missing data of outer electron energy levels. The energy of these electron levels missing in published tables, was found to be in the 23-24 and 6-7 eV energy ranges respectively. The probability of Auger emission was calculated as an interaction of wave function of the initial and final electron states. The wave functions were calculated using the Hartree-Fock-Slater approximation with relativistic correction. The equations were solved using a spherical symmetry potential. The error for inner shell level is less than 10%, it is increased to the order of 10-15% for the outer shells. The width of the Auger process changes from 0.1 to 1.2 eV for atomic number Z from 5 to 70. The fluorescence yield width changes five orders of magnitude in this range. Auger electron emission width from the K shell changes from 10 -2 to ˜1 eV with Z changing from 10 to 64, depending on the final state. For the L shell it changes from 0 to 0.25 when it Z changes from 20 to 64.

Calculation of the X-Ray emission K and L 2,3 bands of metallic magnesium and aluminum with allowance for multielectron effects

NASA Astrophysics Data System (ADS)

Ovcharenko, R. E.; Tupitsyn, I. I.; Savinov, E. P.; Voloshina, E. N.; Dedkov, Yu. S.; Shulakov, A. S.

2014-01-01

A procedure is proposed to calculate the shape of the characteristic X-ray emission bands of metals with allowance for multielectron effects. The effects of the dynamic screening of a core vacancy by conduction electrons and the Auger effect in the valence band are taken into account. The dynamic screening of a core vacancy, which is known to be called the MND (Mahan-Nozeieres-De Dominics) effect, is taken into account by an ab initio band calculation of crystals using the PAW (projected augmented waves) method. The Auger effect is taken into account by a semiempirical method using the approximation of a quadratic dependence of the level width in the valence band on the difference between the level energy and the Fermi energy. The proposed calculation procedure is used to describe the X-ray emission K and L 2,3 bands of metallic magnesium and aluminum crystals. The calculated spectra agree well with the experimental bands both near the Fermi level and in the low-energy part of the spectra in all cases.

Energy levels, wavelengths, and transition rates of multipole transitions (E1, E2, M1, M2) in Au{sup 67+} and Au{sup 66+} ions

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

Hamasha, Safeia, E-mail: safeia@hu.edu.jo

2013-11-15

The fully relativistic configuration interaction method of the FAC code is used to calculate atomic data for multipole transitions in Mg-like Au (Au{sup 67+}) and Al-like Au (Au{sup 66+}) ions. Generated atomic data are important in the modeling of M-shell spectra for heavy Au ions and Au plasma diagnostics. Energy levels, oscillator strengths and transition rates are calculated for electric-dipole (E1), electric quadrupole (E2), magnetic dipole (M1), and magnetic quadrupole (M2) for transitions between excited and ground states 3l−nl{sup ′}, such that n=4,5,6,7. The local central potential is derived using the Dirac–Fock–Slater method. Correlation effects to all orders are consideredmore » by the configuration interaction expansion. All relativistic effects are included in the calculations. Calculated energy levels are compared against published values that were calculated using the multi-reference many body perturbation theory, which includes higher order QED effects. Favorable agreement was observed, with less than 0.15% difference.« less

Converging ligand-binding free energies obtained with free-energy perturbations at the quantum mechanical level.

PubMed

Olsson, Martin A; Söderhjelm, Pär; Ryde, Ulf

2016-06-30

In this article, the convergence of quantum mechanical (QM) free-energy simulations based on molecular dynamics simulations at the molecular mechanics (MM) level has been investigated. We have estimated relative free energies for the binding of nine cyclic carboxylate ligands to the octa-acid deep-cavity host, including the host, the ligand, and all water molecules within 4.5 Å of the ligand in the QM calculations (158-224 atoms). We use single-step exponential averaging (ssEA) and the non-Boltzmann Bennett acceptance ratio (NBB) methods to estimate QM/MM free energy with the semi-empirical PM6-DH2X method, both based on interaction energies. We show that ssEA with cumulant expansion gives a better convergence and uses half as many QM calculations as NBB, although the two methods give consistent results. With 720,000 QM calculations per transformation, QM/MM free-energy estimates with a precision of 1 kJ/mol can be obtained for all eight relative energies with ssEA, showing that this approach can be used to calculate converged QM/MM binding free energies for realistic systems and large QM partitions. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

Converging ligand‐binding free energies obtained with free‐energy perturbations at the quantum mechanical level

PubMed Central

Olsson, Martin A.; Söderhjelm, Pär

2016-01-01

In this article, the convergence of quantum mechanical (QM) free‐energy simulations based on molecular dynamics simulations at the molecular mechanics (MM) level has been investigated. We have estimated relative free energies for the binding of nine cyclic carboxylate ligands to the octa‐acid deep‐cavity host, including the host, the ligand, and all water molecules within 4.5 Å of the ligand in the QM calculations (158–224 atoms). We use single‐step exponential averaging (ssEA) and the non‐Boltzmann Bennett acceptance ratio (NBB) methods to estimate QM/MM free energy with the semi‐empirical PM6‐DH2X method, both based on interaction energies. We show that ssEA with cumulant expansion gives a better convergence and uses half as many QM calculations as NBB, although the two methods give consistent results. With 720,000 QM calculations per transformation, QM/MM free‐energy estimates with a precision of 1 kJ/mol can be obtained for all eight relative energies with ssEA, showing that this approach can be used to calculate converged QM/MM binding free energies for realistic systems and large QM partitions. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:27117350

Energetics using the single point IMOMO (integrated molecular orbital+molecular orbital) calculations: Choices of computational levels and model system

NASA Astrophysics Data System (ADS)

Svensson, Mats; Humbel, Stéphane; Morokuma, Keiji

1996-09-01

The integrated MO+MO (IMOMO) method, recently proposed for geometry optimization, is tested for accurate single point calculations. The principle idea of the IMOMO method is to reproduce results of a high level MO calculation for a large ``real'' system by dividing it into a small ``model'' system and the rest and applying different levels of MO theory for the two parts. Test examples are the activation barrier of the SN2 reaction of Cl-+alkyl chlorides, the C=C double bond dissociation of olefins and the energy of reaction for epoxidation of benzene. The effects of basis set and method in the lower level calculation as well as the effects of the choice of model system are investigated in detail. The IMOMO method gives an approximation to the high level MO energetics on the real system, in most cases with very small errors, with a small additional cost over the low level calculation. For instance, when the MP2 (Møller-Plesset second-order perturbation) method is used as the lower level method, the IMOMO method reproduces the results of very high level MO method within 2 kcal/mol, with less than 50% of additional computer time, for the first two test examples. When the HF (Hartree-Fock) method is used as the lower level method, it is less accurate and depends more on the choice of model system, though the improvement over the HF energy is still very significant. Thus the IMOMO single point calculation provides a method for obtaining reliable local energetics such as bond energies and activation barriers for a large molecular system.

Understanding the photoluminescence characteristics of Eu{sup 3+}-doped double-perovskite by electronic structure calculation

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

Ghosh, Binita; Halder, Saswata; Sinha, T. P.

2016-05-23

Europium-doped luminescent barium samarium tantalum oxide Ba{sub 2}SmTaO{sub 6} (BST) has been investigated by first-principles calculation, and the crystal structure, electronic structure, and optical properties of pure BST and Eu-doped BST have been examined and compared. Based on the calculated results, the luminescence properties and mechanism of Eu-doped BST has been discussed. In the case of Eu-doped BST, there is an impurity energy band at the Fermi level, which is formed by seven spin up energy levels of Eu and act as the luminescent centre, which is evident from the band structure calculations.

Development of a nuclear technique for monitoring water levels in pressurized vehicles

NASA Technical Reports Server (NTRS)

Singh, J. J.; Davis, W. T.; Mall, G. H.

1983-01-01

A new technique for monitoring water levels in pressurized stainless steel cylinders was developed. It is based on differences in attenuation coefficients of water and air for Cs137 (662 keV) gamma rays. Experimentally observed gamma ray counting rates with and without water in model reservoir cylinder were compared with corresponding calculated values for two different gamma ray detection theshold energies. Calculated values include the effects of multiple scattering and attendant gamma ray energy reductions. The agreement between the measured and calculated values is reasonably good. Computer programs for calculating angular and spectral distributions of scattered radition in various media are included.

Out-of-plane (e ,2 e ) measurements and calculations on He autoionizing levels as a function of incident-electron energy

NASA Astrophysics Data System (ADS)

Martin, N. L. S.; Weaver, C. M.; Kim, B. N.; deHarak, B. A.; Zatsarinny, O.; Bartschat, K.

2018-05-01

Out-of-scattering-plane (e ,2 e ) measurements and calculations are reported for the three singlet helium 2 ℓ 2 ℓ' autoionizing levels, with 80, 100, 120, 150, and 488 eV incident-electron energies, and scattering angles 60∘, 50 .8∘ , 45∘, 39 .2∘ , and 20 .5∘ , respectively. The kinematics are the same in all cases: the momentum transfer is K =2.1 a.u., and ejected electrons are detected in a plane that contains the momentum-transfer direction and is perpendicular to the scattering plane. The results are presented as (e ,2 e ) angular distributions energy integrated over each level. They are compared with fully nonperturbative B -spline R -matrix and hybrid second-order distorted-wave + R -matrix calculations.

Variational study on the vibrational level structure and vibrational level mixing of highly vibrationally excited S₀ D₂CO.

PubMed

Rashev, Svetoslav; Moule, David C; Rashev, Vladimir

2012-11-01

We perform converged high precision variational calculations to determine the frequencies of a large number of vibrational levels in S(0) D(2)CO, extending from low to very high excess vibrational energies. For the calculations we use our specific vibrational method (recently employed for studies on H(2)CO), consisting of a combination of a search/selection algorithm and a Lanczos iteration procedure. Using the same method we perform large scale converged calculations on the vibrational level spectral structure and fragmentation at selected highly excited overtone states, up to excess vibrational energies of ∼17,000 cm(-1), in order to study the characteristics of intramolecular vibrational redistribution (IVR), vibrational level density and mode selectivity. Copyright © 2012 Elsevier B.V. All rights reserved.

Theoretical Study of Energy Levels and Transition Probabilities of Boron Atom

NASA Astrophysics Data System (ADS)

Tian Yi, Zhang; Neng Wu, Zheng

2009-08-01

Full Text PDF Though the electrons configuration for boron atom is simple and boron atom has long been of interest for many researchers, the theoretical studies for properties of BI are not systematic, there are only few results reported on energy levels of high excited states of boron, and transition measurements are generally restricted to transitions involving ground states and low excited states without considering fine structure effects, provided only multiplet results, values for transitions between high excited states are seldom performed. In this article, by using the scheme of the weakest bound electron potential model theory calculations for energy levels of five series are performed and with the same method we give the transition probabilities between excited states with considering fine structure effects. The comprehensive set of calculations attempted in this paper could be of some value to workers in the field because of the lack of published calculations for the BI systems. The perturbations coming from foreign perturbers are taken into account in studying the energy levels. Good agreement between our results and the accepted values taken from NIST has been obtained. We also reported some values of energy levels and transition probabilities not existing on the NIST data bases.

Energy states, transport, and magnetotransport in diluted magnetic semiconductor (Ga, Mn)As with quantum well InGaAs.

PubMed

Shchurova, L Yu; Kulbachinskii, V A

2011-03-01

We investigate energy levels, thermodynamic, transport and magnetotransport properties of holes in GaAs structure with quantum well InGaAs delta-doped by C and Mn. We present self-consistent calculations for energy levels in the quantum well for different degrees of ionization of Mn impurity. The magnetoresistance of holes in the quantum well is calculated. We explain observed negative magnetoresistance by the reduction of spin-flip scattering on magnetic ions due to aligning of spins with magnetic field.

Wavelengths, Transition Probabilities, and Energy Levels for the Spectra of Strontium Ions (Sr II through Sr XXXVIII)

NASA Astrophysics Data System (ADS)

Sansonetti, J. E.

2012-03-01

Energy levels, with designations and uncertainties, have been compiled for the spectra of strontium (Z=38) ions from singly ionized to hydrogen-like. Wavelengths with classifications, intensities, and transition probabilities are also tabulated. In addition, ground states and ionization energies are listed. For many ionization stages experimental data are available; however for those for which only theoretical calculations or fitted values exist, these are reported. There are a few ionization stages for which only a calculated ionization potential is available.

Systematization of experimental data on the spectra of 3s--3p and 3p--3d transitions of Ar IX (436--861 A)

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

Kramida, A.E.

1985-04-01

The article correlates and systematizes published data on the wavelengths of lines in the spectra of argon obtained by various authors by the so-called beam-foil method. The energies of the levels are compared with the results of an extrapolation along an isoelectronic sequence, and the lifetimes of the levels are compared with theoretical calculations. The energies of all 26 energy levels of the 2p/sup 5/3s, 3p and 3d configurations of Ar IX are determined and refined. Forty-five transitions between these configurations in the 436--861 A region are identified. The identifications are supported by combinations according to the Ritz principle andmore » by a semiempirical calculation of the energies of the levels.« less

Estimating neutron dose equivalent rates from heavy ion reactions around 10 MeV amu(-1) using the PHITS code.

PubMed

Iwamoto, Yosuke; Ronningen, R M; Niita, Koji

2010-04-01

It has been sometimes necessary for personnel to work in areas where low-energy heavy ions interact with targets or with beam transport equipment and thereby produce significant levels of radiation. Methods to predict doses and to assist shielding design are desirable. The Particle and Heavy Ion Transport code System (PHITS) has been typically used to predict radiation levels around high-energy (above 100 MeV amu(-1)) heavy ion accelerator facilities. However, predictions by PHITS of radiation levels around low-energy (around 10 MeV amu(-1)) heavy ion facilities to our knowledge have not yet been investigated. The influence of the "switching time" in PHITS calculations of low-energy heavy ion reactions, defined as the time when the JAERI Quantum Molecular Dynamics model (JQMD) calculation stops and the Generalized Evaporation Model (GEM) calculation begins, was studied using neutron energy spectra from 6.25 MeV amu(-1) and 10 MeV amu(-1) (12)C ions and 10 MeV amu(-1) (16)O ions incident on a copper target. Using a value of 100 fm c(-1) for the switching time, calculated neutron energy spectra obtained agree well with the experimental data. PHITS was then used with the switching time of 100 fm c(-1) to simulate an experimental study by Ohnesorge et al. by calculating neutron dose equivalent rates produced by 3 MeV amu(-1) to 16 MeV amu(-1) (12)C, (14)N, (16)O, and (20)Ne beams incident on iron, nickel and copper targets. The calculated neutron dose equivalent rates agree very well with the data and follow a general pattern which appears to be insensitive to the heavy ion species but is sensitive to the target material.

The interaction of MnH(X 7Σ+) with He: Ab initio potential energy surface and bound states

NASA Astrophysics Data System (ADS)

Turpin, Florence; Halvick, Philippe; Stoecklin, Thierry

2010-06-01

The potential energy surface of the ground state of the He-MnH(X Σ7+) van der Waals complex is presented. Within the supermolecular approach of intermolecular energy calculations, a grid of ab initio points was computed at the multireference configuration interaction level using the aug-cc-pVQZ basis set for helium and hydrogen and the relativistic aug-cc-pVQZ-DK basis set for manganese. The potential energy surface was then fitted to a global analytical form which main features are discussed. As a first application of this potential energy surface, we present accurate calculations of bound energy levels of the H3e-MnH and H4e-MnH complexes.

The interaction of MnH(X 7Sigma+) with He: ab initio potential energy surface and bound states.

PubMed

Turpin, Florence; Halvick, Philippe; Stoecklin, Thierry

2010-06-07

The potential energy surface of the ground state of the He-MnH(X (7)Sigma(+)) van der Waals complex is presented. Within the supermolecular approach of intermolecular energy calculations, a grid of ab initio points was computed at the multireference configuration interaction level using the aug-cc-pVQZ basis set for helium and hydrogen and the relativistic aug-cc-pVQZ-DK basis set for manganese. The potential energy surface was then fitted to a global analytical form which main features are discussed. As a first application of this potential energy surface, we present accurate calculations of bound energy levels of the (3)He-MnH and (4)He-MnH complexes.

Critical evaluation of energy intake using the Goldberg cut-off for energy intake:basal metabolic rate. A practical guide to its calculation, use and limitations.

PubMed

Black, A E

2000-09-01

To re-state the principles underlying the Goldberg cut-off for identifying under-reporters of energy intake, re-examine the physiological principles and update the values to be substituted into the equation for calculating the cut-off, and to examine its use and limitations. New values are suggested for each element of the Goldberg equation. The physical activity level (PAL) for comparison with energy intake:basal metabolic rate (EI:BMR) should be selected to reflect the population under study; the PAL value of 1.55 x BMR is not necessarily the value of choice. The suggested value for average within-subject variation in energy intake is 23% (unchanged), but other sources of variation are increased in the light of new data. For within-subject variation in measured and estimated BMR, 4% and 8.5% respectively are suggested (previously 2.5% and 8%), and for total between-subject variation in PAL, the suggested value is 15% (previously 12.5%). The effect of these changes is to widen the confidence limits and reduce the sensitivity of the cut-off. The Goldberg cut-off can be used to evaluate the mean population bias in reported energy intake, but information on the activity or lifestyle of the population is needed to choose a suitable PAL energy requirement for comparison. Sensitivity for identifying under-reporters at the individual level is limited. In epidemiological studies information on home, leisure and occupational activity is essential in order to assign subjects to low, medium or high PAL levels before calculating the cut-offs. In small studies, it is desirable to measure energy expenditure, or to calculate individual energy requirements, and to compare energy intake directly with energy expenditure.

Relativistic MR–MP Energy Levels for L-shell Ions of Silicon

DOE PAGES

Santana, Juan A.; Lopez-Dauphin, Nahyr A.; Beiersdorfer, Peter

2018-01-15

Level energies are reported for Si v, Si vi, Si vii, Si viii, Si ix, Si x, Si xi, and Si xii. The energies have been calculated with the relativistic Multi-Reference Møller–Plesset Perturbation Theory method and include valence and K-vacancy states with nl up to 5f. The accuracy of the calculated level energies is established by comparison with the recommended data listed in the National Institute of Standards and Technology (NIST) online database. The average deviation of valence level energies ranges from 0.20 eV in Si v to 0.04 eV in Si xii. For K-vacancy states, the available values recommendedmore » in the NIST database are limited to Si xii and Si xiii. The average energy deviation is below 0.3 eV for K-vacancy states. The extensive and accurate data set presented here greatly augments the amount of available reference level energies. Here, we expect our data to ease the line identification of L-shell ions of Si in celestial sources and laboratory-generated plasmas, and to serve as energy references in the absence of more accurate laboratory measurements.« less

Relativistic MR–MP Energy Levels for L-shell Ions of Silicon

NASA Astrophysics Data System (ADS)

Santana, Juan A.; Lopez-Dauphin, Nahyr A.; Beiersdorfer, Peter

2018-01-01

Level energies are reported for Si V, Si VI, Si VII, Si VIII, Si IX, Si X, Si XI, and Si XII. The energies have been calculated with the relativistic Multi-Reference Møller–Plesset Perturbation Theory method and include valence and K-vacancy states with nl up to 5f. The accuracy of the calculated level energies is established by comparison with the recommended data listed in the National Institute of Standards and Technology (NIST) online database. The average deviation of valence level energies ranges from 0.20 eV in Si V to 0.04 eV in Si XII. For K-vacancy states, the available values recommended in the NIST database are limited to Si XII and Si XIII. The average energy deviation is below 0.3 eV for K-vacancy states. The extensive and accurate data set presented here greatly augments the amount of available reference level energies. We expect our data to ease the line identification of L-shell ions of Si in celestial sources and laboratory-generated plasmas, and to serve as energy references in the absence of more accurate laboratory measurements.

VizieR Online Data Catalog: Relativistic MR-MP energy levels for Si (Santana+, 2018)

NASA Astrophysics Data System (ADS)

Santana, J. A.; Lopez-Dauphin, N. A.; Beiersdorfer, P.

2018-03-01

Level energies are reported for Si V, Si VI, Si VII, Si VIII, Si IX, Si X, Si XI, and Si XII. The energies have been calculated with the relativistic Multi- Reference Moller-Plesset Perturbation Theory method and include valence and K-vacancy states with nl up to 5f. The accuracy of the calculated level energies is established by comparison with the recommended data listed in the National Institute of Standards and Technology (NIST) online database. The average deviation of valence level energies ranges from 0.20eV in SiV to 0.04eV in SiXII. For K-vacancy states, the available values recommended in the NIST database are limited to Si XII and Si XIII. The average energy deviation is below 0.3eV for K-vacancy states. The extensive and accurate data set presented here greatly augments the amount of available reference level energies. We expect our data to ease the line identification of L-shell ions of Si in celestial sources and laboratory-generated plasmas, and to serve as energy references in the absence of more accurate laboratory measurements. (1 data file).

Relativistic MR–MP Energy Levels for L-shell Ions of Silicon

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

Santana, Juan A.; Lopez-Dauphin, Nahyr A.; Beiersdorfer, Peter

Level energies are reported for Si v, Si vi, Si vii, Si viii, Si ix, Si x, Si xi, and Si xii. The energies have been calculated with the relativistic Multi-Reference Møller–Plesset Perturbation Theory method and include valence and K-vacancy states with nl up to 5f. The accuracy of the calculated level energies is established by comparison with the recommended data listed in the National Institute of Standards and Technology (NIST) online database. The average deviation of valence level energies ranges from 0.20 eV in Si v to 0.04 eV in Si xii. For K-vacancy states, the available values recommendedmore » in the NIST database are limited to Si xii and Si xiii. The average energy deviation is below 0.3 eV for K-vacancy states. The extensive and accurate data set presented here greatly augments the amount of available reference level energies. Here, we expect our data to ease the line identification of L-shell ions of Si in celestial sources and laboratory-generated plasmas, and to serve as energy references in the absence of more accurate laboratory measurements.« less

Tunneling Splittings in Vibronic Structure of CH_3F^+ ( X^2E): Studied by High Resolution Photoelectron Spectra and AB Initio Theoretical Method

NASA Astrophysics Data System (ADS)

Mo, Yuxiang; Gao, Shuming; Dai, Zuyang; Li, Hua

2013-06-01

We report a combined experimental and theoretical study on the vibronic structure of CH_3F^+. The results show that the tunneling splittings of vibrational energy levels occur in CH_3F^+ due to the Jahn-Teller effect. Experimentally, we have measured a high resolution ZEKE spectrum of CH_3F up to 3500 cm^-^1 above the ground state. Theoretically, we performed an ab initio calculation based on the diabatic model. The adiabatic potential energy surfaces (APES) of CH_3F^+ have been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables. The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the APES have been used to determine the coefficients in the Taylor expansion. The spin-vibronic energy levels have been calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned based on the theoretical calculations. W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004). M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).

Energy levels and radiative rates for transitions in Fe V, Co VI and Ni VII

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Bogdanovich, P.; Keenan, F. P.; Kisielius, R.

2017-03-01

Energy levels, Landé g-factors and radiative lifetimes are reported for the lowest 182 levels of the 3d4, 3d34s and 3d34p configurations of Fe V, Co VI and Ni VII. Additionally, radiative rates (A-values) have been calculated for the E1, E2 and M1 transitions among these levels. The calculations have been performed in a quasi-relativistic approach (QR) with a very large configuration interaction (CI) wavefunction expansion, which has been found to be necessary for these ions. Our calculated energies for all ions are in excellent agreement with the available measurements, for most levels. Discrepancies among various calculations for the radiative rates of E1 transitions in Fe V are up to a factor of two for stronger transitions (f ≥ 0.1), and larger (over an order of magnitude) for weaker ones. The reasons for these discrepancies have been discussed and mainly are due to the differing amount of CI and methodologies adopted. However, there are no appreciable discrepancies in similar data for M1 and E2 transitions, or the g-factors for the levels of Fe V, the only ion for which comparisons are feasible.

High-Level ab initio electronic structure calculations of Water Clusters (H2O)16 and (H2O)17: a new global minimum for (H2O)16

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

Yoo, Soohaeng; Apra, Edoardo; Zeng, Xiao Cheng

The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at the MP2 and CCSD(T) levels of theory and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17 the CCSD(T) calculations confirm the previously found at the MP2 level of theory "interior" arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum.

High-Level ab-initio Electronic Structure Calculations of Water Clusters (H2O)16 and (H2O)17 : a New Global Minimum for (H2O)16

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

Yoo, Soohaeng; Apra, Edoardo; Zeng, X.C.

The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at both the MP2 and CCSD(T) levels of theory, and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17, the CCSD(T) calculations confirm the previously found at the MP2 level of theory interior arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum

Surface shift of the occupied and unoccupied 4f levels of the rare-earth metals

NASA Astrophysics Data System (ADS)

Aldén, M.; Johansson, B.; Skriver, H. L.

1995-02-01

The surface energy shifts of the occupied and unoccupied 4f levels for the lanthanide metals have been calculated from first principles by means of a Green's-function technique within the tight-binding linear muffin-tin orbitals method. We use the concept of complete screening to identify the occupied and unoccupied 4f energy level shifts as the surface segregation energy of a 4fn-1 and 4fn+1 impurity atom, respectively, in a 4fn host metal. The calculations include both initial- and final-state effects and give values that are considerably lower than those measured on polycrystalline samples as well as those found in previous initial-state model calculations. The present theory agrees well with very recent high-resolution, single-crystal film measurements for Gd, Tb, Dy, Ho, Er, Tm, and Lu. We furthermore utilize the unique possibility offered by the lanthanide metals to clarify the roles played by the initial and the different final states of the core-excitation process, permitted by the fact that the so-called initial-state effect is identical upon 4f removal and 4f addition. Surface energy and work function calculations are also reported.

Atomic Data and Spectral Line Intensities for Ni XV

NASA Technical Reports Server (NTRS)

Landi, E.; Bhatia, A. K.

2011-01-01

Electron impact collision strengths, energy levels, oscillator strengths, and spontaneous radiative decay rates are calculated for Ni XV.Weinclude in the calculations the 9 lowest configurations, corresponding to 126 fine structure levels: 3s23p2, 3s3p3, 3s23p3d, 3p4, 3s3p23d, and 3s2 3p4l with l =, s, p, d, f. Collision strengths are calculated at five incident energies for all transitions: 7.8, 18.5, 33.5, 53.5, and 80.2 Ry above the threshold of each transition. An additional energy, very close to the transition threshold, has been added, whose value is between 0.004 and 0.28 Ry depending on the levels involved. Calculations have been carried out using the Flexible Atomic Code and the distorted-wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates calculated in the present work, statistical equilibrium equations for level populations are solved at electron densities covering the 10(exp 8)-10(exp 14)/cu cm range and at an electron temperature of log T(sub e)(K) = 6.4, corresponding to the maximum abundance of Ni XV. Spectral line intensities are calculated, and their diagnostic relevance is discussed. This dataset will be made available in the next version of the CHIANTI database.

A Liquid Level Measurement Technique Outside a Sealed Metal Container Based on Ultrasonic Impedance and Echo Energy

PubMed Central

Zhang, Bin; Wei, Yue-Juan; Liu, Wen-Yi; Zhang, Yan-Jun; Yao, Zong; Zhao, Li-Hui; Xiong, Ji-Jun

2017-01-01

The proposed method for measuring the liquid level focuses on the ultrasonic impedance and echo energy inside a metal wall, to which the sensor is attached directly, not on ultrasonic waves that penetrate the gas–liquid medium of a container. Firstly, by analyzing the sound field distribution characteristics of the sensor in a metal wall, this paper proposes the concept of an "energy circle" and discusses how to calculate echo energy under three different states in detail. Meanwhile, an ultrasonic transmitting and receiving circuit is designed to convert the echo energy inside the energy circle into its equivalent electric power. Secondly, in order to find the two critical states of the energy circle in the process of liquid level detection, a program is designed to help with calculating two critical positions automatically. Finally, the proposed method is evaluated through a series of experiments, and the experimental results indicate that the proposed method is effective and accurate in calibration of the liquid level outside a sealed metal container. PMID:28106857

The sdg interacting-boson model applied to 168Er

NASA Astrophysics Data System (ADS)

Yoshinaga, N.; Akiyama, Y.; Arima, A.

1986-03-01

The sdg interacting-boson model is applied to 168Er. Energy levels and E2 transitions are calculated. This model is shown to solve the problem of anharmonicity regarding the excitation energy of the first Kπ=4+ band relative to that of the first Kπ=2+ one. The level scheme including the Kπ=3+ band is well reproduced and the calculated B(E2)'s are consistent with the experimental data.

Energy levels of a hydrogenic impurity in a parabolic quantum well with a magnetic field

NASA Astrophysics Data System (ADS)

Zang, J. X.; Rustgi, M. L.

1993-07-01

In this paper, we present a calculation of the energy levels of a hydrogenic impurity (or a hydrogenic atom) at the bottom of a one-dimensional parabolic quantum well with a magnetic field normal to the plane of the well. The finite-basis-set variational method is used to calculate the ground state and the excited states with major quantum number less than or equal to 3. The limit of small radial distance and the limit of great radial distance are considered to choose a set of proper basis functions. The results in the limit that the parabolic parameter α=0 are compared with the data of Rösner et al. [J. Phys. B 17, 29 (1984)]. The comparison shows that the present calculation is quite accurate. It is found that the energy levels increase with increasing parabolic parameter α and increase with increasing normalized magnetic-field strength γ except those levels with magnetic quantum number m<0 at small γ.

Estimating Household Travel Energy Consumption in Conjunction with a Travel Demand Forecasting Model

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

Garikapati, Venu M.; You, Daehyun; Zhang, Wenwen

This paper presents a methodology for the calculation of the consumption of household travel energy at the level of the traffic analysis zone (TAZ) in conjunction with information that is readily available from a standard four-step travel demand model system. This methodology embeds two algorithms. The first provides a means of allocating non-home-based trips to residential zones that are the source of such trips, whereas the second provides a mechanism for incorporating the effects of household vehicle fleet composition on fuel consumption. The methodology is applied to the greater Atlanta, Georgia, metropolitan region in the United States and is foundmore » to offer a robust mechanism for calculating the footprint of household travel energy at the level of the individual TAZ; this mechanism makes possible the study of variations in the energy footprint across space. The travel energy footprint is strongly correlated with the density of the built environment, although socioeconomic differences across TAZs also likely contribute to differences in travel energy footprints. The TAZ-level calculator of the footprint of household travel energy can be used to analyze alternative futures and relate differences in the energy footprint to differences in a number of contributing factors and thus enables the design of urban form, formulation of policy interventions, and implementation of awareness campaigns that may produce more-sustainable patterns of energy consumption.« less

Energy levels and radiative rates for Ne-like ions from Cu to Ga

NASA Astrophysics Data System (ADS)

Singh, Narendra; Aggarwal, Sunny

2017-11-01

Energy levels, lifetimes and wave function compositions are computed for 127 fine structural levels in Ne-like ions (Z=29{-}31). Configuration interaction has been included among 51 configurations (generating 1016 levels) and multiconfigurational Dirac-Fock method is used to generate the wave functions. Similar calculations have also been performed using the fully relativistic flexible atomic code (FAC). Transition wavelength, oscillator strength, transition probabilities and line strength are reported for electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1) and magnetic quadrupole (M2) transitions from the ground level. We compared our calculated results with the available data in the literature. The calculated results are found to be in close agreement with the previous results. Further, we predict some new atomic data which may be important for plasma diagnostics.

First-principles approach to calculating energy level alignment at aqueous semiconductor interfaces.

PubMed

Kharche, Neerav; Muckerman, James T; Hybertsen, Mark S

2014-10-24

A first-principles approach is demonstrated for calculating the relationship between an aqueous semiconductor interface structure and energy level alignment. The physical interface structure is sampled using density functional theory based molecular dynamics, yielding the interface electrostatic dipole. The  GW approach from many-body perturbation theory is used to place the electronic band edge energies of the semiconductor relative to the occupied 1b1 energy level in water. The application to the specific cases of nonpolar (101¯0) facets of GaN and ZnO reveals a significant role for the structural motifs at the interface, including the degree of interface water dissociation and the dynamical fluctuations in the interface Zn-O and O-H bond orientations. These effects contribute up to 0.5 eV.

Low cost estimation of the contribution of post-CCSD excitations to the total atomization energy using density functional theory calculations

NASA Astrophysics Data System (ADS)

Sánchez, H. R.; Pis Diez, R.

2016-04-01

Based on the Aλ diagnostic for multireference effects recently proposed [U.R. Fogueri, S. Kozuch, A. Karton, J.M. Martin, Theor. Chem. Acc. 132 (2013) 1], a simple method for improving total atomization energies and reaction energies calculated at the CCSD level of theory is proposed. The method requires a CCSD calculation and two additional density functional theory calculations for the molecule. Two sets containing 139 and 51 molecules are used as training and validation sets, respectively, for total atomization energies. An appreciable decrease in the mean absolute error from 7-10 kcal mol-1 for CCSD to about 2 kcal mol-1 for the present method is observed. The present method provides atomization energies and reaction energies that compare favorably with relatively recent scaled CCSD methods.

Energy Levels and Oscillator Strengths for Ne-like Iron Ions

NASA Astrophysics Data System (ADS)

Zhong, J. Y.; Zhang, J.; Zhao, G.; Lu, X..

2004-02-01

Energy levels and oscillator strengths among the 27 fine-structure levels belonging to the (1s22s2)2p6, 2p53s, 2p53p and 2p53d configurations of neon-like iron ion have been calculated by using three atomic structure codes, RCN/RCG, AUTOSTRUCTURE (AS) and GRASP. The relativistic corrections of the wave functions are taken into account in RCN/RCG calculations. The results well agree with experimental and theoretical data wherever available. Finally the accuracy of three codes was analyzed.

Excitation energies, oscillator strengths and lifetimes in Mg-like vanadium

NASA Astrophysics Data System (ADS)

Gupta, G. P.; Msezane, A. Z.

2013-08-01

Excitation energies from the ground state for 86 fine-structure levels as well as oscillator strengths and radiative decay rates for all fine-structure transitions among the levels of the terms (1s22s22p6)3s2(1S), 3s3p(1,3Po), 3s3d(1,3D), 3s4s(1,3S), 3s4p(1,3Po), 3s4d(1,3D), 3s4f(1,3Fo), 3p2(1S, 3P, 1D), 3p3d(1,3Po, 1,3Do, 1,3Fo), 3p4s(1,3Po), 3p4p(1,3S, 1,3P, 1,3D), 3p4d(1,3Po, 1,3Do, 1,3Fo), 3p4f(1,3D, 1,3F, 1,3G) and 3d2(1S, 3P, 1D,3F,1G) of V XII are calculated using extensive configuration-interaction wave functions obtained with the configuration-interaction version 3 computer code of Hibbert. The important relativistic effects in intermediate coupling are included through the Breit-Pauli approximation. In order to keep our calculated energy splittings as close as possible to the corresponding experimental values, we have made small adjustments to the diagonal elements of the Hamiltonian matrices. The mixing among several fine-structure levels is found to be very strong. Our fine-tuned excitation energies, including their ordering, are in excellent agreement (better than 0.25%) with the available experimental results. From our calculated radiative decay rates, we have also calculated the radiative lifetimes of fine-structure levels. Generally, our calculated data for the excitation energies and radiative decay rates are found to agree reasonably well with other available calculations. However, significant differences between our calculated lifetimes and those from the calculation of Froese Fischer et al (2006 At. Data Nucl. Data Tables 92 607) for a few fine-structure levels, mainly those belonging to the 3p4d configuration, are noted and discussed. Also, our calculated lifetime for the longer-lived level 3s3p(3P1) is found to be in excellent agreement with the corresponding value of Curtis (1991 Phys. Scr. 43 137). ) for all 1108 transitions in V XII are available with the first author ().

Calculations of the binding affinities of protein-protein complexes with the fast multipole method

NASA Astrophysics Data System (ADS)

Kim, Bongkeun; Song, Jiming; Song, Xueyu

2010-09-01

In this paper, we used a coarse-grained model at the residue level to calculate the binding free energies of three protein-protein complexes. General formulations to calculate the electrostatic binding free energy and the van der Waals free energy are presented by solving linearized Poisson-Boltzmann equations using the boundary element method in combination with the fast multipole method. The residue level model with the fast multipole method allows us to efficiently investigate how the mutations on the active site of the protein-protein interface affect the changes in binding affinities of protein complexes. Good correlations between the calculated results and the experimental ones indicate that our model can capture the dominant contributions to the protein-protein interactions. At the same time, additional effects on protein binding due to atomic details are also discussed in the context of the limitations of such a coarse-grained model.

A global ab initio potential for HCN/HNC, exact vibrational energies, and comparison to experiment

NASA Technical Reports Server (NTRS)

Bentley, Joseph A.; Bowman, Joel M.; Gazdy, Bela; Lee, Timothy J.; Dateo, Christopher E.

1992-01-01

An ab initio (i.e., from first principles) calculation of vibrational energies of HCN and HNC is reported. The vibrational calculations were done with a new potential derived from a fit to 1124 ab initio electronic energies which were calculated using the highly accurate CCSD(T) coupled-cluster method in conjunction with a large atomic natural orbital basis set. The properties of this potential are presented, and the vibrational calculations are compared to experiment for 54 vibrational transitions, 39 of which are for zero total angular momentum, J = 0, and 15 of which are for J = 1. The level of agreement with experiment is unprecedented for a triatomic with two nonhydrogen atoms, and demonstrates the capability of the latest computational methods to give reliable predictions on a strongly bound triatomic molecule at very high levels of vibrational excitation.

Determination of the electronic energy levels of colloidal nanocrystals using field-effect transistors and Ab-initio calculations.

PubMed

Bisri, Satria Zulkarnaen; Degoli, Elena; Spallanzani, Nicola; Krishnan, Gopi; Kooi, Bart Jan; Ghica, Corneliu; Yarema, Maksym; Heiss, Wolfgang; Pulci, Olivia; Ossicini, Stefano; Loi, Maria Antonietta

2014-08-27

Colloidal nanocrystals electronic energy levels are determined by strong size-dependent quantum confinement. Understanding the configuration of the energy levels of nanocrystal superlattices is vital in order to use them in heterostructures with other materials. A powerful method is reported to determine the energy levels of PbS nanocrystal assemblies by combining the utilization of electric-double-layer-gated transistors and advanced ab-initio theory. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiconfiguration resonating-group theory of the seven-nucleon system with realistic cluster wave functions

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

Fujiwara, Y.; Tang, Y.C.

1985-02-01

The properties of the seven-nucleon system are examined with a multiconfiguration and multi- channel resonating-group calculation. The cluster internal functions employed explain the charge-form-factor data over a wide range of q/sup 2/ and satisfy the variational stability condition quite well. The model space used is spanned by /sup 3/H+..cap alpha.., n+ /sup 6/Li, n+ /sup 6/Li(, and d+ /sup 5/He cluster configurations. The result shows that the specific distortion of the /sup 3/H+..cap alpha.. system is quite significant. With our multiconfiguration calculation, the ground-state energy is improved by more than 1 MeV. The calculated level spectrum agrees well with themore » level spectrum empirically determined. The energy positions of both natural-parity and unnatural-parity levels are reasonably explained. In addition, we find that, because of centrifugal-barrier effects, the aligned configuration generally makes the most sig- nificant contribution. The characteristics of nucleon-exchange terms are also briefly examined. Here it is found that, at sufficiently high energies where sharp resonance levels do not exist, the essential properties of these terms can already be learned by performing relatively simple single-configuration calculations.« less

Computational Analysis of Hybrid Two-Photon Absorbers with Excited State Absorption

DTIC Science & Technology

2007-03-01

level. This hybrid arrangement creates a complex dynamical system in which the electron carrier concentration of every photo-activated energy level...spatiotemporal details of the electron population densities of each photo-activated energy level as well as the pulse shape in space and time. The main...experiments at low input energy . However, further additions must be done to the calculation of the optical path for high input energy . 1 15. SUBJECT TERM

Study on Calculation of Liquid Level And Storage of Tanks for LNG-fueled Vessels

NASA Astrophysics Data System (ADS)

Li, Kun; Wang, Guoqing; Liu, Chang

2018-01-01

As the ongoing development of the application of LNG as a clean energy in waterborne transport industry, the fleet scale of LNG-fueled vessels enlarged and the safety operation has attracted more attention in the industry. Especially the accurate detection of liquid level of LNG tanks is regarded as an important issue to ensure a safe and stable operation of LNG-fueled ships and a key parameter to keep the proper functioning of marine fuel storage system, supply system and safety control system. At present, detection of LNG tank liquid level mainly adopts differential pressure detection method. Liquid level condition could be found from the liquid level reference tables. However in practice, since LNG-fueled vessels are generally not in a stationary state, liquid state within the LNG tanks will constantly change, the detection of storage of tanks only by reference to the tables will cause deviation to some extent. By analyzing the temperature under different pressure, the effects of temperature change on density and volume integration calculation, a method of calculating the liquid level and storage of LNG tanks is put forward making the calculation of liquid level and actual storage of LNG tanks more accurately and providing a more reliable basis for the calculation of energy consumption level and operation economy for LNG-fueled vessels.

Critically Evaluated Energy Levels, Spectral Lines, Transition Probabilities, and Intensities of Neutral Vanadium (V i)

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

Saloman, Edward B.; Kramida, Alexander

2017-08-01

The energy levels, observed spectral lines, and transition probabilities of the neutral vanadium atom, V i, have been compiled. Also included are values for some forbidden lines that may be of interest to the astrophysical community. Experimental Landé g -factors and leading percentage compositions for the levels are included where available, as well as wavelengths calculated from the energy levels (Ritz wavelengths). Wavelengths are reported for 3985 transitions, and 549 energy levels are determined. The observed relative intensities normalized to a common scale are provided.

Nuclear shape evolution based on microscopic level densities

DOE PAGES

Ward, D. E.; Carlsson, B. G.; Døssing, T.; ...

2017-02-27

Here, by combining microscopically calculated level densities with the Metropolis walk method, we develop a consistent framework for treating the energy and angular-momentum dependence of the nuclear shape evolution in the fission process. For each nucleus under consideration, the level density is calculated microscopically for each of more than five million shapes with a recently developed combinatorial method. The method employs the same single-particle levels as those used for the extraction of the pairing and shell contributions to the macroscopic-microscopic deformation-energy surface. Containing no new parameters, the treatment is suitable for elucidating the energy dependence of the dynamics of warmmore » nuclei on pairing and shell effects. It is illustrated for the fission fragment mass distribution for several uranium and plutonium isotopes of particular interest.« less

Electron correlation within the relativistic no-pair approximation

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

Almoukhalalati, Adel; Saue, Trond, E-mail: trond.saue@irsamc.ups-tlse.fr; Knecht, Stefan

This paper addresses the definition of correlation energy within 4-component relativistic atomic and molecular calculations. In the nonrelativistic domain the correlation energy is defined as the difference between the exact eigenvalue of the electronic Hamiltonian and the Hartree-Fock energy. In practice, what is reported is the basis set correlation energy, where the “exact” value is provided by a full Configuration Interaction (CI) calculation with some specified one-particle basis. The extension of this definition to the relativistic domain is not straightforward since the corresponding electronic Hamiltonian, the Dirac-Coulomb Hamiltonian, has no bound solutions. Present-day relativistic calculations are carried out within themore » no-pair approximation, where the Dirac-Coulomb Hamiltonian is embedded by projectors eliminating the troublesome negative-energy solutions. Hartree-Fock calculations are carried out with the implicit use of such projectors and only positive-energy orbitals are retained at the correlated level, meaning that the Hartree-Fock projectors are frozen at the correlated level. We argue that the projection operators should be optimized also at the correlated level and that this is possible by full Multiconfigurational Self-Consistent Field (MCSCF) calculations, that is, MCSCF calculations using a no-pair full CI expansion, but including orbital relaxation from the negative-energy orbitals. We show by variational perturbation theory that the MCSCF correlation energy is a pure MP2-like correlation expression, whereas the corresponding CI correlation energy contains an additional relaxation term. We explore numerically our theoretical analysis by carrying out variational and perturbative calculations on the two-electron rare gas atoms with specially tailored basis sets. In particular, we show that the correlation energy obtained by the suggested MCSCF procedure is smaller than the no-pair full CI correlation energy, in accordance with the underlying minmax principle and our theoretical analysis. We also show that the relativistic correlation energy, obtained from no-pair full MCSCF calculations, scales at worst as X{sup −2} with respect to the cardinal number X of our correlation-consistent basis sets optimized for the two-electron atoms. This is better than the X{sup −1} scaling suggested by previous studies, but worse than the X{sup −3} scaling observed in the nonrelativistic domain. The well-known 1/Z- expansion in nonrelativistic atomic theory follows from coordinate scaling. We point out that coordinate scaling for consistency should be accompanied by velocity scaling. In the nonrelativistic domain this comes about automatically, whereas in the relativistic domain an explicit scaling of the speed of light is required. This in turn explains why the relativistic correlation energy to the lowest order is not independent of nuclear charge, in contrast to nonrelativistic theory.« less

Fission dynamics with microscopic level densities

NASA Astrophysics Data System (ADS)

Randrup, Jørgen; Ward, Daniel; Carlsson, Gillis; Døssing, Thomas; Möller, Peter; Åberg, Sven

2018-03-01

Working within the Langevin framework of nuclear shape dynamics, we study the dependence of the evolution on the degree of excitation. As the excitation energy of the fissioning system is increased, the pairing correlations and the shell effects diminish and the effective potential-energy surface becomes ever more liquid-drop like. This feature can be included in the treatment in a formally well-founded manner by using the local level densities as a basis for the shape evolution. This is particularly easy to understand and implement in the Metropolis treatment where the evolution is simulated by means of a random walk on the five-dimensional lattice of shapes for which the potential energy has been tabulated. Because the individual steps between two neighboring lattice sites are decided on the basis of the ratio of the statistical weights, what is needed is the ratio of the local level densities for those shapes, evaluated at the associated local excitation energies. For this purpose, we adapt a recently developed combinatorial method for calculating level densities which employs the same single-particle levels as those that were used for the calculation of the pairing and shell contributions to the macroscopic-microscopic deformation-energy surface. For each nucleus under consideration, the level density (for a fixed total angular momentum) is calculated microscopically for each of the over five million shapes given in the three-quadratic-surface parametrization. This novel treatment, which introduces no new parameters, is illustrated for the fission fragment mass distributions for selected uranium and plutonium cases.

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

Öner, Nazmiye, E-mail: fizikcinaz@gmail.com; Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Avci, Davut, E-mail: davci@sakarya.edu.tr

Quantum mechanical calculations on cis-2, 6-bis (2-chlorophenyl)-3, 3-dimethylpiperidin-4-one were performed by using HSEH1PBE level of density functional theory (DFT) with 6-311++G (d, p) basis set. Geometric parameters of the title molecule in the ground state were found to be in good agreement with experimental data. The frontier molecular orbitals (HOMO and LUMO) were simulated by the same level. Small energy gap between the HOMO and LUMO is an indicator molecular charge transfer within the title molecule. The electronegativity, chemical hardness and softness were also calculated by using HOMO and LUMO energies. Dipole moment, polarizability and hyperpolarizability parameters were also calculatedmore » by using HSEH1PBE level. All calculations were carried out with the GAUSSIAN 09 package program.« less

Continuum Level Density in Complex Scaling Method

NASA Astrophysics Data System (ADS)

Suzuki, R.; Myo, T.; Katō, K.

2005-11-01

A new calculational method of continuum level density (CLD) at unbound energies is studied in the complex scaling method (CSM). It is shown that the CLD can be calculated by employing the discretization of continuum states in the CSM without any smoothing technique.

Complexes and saddle point structures, vibrational frequencies and relative energies of intermediates for CH2Br + HBr «-» CH3Br + Br

NASA Astrophysics Data System (ADS)

Espinosa-Garcia, J.

Ab initio molecular orbital theory was used to study parts of the reaction between the CH2Br radical and the HBr molecule, and two possibilities were analysed: attack on the hydrogen and attack on the bromine of the HBr molecule. Optimized geometries and harmonic vibrational frequencies were calculated at the second-order Moller-Plesset perturbation theory levels, and comparison with available experimental data was favourable. Then single-point calculations were performed at several higher levels of calculation. In the attack on the hydrogen of HBr, two stationary points were located on the direct hydrogen abstraction reaction path: a very weak hydrogen bonded complex of reactants, C···HBr, close to the reactants, followed by the saddle point (SP). The effects of level of calculation (method + basis set), spin projection, zeropoint energy, thermal corrections (298K), spin-orbit coupling and basis set superposition error (BSSE) on the energy changes were analysed. Taking the reaction enthalpy (298K) as reference, agreement with experiment was obtained only when high correlation energy and large basis sets were used. It was concluded that at room temperature (i.e., with zero-point energy and thermal corrections), when the BSSE was included, the complex disappears and the activation enthalpy (298K) ranges from 0.8kcal mol-1 to 1.4kcal mol-1 above the reactants, depending on the level of calculation. It was concluded also that this result is the balance of a complicated interplay of many factors, which are affected by uncertainties in the theoretical calculations. Finally, another possible complex (X complex), which involves the alkyl radical being attracted to the halogen end of HBr (C···BrH), was explored also. It was concluded that this X complex does not exist at room temperature.

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

PubMed

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

2010-05-01

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

Multiscale Quantum Mechanics/Molecular Mechanics Simulations with Neural Networks.

PubMed

Shen, Lin; Wu, Jingheng; Yang, Weitao

2016-10-11

Molecular dynamics simulation with multiscale quantum mechanics/molecular mechanics (QM/MM) methods is a very powerful tool for understanding the mechanism of chemical and biological processes in solution or enzymes. However, its computational cost can be too high for many biochemical systems because of the large number of ab initio QM calculations. Semiempirical QM/MM simulations have much higher efficiency. Its accuracy can be improved with a correction to reach the ab initio QM/MM level. The computational cost on the ab initio calculation for the correction determines the efficiency. In this paper we developed a neural network method for QM/MM calculation as an extension of the neural-network representation reported by Behler and Parrinello. With this approach, the potential energy of any configuration along the reaction path for a given QM/MM system can be predicted at the ab initio QM/MM level based on the semiempirical QM/MM simulations. We further applied this method to three reactions in water to calculate the free energy changes. The free-energy profile obtained from the semiempirical QM/MM simulation is corrected to the ab initio QM/MM level with the potential energies predicted with the constructed neural network. The results are in excellent accordance with the reference data that are obtained from the ab initio QM/MM molecular dynamics simulation or corrected with direct ab initio QM/MM potential energies. Compared with the correction using direct ab initio QM/MM potential energies, our method shows a speed-up of 1 or 2 orders of magnitude. It demonstrates that the neural network method combined with the semiempirical QM/MM calculation can be an efficient and reliable strategy for chemical reaction simulations.

First-principles approach to calculating energy level alignment at aqueous semiconductor interfaces

DOE PAGES

Kharche, Neerav; Muckerman, James T.; Hybertsen, Mark S.

2014-10-21

A first-principles approach is demonstrated for calculating the relationship between an aqueous semiconductor interface structure and energy level alignment. The physical interface structure is sampled using density functional theory based molecular dynamics, yielding the interface electrostatic dipole. The GW approach from many-body perturbation theory is used to place the electronic band edge energies of the semiconductor relative to the occupied 1 b₁ energy level in water. The application to the specific cases of nonpolar (101¯0 ) facets of GaN and ZnO reveals a significant role for the structural motifs at the interface, including the degree of interface water dissociation andmore » the dynamical fluctuations in the interface Zn-O and O-H bond orientations. As a result, these effects contribute up to 0.5 eV.« less

Electronic energy level alignment at metal-molecule interfaces with a GW approach

NASA Astrophysics Data System (ADS)

Tamblyn, Isaac; Darancet, Pierre; Quek, Su Ying; Bonev, Stanimir A.; Neaton, Jeffrey B.

2011-11-01

Using density functional theory and many-body perturbation theory within a GW approximation, we calculate the electronic structure of a metal-molecule interface consisting of benzene diamine (BDA) adsorbed on Au(111). Through direct comparison with photoemission data, we show that a conventional G0W0 approach can underestimate the energy of the adsorbed molecular resonance relative to the Au Fermi level by up to 0.8 eV. The source of this discrepancy is twofold: a 0.7 eV underestimate of the gas phase ionization energy (IE), and a 0.2 eV overestimate of the Au work function. Refinements to self-energy calculations within the GW framework that account for deviations in both the Au work function and BDA gas-phase IE can result in an interfacial electronic level alignment in quantitative agreement with experiment.

Energy-level alignment in organic dye-sensitized TiO2 from GW calculations.

PubMed

Umari, P; Giacomazzi, L; De Angelis, F; Pastore, M; Baroni, Stefano

2013-07-07

The electronic energy levels of some representative isolated and oxide-supported organic dyes, relevant for photovoltaic applications, are investigated using many-body perturbation theory within the GW approximation. We consider a set of all-organic dyes (denominated L0, L2, L3, and L4) featuring the same donor and anchor groups and differing for the linker moieties. We first calculate the energy levels of the isolated molecules, thus allowing us to address the effects of the different linker groups, and resulting in good agreement with photo-electron spectroscopic and electrochemical data. We then consider the L0 dye adsorbed on the (101) surface of anatase-TiO2. We find a density of occupied states in agreement with experimental photo-electron data. The HOMO-LUMO energy gap of the L0 dye is found to be reduced by ~1 eV upon adsorption. Our results validate the reliability of GW calculations for photovoltaic applications and point to their potential as a powerful tool for the screening and rational design of new components of electrochemical solar cells.

Level Density in the Complex Scaling Method

NASA Astrophysics Data System (ADS)

Suzuki, R.; Myo, T.; Katō, K.

2005-06-01

It is shown that the continuum level density (CLD) at unbound energies can be calculated with the complex scaling method (CSM), in which the energy spectra of bound states, resonances and continuum states are obtained in terms of L(2) basis functions. In this method, the extended completeness relation is applied to the calculation of the Green functions, and the continuum-state part is approximately expressed in terms of discretized complex scaled continuum solutions. The obtained result is compared with the CLD calculated exactly from the scattering phase shift. The discretization in the CSM is shown to give a very good description of continuum states. We discuss how the scattering phase shifts can inversely be calculated from the discretized CLD using a basis function technique in the CSM.

Lifetimes and wave functions of ozone metastable vibrational states near the dissociation limit in a full-symmetry approach

NASA Astrophysics Data System (ADS)

Lapierre, David; Alijah, Alexander; Kochanov, Roman; Kokoouline, Viatcheslav; Tyuterev, Vladimir

2016-10-01

Energies and lifetimes (widths) of vibrational states above the lowest dissociation limit of O163 were determined using a previously developed efficient approach, which combines hyperspherical coordinates and a complex absorbing potential. The calculations are based on a recently computed potential energy surface of ozone determined with a spectroscopic accuracy [Tyuterev et al., J. Chem. Phys. 139, 134307 (2013), 10.1063/1.4821638]. The effect of permutational symmetry on rovibrational dynamics and the density of resonance states in O3 is discussed in detail. Correspondence between quantum numbers appropriate for short- and long-range parts of wave functions of the rovibrational continuum is established. It is shown, by symmetry arguments, that the allowed purely vibrational (J =0 ) levels of O163 and O183, both made of bosons with zero nuclear spin, cannot dissociate on the ground-state potential energy surface. Energies and wave functions of bound states of the ozone isotopologue O163 with rotational angular momentum J =0 and 1 up to the dissociation threshold were also computed. For bound levels, good agreement with experimental energies is found: The rms deviation between observed and calculated vibrational energies is 1 cm-1. Rotational constants were determined and used for a simple identification of vibrational modes of calculated levels.

New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

PubMed

Ghoshal, Sourav; Hazra, Montu K

2014-04-03

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

Neutral-atom electron binding energies from relaxed-orbital relativistic Hartree-Fock-Slater calculations for Z between 2 and 106

NASA Technical Reports Server (NTRS)

Huang, K.-N.; Aoyagi, M.; Mark, H.; Chen, M. H.; Crasemann, B.

1976-01-01

Electron binding energies in neutral atoms have been calculated relativistically, with the requirement of complete relaxation. Hartree-Fock-Slater wave functions served as zeroth-order eigenfunctions to compute the expectation of the total Hamiltonian. A first-order correction to the local approximation was thus included. Quantum-electrodynamic corrections were made. For all elements with atomic numbers ranging from 2 to 106, the following quantities are listed: total energies, electron kinetic energies, electron-nucleus potential energies, electron-electron potential energies consisting of electrostatic and Breit interaction (magnetic and retardation) terms, and vacuum polarization energies. Binding energies including relaxation are listed for all electrons in all atoms over the indicated range of atomic numbers. A self-energy correction is included for the 1s, 2s, and 2p(1/2) levels. Results for selected atoms are compared with energies calculated by other methods and with experimental values.

A potential energy surface for the process H2 + H2O yielding H + H + H2O - Ab initio calculations and analytical representation

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

1991-01-01

Extensive ab initio calculations on the ground state potential energy surface of H2 + H2O were performed using a large contracted Gaussian basis set and a high level of correlation treatment. An analytical representation of the potential energy surface was then obtained which reproduces the calculated energies with an overall root-mean-square error of only 0.64 mEh. The analytic representation explicitly includes all nine internal degrees of freedom and is also well behaved as the H2 dissociates; it thus can be used to study collision-induced dissociation or recombination of H2. The strategy used to minimize the number of energy calculations is discussed, as well as other advantages of the present method for determining the analytical representation.

A rotamer energy level study of sulfuric acid.

PubMed

Partanen, Lauri; Pesonen, Janne; Sjöholm, Elina; Halonen, Lauri

2013-10-14

It is a common approach in quantum chemical calculations for polyatomic molecules to rigidly constrain some of the degrees of freedom in order to make the calculations computationally feasible. However, the presence of the rigid constraints also affects the kinetic energy operator resulting in the frozen mode correction, originally derived by Pesonen [J. Chem. Phys. 139, 144310 (2013)]. In this study, we compare the effects of this correction to several different approximations to the kinetic energy operator used in the literature, in the specific case of the rotamer energy levels of sulfuric acid. The two stable conformers of sulfuric acid are connected by the rotations of the O-S-O-H dihedral angles and possess C2 and Cs symmetry in the order of increasing energy. Our results show that of the models tested, the largest differences with the frozen mode corrected values were obtained by simply omitting the passive degrees of freedom. For the lowest 17 excited states, this inappropriate treatment introduces an increase of 9.6 cm(-1) on average, with an increase of 8.7 cm(-1) in the zero-point energies. With our two-dimensional potential energy surface calculated at the CCSD(T)-F12a/VDZ-F12 level, we observe a radical shift in the density of states compared to the harmonic picture, combined with an increase in zero point energy. Thus, we conclude that the quantum mechanical inclusion of the different conformers of sulfuric acid have a significant effect on its vibrational partition function, suggesting that it will also have an impact on the computational values of the thermodynamic properties of any reactions where sulfuric acid plays a role. Finally, we also considered the effect of the anharmonicities for the other vibrational degrees of freedom with a VSCF-calculation at the DF-MP2-F12/VTZ-F12 level of theory but found that the inclusion of the other conformer had the more important effect on the vibrational partition function.

The energy level alignment at metal–molecule interfaces using Wannier–Koopmans method

DOE PAGES

Ma, Jie; Liu, Zhen-Fei; Neaton, Jeffrey B.; ...

2016-06-30

We apply a recently developed Wannier-Koopmans method (WKM), based on density functional theory (DFT), to calculate the electronic energy level alignment at an interface between a molecule and metal substrate. We consider two systems: benzenediamine on Au (111), and a bipyridine-Au molecular junction. The WKM calculated level alignment agrees well with the experimental measurements where available, as well as previous GW and DFT + Σ results. These results suggest that the WKM is a general approach that can be used to correct DFT eigenvalue errors, not only in bulk semiconductors and isolated molecules, but also in hybrid interfaces.

Electron-Impact Excitation Cross Sections for Modeling Non-Equilibrium Gas

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Liu, Yen; Panesi, Marco; Munafo, Alessandro; Wray, Alan; Carbon, Duane F.

2015-01-01

In order to provide a database for modeling hypersonic entry in a partially ionized gas under non-equilibrium, the electron-impact excitation cross sections of atoms have been calculated using perturbation theory. The energy levels covered in the calculation are retrieved from the level list in the HyperRad code. The downstream flow-field is determined by solving a set of continuity equations for each component. The individual structure of each energy level is included. These equations are then complemented by the Euler system of equations. Finally, the radiation field is modeled by solving the radiative transfer equation.

Energy levels and radiative transition rates for Ge XXXI, As XXXII, and Se XXXIII

NASA Astrophysics Data System (ADS)

Aggarwal, Sunny; Singh, J.; Jha, A. K. S.; Mohan, Man

2014-07-01

Fine-structure energies of the 67 levels belonging to the 1s2, 1s 2l, 1s3l, 1s4l, 1s5l, and 1s6l configurations of Ge XXXI, As XXXII, and Se XXXIII have been calculated using the General-Purpose Relativistic Atomic Structure Package. In addition, radiative rates, oscillator strengths, transition wavelengths, and line strengths have been calculated for all electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transitions among these levels. Lifetimes are also presented for all excited levels of these three ions. We have compared our results with the results available in the literature and the accuracy of the data is assessed. We predict new energy levels, oscillator strengths, and transition probabilities where no other theoretical or experimental results are available, which will form the basis for future experimental work.

Synthesis, spectroscopic (FT-IR, FT-Raman, UV and NMR) and computational studies on 3t-pentyl-2r,6c-diphenylpiperidin-4-one semicarbazone

NASA Astrophysics Data System (ADS)

Arockia doss, M.; Savithiri, S.; Rajarajan, G.; Thanikachalam, V.; Saleem, H.

2015-09-01

The structural and spectroscopic studies of 3t-pentyl-2r,6c-diphenylpiperidin-4-one semicarbazone (PDPOSC) were made by adopting B3LYP/HF levels theory using 6-311++G(d,p) basis set. The FT-IR and Raman spectra were recorded in solid phase, the fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. DFT method indicates that B3LYP is superior to HF method for molecular vibrational analysis. UV-vis spectrum of the compound was recorded in different solvents in the region of 200-800 nm and the electronic properties such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies were evaluated by time-dependent DFT (TD-DFT) approach. The polarizability and first order hyperpolarizability of the title molecule were calculated and interpreted. The hyperconjugative interaction energy (E(2)) and electron densities of donor (i) and acceptor (j) bonds were calculated using NBO analysis. In addition, MEP and atomic charges of carbon, nitrogen and oxygen were calculated using B3LYP/6-311++G(d,p) level theory. Moreover, thermodynamic properties of the title compound were calculated by B3LYP/HF, levels using 6-311++G(d,p) basis set. The 1H and 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.

Saving time and energy with oversubscription and semi-direct Møller-Plesset second order perturbation methods.

PubMed

Fought, Ellie L; Sundriyal, Vaibhav; Sosonkina, Masha; Windus, Theresa L

2017-04-30

In this work, the effect of oversubscription is evaluated, via calling 2n, 3n, or 4n processes for n physical cores, on semi-direct MP2 energy and gradient calculations and RI-MP2 energy calculations with the cc-pVTZ basis using NWChem. Results indicate that on both Intel and AMD platforms, oversubscription reduces total time to solution on average for semi-direct MP2 energy calculations by 25-45% and reduces total energy consumed by the CPU and DRAM on average by 10-15% on the Intel platform. Semi-direct gradient time to solution is shortened on average by 8-15% and energy consumption is decreased by 5-10%. Linear regression analysis shows a strong correlation between time to solution and total energy consumed. Oversubscribing during RI-MP2 calculations results in performance degradations of 30-50% at the 4n level. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Effects of Shape and Strain Distribution of Quantum Dots on Optical Transition in the Quantum Dot Infrared Photodetectors

PubMed Central

2008-01-01

We present a systemic theoretical study of the electronic properties of the quantum dots inserted in quantum dot infrared photodetectors (QDIPs). The strain distribution of three different shaped quantum dots (QDs) with a same ratio of the base to the vertical aspect is calculated by using the short-range valence-force-field (VFF) approach. The calculated results show that the hydrostatic strain ɛHvaries little with change of the shape, while the biaxial strain ɛBchanges a lot for different shapes of QDs. The recursion method is used to calculate the energy levels of the bound states in QDs. Compared with the strain, the shape plays a key role in the difference of electronic bound energy levels. The numerical results show that the deference of bound energy levels of lenslike InAs QD matches well with the experimental results. Moreover, the pyramid-shaped QD has the greatest difference from the measured experimental data. PMID:20596318

Ab initio non-adiabatic study of the 4pσ B'' 1Σ+u state of H2

NASA Astrophysics Data System (ADS)

Glass-Maujean, M.; Schmoranzer, H.

2018-05-01

Fully ab initio non-adiabatic multichannel quantum defect calculations of the 4pσ B'' 1∑u+ energy levels, line intensities and widths, based on the latest quantum-chemical clamped-nuclei calculations of Wolniewicz and collaborators are presented for H2. The B″ state corresponds to the inner well of the ? state. The B'' v ≥ 1 levels are rapidly predissociated through vibrational coupling with the 3pσ B' 1Σ+u continuum so that coupled-equation calculations become unstable. Multichannel quantum defect theory, on the other hand, is demonstrated to be particularly suited to this situation. Experimental data as level energies, line intensities and dissociation widths were revisited and corrected. Reinvestigating previously published spectra, several new lines were assigned.

Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

NASA Astrophysics Data System (ADS)

Frisch, Michael J.; Binkley, J. Stephen; Schaefer, Henry F., III

1984-08-01

The relative energies of the stationary points on the FH2 and H2CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Møller-Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H2→FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol-1 of the experimental value using the largest basis set considered. The qualitative features of the H2CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended.

The unrestricted Hartree-Fock self consistent field calculation for spin density wave state in metallic carbon nanotube

NASA Astrophysics Data System (ADS)

Kobayashi, Katsushi

1997-06-01

The possibility of a spin density wave (SDW) state in a metallic carbon nanotube (CN) and its electronic properties are investigated within the Hartree-Fock self consistent field (SCF) energy-band calculation. Two kinds of spatial SDW states are assumed in this study. Each assumed SDW on the wave function is constructed with the degenerate π orbital in the metallic CN system. The results calculated for the one SDW model of CN always have a relative stability (˜ 0.1 eV/cell) in SCF total energy compared with the original model in which no SDW is assumed. All the results calculated for another SDW model are completely equal to the original one. Moreover, in the energy dispersion of the former stable SDW model, the degenerate π level found in the original model disappears and the band gap (3-5 eV) occurs around at the Fermi level. The energetic stability and the band gap are also found in the π-electron band calculation within the Hubbard Hamiltonian.

An ab initio potential energy surface for the formic acid dimer: zero-point energy, selected anharmonic fundamental energies, and ground-state tunneling splitting calculated in relaxed 1-4-mode subspaces.

PubMed

Qu, Chen; Bowman, Joel M

2016-09-14

We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.

Atomic Data and Spectral Line Intensities for Ni XI

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Landi, E.

2010-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ni XI. We include in the calculations the 10 lowest configurations, corresponding to 164 fine structure levels: 3s(sup 2)3p(sup 6), 3s(sup 2)3p(sup 5)3d, 3s(sup 2)3p(sup 4)3d(sup 2), 3s3p(sup 6)3d, 3s(sup 2)3p(sup 5)4l and 3s3p6 4l with l =.s, p, d. Collision strengths are calculated at five incident energies for all transitions: 7.1, 16.8, 30.2, 48.7 and 74.1 Ry above the threshold of each transition. An additional energy, very close to the transition threshold, has been added, whose value is between 0.06 Ry and 0.25 Ry depending on the lower level. Calculations have been carried out using the Flexible Atomic Code and the distorted wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates of the present work, combined with Close Coupling collision excitation rate coefficient available in the literature for the lowest 17 levels, statistical equilibrium equations for level populations are solved at electron densities covering the 10(exp 8)-10(exp 14) cu cm range and at an electron temperature of logT(sub c)(K)=6.1, corresponding to the maximum abundance of Ni XI. Spectral line intensities are calculated, and their diagnostic relevance is discussed. This dataset will be made available in the next version of the CHIANTI database.

Blinking fluorescence of single donor-acceptor pairs: important role of "dark'' states in resonance energy transfer via singlet levels.

PubMed

Osad'ko, I S; Shchukina, A L

2012-06-01

The influence of triplet levels on Förster resonance energy transfer via singlet levels in donor-acceptor (D-A) pairs is studied. Four types of D-A pair are considered: (i) two-level donor and two-level acceptor, (ii) three-level donor and two-level acceptor, (iii) two-level donor and three-level acceptor, and (iv) three-level donor and three-level acceptor. If singlet-triplet transitions in a three-level acceptor molecule are ineffective, the energy transfer efficiency E=I_{A}/(I_{A}+I_{D}), where I_{D} and I_{A} are the average intensities of donor and acceptor fluorescence, can be described by the simple theoretical equation E(F)=FT_{D}/(1+FT_{D}). Here F is the rate of energy transfer, and T_{D} is the donor fluorescence lifetime. In accordance with the last equation, 100% of the donor electronic energy can be transferred to an acceptor molecule at FT_{D}≫1. However, if singlet-triplet transitions in a three-level acceptor molecule are effective, the energy transfer efficiency is described by another theoretical equation, E(F)=F[over ¯](F)T_{D}/[1+F[over ¯](F)T_{D}]. Here F[over ¯](F) is a function of F depending on singlet-triplet transitions in both donor and acceptor molecules. Expressions for the functions F[over ¯](F) are derived. In this case the energy transfer efficiency will be far from 100% even at FT_{D}≫1. The character of the intensity fluctuations of donor and acceptor fluorescence indicates which of the two equations for E(F) should be used to find the value of the rate F. Therefore, random time instants of photon emission in both donor and acceptor fluorescence are calculated by the Monte Carlo method for all four types of D-A pair. Theoretical expressions for start-stop correlators (waiting time distributions) in donor and acceptor fluorescence are derived. The probabilities w_{N}^{D}(t) and w_{N}^{A}(t) of finding N photons of donor and acceptor fluorescence in the time interval t are calculated for various values of the energy transfer rate F and for all four types of D-A pair. Comparison of the calculated D and A fluorescence trajectories with those measured by Weiss and co-workers proves the important role of triplet levels in energy transfer via singlet levels.

Fine structure transitions in Fe XIV

NASA Astrophysics Data System (ADS)

Nahar, Sultana N.

2013-07-01

Results are reported for Fe XIV energy levels and transitions obtained from the ab initio relativistic Breit-Pauli R-matrix (BPRM) method. BPRM method developed under the Iron Project is capable of calculating very large number of fine structure energy levels and corresponding transitions. However, unlike in the atomic structure calculations, where levels are identified spectroscopically based on the leading percentage contributions of configurations, BPRM is incapable of such identification of the levels and hence the transitions. The main reason for it is that the percentage contributions can not be determined exactly from the large number of channels in the R-matrix space. The present report describes an identification method that uses considerations of quantum defects of channels, contributions of channel from outer regions, Hund's rule, and angular momenta algebra for addition and completeness of fine structure components. The present calculations are carried out using a close coupling wave function expansion that included 26 core excitations from configurations 2s22p63s2, 2s22p63s3p,2s22p63p2,2s22p63s3d, and 2s22p63p3d. A total of 1002 fine structure levels with n ⩽ 10, l⩽9, and 0.5 ⩽J⩽ 9.5 with even and odd parities and the corresponding 130,520 electric dipole allowed (E1) fine structure transitions, a most complete set for astrophysical modelings of spectral analysis and opacities, is presented. Large number of new energy levels are found and identified. The energies agree very well, mostly in less than 1% with the highest being 1.9%, with the 68 observed fine structure levels. While the high lying levels may have some uncertainty, an overall accuracy of energy levels should be within 10%. BPRM transitions have been benchmarked with the existing most accurate calculated transition probabilities with very good agreement for most cases. Based on the accuracy of the method and comparisons, most of the transitions can be rated with A (⩽10%) to C (⩽30%).

Method and basis set dependence of anharmonic ground state nuclear wave functions and zero-point energies: application to SSSH.

PubMed

Kolmann, Stephen J; Jordan, Meredith J T

2010-02-07

One of the largest remaining errors in thermochemical calculations is the determination of the zero-point energy (ZPE). The fully coupled, anharmonic ZPE and ground state nuclear wave function of the SSSH radical are calculated using quantum diffusion Monte Carlo on interpolated potential energy surfaces (PESs) constructed using a variety of method and basis set combinations. The ZPE of SSSH, which is approximately 29 kJ mol(-1) at the CCSD(T)/6-31G* level of theory, has a 4 kJ mol(-1) dependence on the treatment of electron correlation. The anharmonic ZPEs are consistently 0.3 kJ mol(-1) lower in energy than the harmonic ZPEs calculated at the Hartree-Fock and MP2 levels of theory, and 0.7 kJ mol(-1) lower in energy at the CCSD(T)/6-31G* level of theory. Ideally, for sub-kJ mol(-1) thermochemical accuracy, ZPEs should be calculated using correlated methods with as big a basis set as practicable. The ground state nuclear wave function of SSSH also has significant method and basis set dependence. The analysis of the nuclear wave function indicates that SSSH is localized to a single symmetry equivalent global minimum, despite having sufficient ZPE to be delocalized over both minima. As part of this work, modifications to the interpolated PES construction scheme of Collins and co-workers are presented.

Method and basis set dependence of anharmonic ground state nuclear wave functions and zero-point energies: Application to SSSH

NASA Astrophysics Data System (ADS)

Kolmann, Stephen J.; Jordan, Meredith J. T.

2010-02-01

One of the largest remaining errors in thermochemical calculations is the determination of the zero-point energy (ZPE). The fully coupled, anharmonic ZPE and ground state nuclear wave function of the SSSH radical are calculated using quantum diffusion Monte Carlo on interpolated potential energy surfaces (PESs) constructed using a variety of method and basis set combinations. The ZPE of SSSH, which is approximately 29 kJ mol-1 at the CCSD(T)/6-31G∗ level of theory, has a 4 kJ mol-1 dependence on the treatment of electron correlation. The anharmonic ZPEs are consistently 0.3 kJ mol-1 lower in energy than the harmonic ZPEs calculated at the Hartree-Fock and MP2 levels of theory, and 0.7 kJ mol-1 lower in energy at the CCSD(T)/6-31G∗ level of theory. Ideally, for sub-kJ mol-1 thermochemical accuracy, ZPEs should be calculated using correlated methods with as big a basis set as practicable. The ground state nuclear wave function of SSSH also has significant method and basis set dependence. The analysis of the nuclear wave function indicates that SSSH is localized to a single symmetry equivalent global minimum, despite having sufficient ZPE to be delocalized over both minima. As part of this work, modifications to the interpolated PES construction scheme of Collins and co-workers are presented.

Accurate calculation of dynamic Stark shifts and depopulation rates of Rydberg energy levels induced by blackbody radiation. Hydrogen, helium, and alkali-metal atoms

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

Farley, J.W.; Wing, W.H.

1981-05-01

A highly excited (Rydberg) atom bathed in blackbody radiation is perturbed in two ways. A dynamic Stark shift is induced by the off-resonant components of the blackbody radiation. Additionally, electric-dipole transitions to other atomic energy levels are induced by the resonant components of the blackbody radiation. This depopulation effect shortens the Rydberg-state lifetime, thereby broadening the energy level. Calculations of these two effects in many states of hydrogen, helium, and the alkali-metal atoms Li, Na, K, Rb, and Cs are presented for T = 300 K. Contributions from the entire blackbody spectrum and from both discrete and continuous perturbing statesmore » are included. The accuracy is considerably greater than that of previous estimates.« less

Recent advances in QM/MM free energy calculations using reference potentials.

PubMed

Duarte, Fernanda; Amrein, Beat A; Blaha-Nelson, David; Kamerlin, Shina C L

2015-05-01

Recent years have seen enormous progress in the development of methods for modeling (bio)molecular systems. This has allowed for the simulation of ever larger and more complex systems. However, as such complexity increases, the requirements needed for these models to be accurate and physically meaningful become more and more difficult to fulfill. The use of simplified models to describe complex biological systems has long been shown to be an effective way to overcome some of the limitations associated with this computational cost in a rational way. Hybrid QM/MM approaches have rapidly become one of the most popular computational tools for studying chemical reactivity in biomolecular systems. However, the high cost involved in performing high-level QM calculations has limited the applicability of these approaches when calculating free energies of chemical processes. In this review, we present some of the advances in using reference potentials and mean field approximations to accelerate high-level QM/MM calculations. We present illustrative applications of these approaches and discuss challenges and future perspectives for the field. The use of physically-based simplifications has shown to effectively reduce the cost of high-level QM/MM calculations. In particular, lower-level reference potentials enable one to reduce the cost of expensive free energy calculations, thus expanding the scope of problems that can be addressed. As was already demonstrated 40 years ago, the usage of simplified models still allows one to obtain cutting edge results with substantially reduced computational cost. This article is part of a Special Issue entitled Recent developments of molecular dynamics. Copyright © 2014. Published by Elsevier B.V.

Precise calculation of quasienergies of a driven two-level atom based on the Guo-Wu-Van Woerkom solution

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

Wang Yi; Zhang Jingtao; Xu Zhizhan

2010-07-15

The exact algebraic solution recently obtained by Guo, Wu, and Van Woerkom (Phys. Rev. A 73 (2006) 023419) made possible accurate calculations of quasienergies of a driven two-level atom with an arbitrary original energy spacing and laser intensity. Due to the complication of the analytic solutions that involves an infinite number of infinite determinants, many mathematical difficulties must be overcome to obtain precise values of quasienergies. In this paper, with a further developed algebraic method, we show how to solve the computational problem completely and results are presented in a data table. With this table, one can easily obtain allmore » quasienergies of a driven two-level atom with an arbitrary original energy spacing and arbitrary intensity and frequency of the driving laser. The numerical solution technique developed here can be applied to the calculation of Freeman resonances in photoelectron energy spectra. As an example for applications, we show how to use the data table to calculate the peak laser intensity at which a Freeman resonance occurs in the transition between the ground Xe 5p P{sub 3/2} state and the Rydberg state Xe 8p P{sub 3/2}.« less

Synthesis, electronic structure investigation of 3-pentyl-2,6-di(furan-2-yl)piperidin-4-one by FT-IR, FT-Raman and UV-Visible spectral studies and ab initio/DFT calculations.

PubMed

Arockia Doss, M; Savithiri, S; Rajarajan, G; Thanikachalam, V; Anbuselvan, C

2015-12-05

FT-IR and FT-Raman spectra of 3-pentyl-2,6-di(furan-2-yl) piperidin-4-one (3-PFPO) were recorded in the solid phase. The structural and spectroscopic analyses of 3-PFPO were made by using B3LYP/HF level with 6-311++G(d, p) basis set. The fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Comparison of the observed fundamental vibrational frequencies of 3-PFPO with calculated results by HF and DFT methods indicates that B3LYP is superior to HF method for molecular vibrational problems. The electronic properties such as excitation energies, oscillator strength, wavelengths and HOMO-LUMO energies were obtained by time-dependent DFT (TD-DFT) approach. The polarizability and first order hyperpolarizability of the title molecule were calculated and interpreted. The hyperconjugative interaction energy (E((2))) and electron densities of donor (i) and acceptor (j) bonds were calculated using NBO analysis. In addition, MEP and atomic charges of carbon, nitrogen, oxygen and hydrogen were calculated using B3LYP/6-311++G(d, p) level theory. Moreover, thermodynamic properties (heat capacities, entropy and enthalpy) of the title compound at different temperatures were calculated in gas phase. Copyright © 2015 Elsevier B.V. All rights reserved.

Constructing the GW self-energy of a point defect from the perfect crystal and the near neighborhood of the defect

NASA Astrophysics Data System (ADS)

Skachkov, Dmitry; van Schilfgaarde, Mark; Lambrecht, Walter

The full-potential linearized muffin-tin orbital method allows for a real space representation of the GW or quasi-particle self-consistent (QS)GW self-energy ΣR , L ; R' + T , L'. This can be used to construct the self-energy matrix for a point defect system in a large supercell from that of the perfect crystal in the primitive cell and the self-energy of the defect site and its near neighborhood, obtained self-consistently in a smaller supercell. At the interface between both regions we can average the two types of ΣR , L ; R' + T , L' matrix blocks. The result relies on the limited range of the self-energy matrix in real space. It means that we can calculate the quasiparticle energy levels of the defect system at essentially the cost of a DFT calculation and a few QSGW calculations for relatively small systems. The approach presently focuses on quasiparticle energy levels of band structures of the defect system rather than total energies. We will present test results for AsGa\\ in GaAs, ZnGe in ZnGeN2, NO, VO, VZn, and NO - VZn in ZnO. Supported by the US-DOE-BES under Grant No. DE-SC0008933.

Anab InitioStudy of the NH2+Absorption Spectrum

NASA Astrophysics Data System (ADS)

Osmann, Gerald; Bunker, P. R.; Jensen, Per; Kraemer, W. P.

1997-12-01

In a previous publication (1997. P. Jensen,J. Mol. Spectrosc.181,207-214), rotation-vibration energy levels for the electronic ground stateX˜3B1of the amidogen ion, NH2+, were predicted using the MORBID Hamiltonian and computer program with anab initiopotential energy surface. In the present paper we calculate a newab initiopotential energy surface for theX˜3B1state, and we calculateab initiothe potential energy surfaces of theã1A1andb˜1B1excited singlet electronic states (which become degenerate as a1Δ state at linearity). We use the multireference configuration interaction (MR-CI) level of theory with molecular orbital bases that are optimized separately for each state by complete-active-space SCF (CASSCF) calculations. For theX˜state we use the MORBID Hamiltonian and computer program to obtain the rotation-vibration energies. For theãandb˜excited singlet electronic states we calculate the rovibronic energy levels using the RENNER Hamiltonian and computer program. We also calculateab initiothe dipole moment surfaces for theX˜,ã, andb˜electronic states, and the out-of-plane transition moment surface for theb˜←ãelectronic transition. We use this information to simulate absorption spectra withinX˜3B1andã1A1state and of theb˜1B1← ã1A1transition in order to aid in the search for them.

Mass-number and excitation-energy dependence of the spin cutoff parameter

DOE PAGES

Grimes, S. M.; Voinov, A. V.; Massey, T. N.

2016-07-12

Here, the spin cutoff parameter determining the nuclear level density spin distribution ρ(J) is defined through the spin projection as < J 2 z > 1/2 or equivalently for spherical nuclei, (< J(J+1) >/3) 1/2. It is needed to divide the total level density into levels as a function of J. To obtain the total level density at the neutron binding energy from the s-wave resonance count, the spin cutoff parameter is also needed. The spin cutoff parameter has been calculated as a function of excitation energy and mass with a super-conducting Hamiltonian. Calculations have been compared with two commonlymore » used semiempirical formulas. A need for further measurements is also observed. Some complications for deformed nuclei are discussed. The quality of spin cut off parameter data derived from isomeric ratio measurement is examined.« less

Statistical properties of Pu 243 , and Pu 242 ( n , γ ) cross section calculation

DOE PAGES

Laplace, T. A.; Zeiser, F.; Guttormsen, M.; ...

2016-01-29

The level density and γ-ray strength function (γSF) of 243Pu have been measured in the quasicontinuum using the Oslo method. Excited states in 243Pu were populated using the 242Pu(d,p) reaction. The level density closely follows the constant-temperature level density formula for excitation energies above the pairing gap. The γSF displays a double-humped resonance at low energy as also seen in previous investigations of actinide isotopes. The structure is interpreted as the scissors resonance and has a centroid of ω SR = 2.42(5) MeV and a total strength of B SR = 10.1(15) μ 2 N, which is in excellent agreementmore » with sum-rule estimates. Lastly, the measured level density and γSF were used to calculate the 242Pu(n,γ) cross section in a neutron energy range for which there were previously no measured data.« less

The energy level alignment at metal–molecule interfaces using Wannier–Koopmans method

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

Ma, Jie; Wang, Lin-Wang, E-mail: lwwang@lbl.gov; Liu, Zhen-Fei

2016-06-27

We apply a recently developed Wannier–Koopmans method (WKM), based on density functional theory (DFT), to calculate the electronic energy level alignment at an interface between a molecule and metal substrate. We consider two systems: benzenediamine on Au (111), and a bipyridine-Au molecular junction. The WKM calculated level alignment agrees well with the experimental measurements where available, as well as previous GW and DFT + Σ results. Our results suggest that the WKM is a general approach that can be used to correct DFT eigenvalue errors, not only in bulk semiconductors and isolated molecules, but also in hybrid interfaces.

Calculation of levels, transition rates, and lifetimes for the arsenic isoelectronic sequence Sn XVIII-Ba XXIV, W XLII

NASA Astrophysics Data System (ADS)

Wang, K.; Chen, Z. B.; Chen, C. Y.; Yan, J.; Dang, W.; Zhao, X. H.; Yang, X.

2017-09-01

Multi-configuration Dirac-Fock (MCDF) calculations of energy levels, wavelengths, oscillator strengths, lifetimes, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), magnetic quadrupole (M2) transition rates are reported for the arsenic isoelectronic sequence Sn XVIII-Ba XXIV, W XLII. Results are presented among the 86 levels of the 4s2 4p3, 4 s 4p4, 4p5, 4s2 4p2 4 d, and 4 s 4p3 4 d configurations in each ion. The relativistic atomic structure package GRASP2K is adopted for the calculations, in which the contributions from the correlations within the n ≤ 7 complexes, Breit interaction (BI) and quantum electrodynamics (QED) effects are taking into account. The many-body perturbation theory (MBPT) method is also employed as an independent calculation for comparison purposes, taking W XLII as an example. Calculated results are compared with data from other calculations and the observed values from the Atomic Spectra Database (ASD) of the National Institute of Standards and Technology (NIST). Good agreements are obtained. i.e, the accuracy of our energy levels is assessed to be better than 0.6%. These accurate theoretical data should be useful for diagnostics of hot plasmas in fusion devices.

Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry

NASA Astrophysics Data System (ADS)

Varandas, António J. C.

2018-04-01

Because the one-electron basis set limit is difficult to reach in correlated post-Hartree-Fock ab initio calculations, the low-cost route of using methods that extrapolate to the estimated basis set limit attracts immediate interest. The situation is somewhat more satisfactory at the Hartree-Fock level because numerical calculation of the energy is often affordable at nearly converged basis set levels. Still, extrapolation schemes for the Hartree-Fock energy are addressed here, although the focus is on the more slowly convergent and computationally demanding correlation energy. Because they are frequently based on the gold-standard coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)], correlated calculations are often affordable only with the smallest basis sets, and hence single-level extrapolations from one raw energy could attain maximum usefulness. This possibility is examined. Whenever possible, this review uses raw data from second-order Møller-Plesset perturbation theory, as well as CCSD, CCSD(T), and multireference configuration interaction methods. Inescapably, the emphasis is on work done by the author's research group. Certain issues in need of further research or review are pinpointed.

Electron Transport and Nonlinear Optical Properties of Substituted Aryldimesityl Boranes: A DFT Study

PubMed Central

Pandith, Altaf Hussain; Islam, Nasarul

2014-01-01

A comprehensive theoretical study was carried out on a series of aryldimesityl borane (DMB) derivatives using Density Functional theory. Optimized geometries and electronic parameters like electron affinity, reorganization energy, frontiers molecular contours, polarizability and hyperpolarizability have been calculated by employing B3PW91/6-311++G (d, p) level of theory. Our results show that the Hammett function and geometrical parameters correlates well with the reorganization energies and hyperpolarizability for the series of DMB derivatives studied in this work. The orbital energy study reveals that the electron releasing substituents increase the LUMO energies and electron withdrawing substituents decrease the LUMO energies, reflecting the electron transport character of aryldimesityl borane derivatives. From frontier molecular orbitals diagram it is evident that mesityl rings act as the donor, while the phenylene and Boron atom appear as acceptors in these systems. The calculated hyperpolarizability of secondary amine derivative of DMB is 40 times higher than DMB (1). The electronic excitation contributions to the hyperpolarizability studied by using TDDFT calculation shows that hyperpolarizability correlates well with dipole moment in ground and excited state and excitation energy in terms of the two-level model. Thus the results of these calculations can be helpful in designing the DMB derivatives for efficient electron transport and nonlinear optical material by appropriate substitution with electron releasing or withdrawing substituents on phenyl ring of DMB system. PMID:25479382

Calculation of SF6-/SF6 and Cl-/CFCl3 electron attachment cross sections in the energy range 0-100 meV

NASA Technical Reports Server (NTRS)

Chutjian, A.

1982-01-01

Electron attachment cross sections for the processes SF6-/SF6 and Cl-/CFCl3 are calculated in a local theory using a model in which diatomic-like potential energy curves for the normal modes are constructed from available spectroscopic data. Thermally populated vibrational and rotational levels are included. Good agreement is found with experimental cross sections in the energy range 5-100 meV for a particular choice of potential energy curve parameters.

Carbon Monoxide Hydrogenation on Ice Surfaces.

PubMed

Kuwahata, Kazuaki; Ohno, Kaoru

2018-03-14

We have performed density functional calculations to investigate the carbon monoxide hydrogenation reaction (H+CO→HCO), which is important in interstellar clouds. We found that the activation energy of the reaction on amorphous ice is lower than that on crystalline ice. In the course of this study, we demonstrated that it is roughly possible to use the excitation energy of the reactant molecule (CO) in place of the activation energy. This relationship holds also for small water clusters at the CCSD level of calculation and the two-layer-level ONIOM (CCSD : X3LYP) calculation. Generally, since it is computationally demanding to estimate activation energies of chemical reactions in a circumstance of many water molecules, this relationship enables one to determine the activation energy of this reaction on ice surfaces from the knowledge of the excitation energy of CO only. Incorporating quantum-tunneling effects, we discuss the reaction rate on ice surfaces. Our estimate that the reaction rate on amorphous ice is almost twice as large as that on crystalline ice is qualitatively consistent with the experimental evidence reported by Hidaka et al. [Chem. Phys. Lett., 2008, 456, 36.]. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Renner-Teller effect in HCCCl(+)(X̃(2)Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations.

PubMed

Sun, Wei; Dai, Zuyang; Wang, Jia; Mo, Yuxiang

2015-05-21

The spin-vibronic energy levels of the chloroacetylene cation up to 4000 cm(-1) above the ground state have been measured using the one-photon zero-kinetic energy photoelectron spectroscopic method. The spin-vibronic energy levels have also been calculated using a diabatic model, in which the potential energy surfaces are expressed by expansions of internal coordinates, and the Hamiltonian matrix equation is solved using a variational method with harmonic basis functions. The calculated spin-vibronic energy levels are in good agreement with the experimental data. The Renner-Teller (RT) parameters describing the vibronic coupling for the H-C≡C bending mode (ε4), Cl-C≡C bending mode (ε5), the cross-mode vibronic coupling (ε45) of the two bending vibrations, and their vibrational frequencies (ω4 and ω5) have also been determined using an effective Hamiltonian matrix treatment. In comparison with the spin-orbit interaction, the RT effect in the H-C≡C bending (ε4) mode is strong, while the RT effect in the Cl-C≡C bending mode is weak. There is a strong cross-mode vibronic coupling of the two bending vibrations, which may be due to a vibronic resonance between the two bending vibrations. The spin-orbit energy splitting of the ground state has been determined for the first time and is found to be 209 ± 2 cm(-1).

Effects of internal gain assumptions in building energy calculations

NASA Astrophysics Data System (ADS)

Christensen, C.; Perkins, R.

1981-01-01

The utilization of direct solar gains in buildings can be affected by operating profiles, such as schedules for internal gains, thermostat controls, and ventilation rates. Building energy analysis methods use various assumptions about these profiles. The effects of typical internal gain assumptions in energy calculations are described. Heating and cooling loads from simulations using the DOE 2.1 computer code are compared for various internal gain inputs: typical hourly profiles, constant average profiles, and zero gain profiles. Prototype single-family-detached and multifamily-attached residential units are studied with various levels of insulation and infiltration. Small detached commercial buildings and attached zones in large commercial buildings are studied with various levels of internal gains. The results indicate that calculations of annual heating and cooling loads are sensitive to internal gains, but in most cases are relatively insensitive to hourly variations in internal gains.

An ab initio global potential-energy surface for NH2(A(2)A') and vibrational spectrum of the Renner-Teller A(2)A'-X(2)A" system.

PubMed

Zhou, Shulan; Li, Zheng; Xie, Daiqian; Lin, Shi Ying; Guo, Hua

2009-05-14

A global potential-energy surface for the first excited electronic state of NH(2)(A(2)A(')) has been constructed by three-dimensional cubic spline interpolation of more than 20,000 ab initio points, which were calculated at the multireference configuration-interaction level with the Davidson correction using the augmented correlation-consistent polarized valence quadruple-zeta basis set. The (J=0) vibrational energy levels for the ground (X(2)A(")) and excited (A(2)A(')) electronic states of NH(2) were calculated on our potential-energy surfaces with the diagonal Renner-Teller terms. The results show a good agreement with the experimental vibrational frequencies of NH(2) and its isotopomers.

Ab initio Study on Ionization Energies of 3-Amino-1-propanol

NASA Astrophysics Data System (ADS)

Wang, Ke-dong; Jia, Ying-bin; Lai, Zhen-jiang; Liu, Yu-fang

2011-06-01

Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311++G** level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the intramolecular OH···N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molecular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of photoelectron spectra is interpreted.

Extended Fenske-Hall LCAO MO calculations of core-level shifts in solid P compounds

NASA Astrophysics Data System (ADS)

Franke, R.; Chassé, T.; Reinhold, J.; Streubel, P.; Szargan, R.

1997-08-01

Extended Fenske-Hall LCAO-MO ΔSCF calculations on solids modelled as H-pseudoatom saturated clusters are reported. The computational results verify the experimentally obtained initial-state (effective atomic charges, Madelung potential) and relaxation-energy contributions to the XPS phosphorus core-level binding energy shifts measured in Na 3PO 3S, Na 3PO 4, Na 2PO 3F and NH 4PF 6 in reference to red phosphorus. It is shown that the different initial-state contributions observed in the studied phosphates are determined by local and nonlocal terms while the relaxation-energy contributions are mainly dependent on the nature of the nearest neighbors of the phosphorus atom.

Fission Dynamics with Microscopic Level Densities

DOE PAGES

Ward, D.; Carlsson, B. G.; Dossing, Th.; ...

2017-01-01

We present a consistent framework for treating the energy and angularmomentum dependence of the shape evolution in the nuclear fission. It combines microscopically calculated level densities with the Metropolis-walk method, has no new parameters, and can elucidate the energy-dependent influence of pairing and shell effects on the dynamics of warm nuclei.

Computational techniques in tribology and material science at the atomic level

NASA Technical Reports Server (NTRS)

Ferrante, J.; Bozzolo, G. H.

1992-01-01

Computations in tribology and material science at the atomic level present considerable difficulties. Computational techniques ranging from first-principles to semi-empirical and their limitations are discussed. Example calculations of metallic surface energies using semi-empirical techniques are presented. Finally, application of the methods to calculation of adhesion and friction are presented.

Towards Accurate Ab Initio Predictions of the Spectrum of Methane

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Kwak, Dochan (Technical Monitor)

2001-01-01

We have carried out extensive ab initio calculations of the electronic structure of methane, and these results are used to compute vibrational energy levels. We include basis set extrapolations, core-valence correlation, relativistic effects, and Born- Oppenheimer breakdown terms in our calculations. Our ab initio predictions of the lowest lying levels are superb.

Atomic Data and Spectral Line Intensities for Ni XXI

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Landi, E.; Fisher, Richard R. (Technical Monitor)

2001-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ni XXI. The configurations used are 2s(sup 2)2p(sup 4), 2s2p(sup 5), 2p(sup 6), 2s(sup 2)2p(sup 3)3s, and 2s(sup 2)3p(sup 3)3d giving rise to 58 fine-structure levels in intermediate coupling. Collision strengths are calculated at five incident energies, 85, 170, 255, 340, and 425 Ry. Excitation rate coefficients are calculated by assuming a Maxwellian electron velocity distribution at an electron temperature of log T(sub e)(K)=6.9, corresponding to maximum abundance of Ni XXI. Using the excitation rate coefficients and the radiative transition rates, statistical equilibrium equations for level populations are solved at electron densities 10(exp 8)-10(exp 14) per cubic centimeter. Relative spectral line intensities are calculated. Proton excitation rates between the lowest three levels have been included in the statistical equilibrium equations. The predicted intensity ratios are compared with available observations.

Crystal field analysis of the energy level structure of Cs2NaAlF6:Cr3+

NASA Astrophysics Data System (ADS)

Rudowicz, C.; Brik, M. G.; Avram, N. M.; Yeung, Y. Y.; Gnutek, P.

2006-06-01

An analysis of the energy level structure of Cr3+ ions in Cs2NaAlF6 crystal is performed using the exchange charge model (ECM) together with the crystal field analysis/microscopic spin Hamiltonian (CFA/MSH) computer package. Utilizing the crystal structure data, our approach enables modelling of the crystal field parameters (CFPs) and thus the energy level structure for Cr3+ ions at the two crystallographically inequivalent sites in Cs2NaAlF6. Using the ECM initial adjustment procedure, the CFPs are calculated in the crystallographic axis system centred at the Cr3+ ion at each site. Additionally the CFPs are also calculated using the superposition model (SPM). The ECM and SPM predicted CFP values match very well. Consideration of the symmetry aspects for the so-obtained CFP datasets reveals that the latter axis system matches the symmetry-adapted axis system related directly to the six Cr-F bonds well. Using the ECM predicted CFPs as an input for the CFA/MSH package, the complete energy level schemes are calculated for Cr3+ ions at the two sites. Comparison of the theoretical results with the experimental spectroscopic data yields satisfactory agreement. Our results confirm that the actual symmetry at both impurity sites I and II in the Cs2NaAlF6:Cr3+ system is trigonal D3d. The ECM predicted CFPs may be used as the initial (starting) parameters for simulations and fittings of the energy levels for Cr3+ ions in structurally similar hosts.

Line Lists for LiF and LiCl in the X 1Σ+ Ground State

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Bernath, Peter F.

2018-03-01

Vibration–rotation line lists for 6LiF, 7LiF, 6Li35Cl, 6Li37Cl, 7Li35Cl, and 7Li37Cl in the X 1Σ+ ground states have been prepared. The rovibrational energy levels have been calculated using potential energy surfaces determined by direct potential-fitting employing the rotational and rovibrational transition frequencies of all isotopologues, and required the inclusion of Born–Oppenheimer breakdown terms. Dipole moment functions calculated ab initio at the MRCI/aug-cc-pwCV5Z level have been used for line strength calculations. Partition functions for temperatures up to 5000 K have been calculated. LiF and LiCl are predicted to be present in the atmospheres of hot rocky exoplanets, brown dwarfs, and cool stars.

Un-catalyzed peptide bond formation between two monomers of glycine, alanine, serine, threonine, and aspartic acid in gas phase: a density functional theory study

NASA Astrophysics Data System (ADS)

Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K.

2016-05-01

In the present report, un-catalyzed peptide bond formation between two monomers of glycine (Gly), alanine (Ala), serine (Ser), threonine (Thr), and aspartic acid (Asp) has been investigated in gas phase via two steps reaction mechanism and concerted mechanism at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. The peptide bond is formed through a nucleophilic reaction via transition states, TS1 and TS2 in stepwise mechanism. The TS1 reveals formation of a new C-N bond while TS2 illustrate the formation of C=O bond. In case of concerted mechanism, C-N bond is formed by a single four-centre transition state (TS3). The energy barrier is used to explain the involvement of energy at each step of the reaction. The energy barrier (20-48 kcal/mol) is required for the transformation of reactant state R1 to TS1 state and intermediate state I1 to TS2 state. The large value of energy barrier is explained in terms of distortion and interaction energies for stepwise mechanism. The energy barrier of TS3 in concerted mechanism is very close to the energy barrier of the first transition state (TS1) of the stepwise mechanism for the formation of Gly-Gly and Ala-Ala di- peptide. However, in case of Ser-Ser, Thr-Thr and Asp-Asp di-peptide, the energy barrier of TS3 is relatively high than that of the energy barrier of TS1 calculated at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. In both the mechanisms, the value of energy barrier calculated at B3LYP/6-31G(d,p) level of theory is greater than that of the value calculated at M062X/6-31G(d,p) level of theory.

Explicit hydration of ammonium ion by correlated methods employing molecular tailoring approach

NASA Astrophysics Data System (ADS)

Singh, Gurmeet; Verma, Rahul; Wagle, Swapnil; Gadre, Shridhar R.

2017-11-01

Explicit hydration studies of ions require accurate estimation of interaction energies. This work explores the explicit hydration of the ammonium ion (NH4+) employing Møller-Plesset second order (MP2) perturbation theory, an accurate yet relatively less expensive correlated method. Several initial geometries of NH4+(H2O)n (n = 4 to 13) clusters are subjected to MP2 level geometry optimisation with correlation consistent aug-cc-pVDZ (aVDZ) basis set. For large clusters (viz. n > 8), molecular tailoring approach (MTA) is used for single point energy evaluation at MP2/aVTZ level for the estimation of MP2 level binding energies (BEs) at complete basis set (CBS) limit. The minimal nature of the clusters upto n ≤ 8 is confirmed by performing vibrational frequency calculations at MP2/aVDZ level of theory, whereas for larger clusters (9 ≤ n ≤ 13) such calculations are effected via grafted MTA (GMTA) method. The zero point energy (ZPE) corrections are done for all the isomers lying within 1 kcal/mol of the lowest energy one. The resulting frequencies in N-H region (2900-3500 cm-1) and in O-H stretching region (3300-3900 cm-1) are in found to be in excellent agreement with the available experimental findings for 4 ≤ n ≤ 13. Furthermore, GMTA is also applied for calculating the BEs of these clusters at coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory with aVDZ basis set. This work thus represents an art of the possible on contemporary multi-core computers for studying explicit molecular hydration at correlated level theories.

Imaging of the outer valence orbitals of CO by electron momentum spectroscopy — Comparison with high level MRSD-CI and DFT calculations

NASA Astrophysics Data System (ADS)

Fan, X. W.; Chen, X. J.; Zhou, S. J.; Zheng, Y.; Brion, C. E.; Frey, R.; Davidson, E. R.

1997-09-01

A newly constructed energy dispersive multichannel electron momentum spectrometer has been used to image the electron density of the outer valence orbitals of CO with high precision. Binding energy spectra are obtained at a coincidence energy resolution of 1.2 eV fwhm. The measured electron density profiles in momentum space for the outer valence orbitals of CO are compared with cross sections calculated using SCF wavefunctions with basis sets of varying complexity up to near-Hartree-Fock limit in quality. The effects of correlation and electronic relaxation on the calculated momentum profiles are investigated using large MRSD-CI calculations of the full ion-neutral overlap distributions, as well as large basis set DFT calculations with local and non-local (gradient corrected) functionals.

Spectroscopic study of the radionuclide 21Na for the astrophysical 17F(α ,p )20Ne reaction rate

NASA Astrophysics Data System (ADS)

Cha, S. M.; Chae, K. Y.; Ahn, S.; Bardayan, D. W.; Chipps, K. A.; Cizewski, J. A.; Howard, M. E.; Kozub, R. L.; Kwak, K.; Manning, B.; Matos, M.; O'Malley, P. D.; Pain, S. D.; Peters, W. A.; Pittman, S. T.; Ratkiewicz, A.; Smith, M. S.; Strauss, S.

2017-08-01

The 24Mg(p ,α )21Na reaction was measured at the Holifield Radioactive Ion Beam Facility of the Oak Ridge National Laboratory to study the spectroscopy of the radionuclide 21Na. A 31-MeV proton beam from the 25 MV tandem accelerator bombarded isotopically enriched 24Mg targets. Recoiling 4He particles were identified by an annular silicon strip detector array. Two energy levels at Ex=6.594 and 7.132 MeV were observed for the first time. By comparing the experimentally obtained angular distributions and distorted wave Born approximation calculations, the spins and parities of 21Na energy levels were constrained. The astrophysically-important 17F(α ,p )20Ne reaction rate was also calculated for the first time using resonance parameters for 12 energy levels.

Model Calculations with Excited Nuclear Fragmentations and Implications of Current GCR Spectra

NASA Astrophysics Data System (ADS)

Saganti, Premkumar

As a result of the fragmentation process in nuclei, energy from the excited states may also contribute to the radiation damage on the cell structure. Radiation induced damage to the human body from the excited states of oxygen and several other nuclei and its fragments are of a concern in the context of the measured abundance of the current galactic cosmic rays (GCR) environment. Nuclear Shell model based calculations of the Selective-Core (Saganti-Cucinotta) approach are being expanded for O-16 nuclei fragments into N-15 with a proton knockout and O-15 with a neutron knockout are very promising. In our on going expansions of these nuclear fragmentation model calculations and assessments, we present some of the prominent nuclei interactions from a total of 190 isotopes that were identified for the current model expansion based on the Quantum Multiple Scattering Fragmentation Model (QMSFRG) of Cucinotta. Radiation transport model calculations with the implementation of these energy level spectral characteristics are expected to enhance the understanding of radiation damage at the cellular level. Implications of these excited energy spectral calculations in the assessment of radiation damage to the human body may provide enhanced understanding of the space radiation risk assessment.

Ab Initio and Analytic Intermolecular Potentials for Ar-CF₄

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

Vayner, Grigoriy; Alexeev, Yuri; Wang, Jiangping

2006-03-09

Ab initio calculations at the CCSD(T) level of theory are performed to characterize the Ar + CF ₄ intermolecular potential. Extensive calculations, with and without a correction for basis set superposition error (BSSE), are performed with the cc-pVTZ basis set. Additional calculations are performed with other correlation consistent (cc) basis sets to extrapolate the Ar---CF₄potential energy minimum to the complete basis set (CBS) limit. Both the size of the basis set and BSSE have substantial effects on the Ar + CF₄ potential. Calculations with the cc-pVTZ basis set and without a BSSE correction, appear to give a good representation ofmore » the potential at the CBS limit and with a BSSE correction. In addition, MP2 theory is found to give potential energies in very good agreement with those determined by the much higher level CCSD(T) theory. Two analytic potential energy functions were determined for Ar + CF₄by fitting the cc-pVTZ calculations both with and without a BSSE correction. These analytic functions were written as a sum of two body potentials and excellent fits to the ab initio potentials were obtained by representing each two body interaction as a Buckingham potential.« less

The tert-butyl cation on zeolite Y: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Rosenbach, Nilton, Jr.; dos Santos, Alex P. A.; Franco, Marcelo; Mota, Claudio J. A.

2010-01-01

The structure and energy of the tert-butyl cation on zeolite Y were calculated at ONIOM(MP2(FULL)/6-31G( d, p):MNDO) level. The results indicated that the tert-butyl cation is a minimum and lies between 40 and 51 kJ mol -1 above in energy to the tert-butoxide, depending on the level of calculation. Both species are stabilized through hydrogen bonding interactions with the framework oxygen atoms. Experimental data of nucleophilic substitution of tert-butylchloride and bromide over NaY impregnated with NaCl or NaBr give additional support for the formation of the tert-butyl cation as a discrete intermediate on zeolite Y, in agreement with the calculations.

Recent advances in QM/MM free energy calculations using reference potentials☆

PubMed Central

Duarte, Fernanda; Amrein, Beat A.; Blaha-Nelson, David; Kamerlin, Shina C.L.

2015-01-01

Background Recent years have seen enormous progress in the development of methods for modeling (bio)molecular systems. This has allowed for the simulation of ever larger and more complex systems. However, as such complexity increases, the requirements needed for these models to be accurate and physically meaningful become more and more difficult to fulfill. The use of simplified models to describe complex biological systems has long been shown to be an effective way to overcome some of the limitations associated with this computational cost in a rational way. Scope of review Hybrid QM/MM approaches have rapidly become one of the most popular computational tools for studying chemical reactivity in biomolecular systems. However, the high cost involved in performing high-level QM calculations has limited the applicability of these approaches when calculating free energies of chemical processes. In this review, we present some of the advances in using reference potentials and mean field approximations to accelerate high-level QM/MM calculations. We present illustrative applications of these approaches and discuss challenges and future perspectives for the field. Major conclusions The use of physically-based simplifications has shown to effectively reduce the cost of high-level QM/MM calculations. In particular, lower-level reference potentials enable one to reduce the cost of expensive free energy calculations, thus expanding the scope of problems that can be addressed. General significance As was already demonstrated 40 years ago, the usage of simplified models still allows one to obtain cutting edge results with substantially reduced computational cost. This article is part of a Special Issue entitled Recent developments of molecular dynamics. PMID:25038480

Analysis of vibrational spectra of 3-halo-1-propanols CH(2)XCH(2)CH(2)OH (X is Cl and Br).

PubMed

Badawi, Hassan M; Förner, Wolfgang

2008-12-01

The conformational stability and the three rotor internal rotations in 3-chloro- and 3-bromo-1-propanols were investigated by DFT-B3LYP/6-311+G and ab initio MP2/6-311+G, MP3/6-311+G and MP4(SDTQ)//MP3/6-311+G levels of theory. On the calculated potential energy surface twelve distinct minima were located all of which were not predicted to have imaginary frequencies at the B3LYP level of theory. The calculated lowest energy minimum in the potential curves of both molecules was predicted to correspond to the Gauche-gauche-trans (Ggt) conformer in excellent agreement with earlier microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the two 3-halo-1-propanols were calculated at the B3LYP/6-311+G level of calculation and found to correspond to an equilibrium mixture of about 32% Ggt, 18% Ggg1, 13% Tgt, 8% Tgg and 8% Gtt conformations for 3-chloro-1-propanol and 34% Ggt, 15% Tgt, 13% Ggg1, 9% Tgg and 7% Gtt conformations for 3-bromo-1-propanol at 298.15K. The nature of the high energy conformations was verified by carrying out solvent experiments using formamide ( epsilon=109.5) and MP3 and MP4//MP3 calculations. The vibrational frequencies of each molecule in its three most stable forms were computed at the B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecules.

Accurate potential energy curves, spectroscopic parameters, transition dipole moments, and transition probabilities of 21 low-lying states of the CO+ cation

NASA Astrophysics Data System (ADS)

Xing, Wei; Shi, Deheng; Zhang, Jicai; Sun, Jinfeng; Zhu, Zunlue

2018-05-01

This paper calculates the potential energy curves of 21 Λ-S and 42 Ω states, which arise from the first two dissociation asymptotes of the CO+ cation. The calculations are conducted using the complete active space self-consistent field method, which is followed by the valence internally contracted multireference configuration interaction approach with the Davidson correction. To improve the reliability and accuracy of the potential energy curves, core-valence correlation and scalar relativistic corrections, as well as the extrapolation of potential energies to the complete basis set limit are taken into account. The spectroscopic parameters and vibrational levels are determined. The spin-orbit coupling effect on the spectroscopic parameters and vibrational levels is evaluated. To better study the transition probabilities, the transition dipole moments are computed. The Franck-Condon factors and Einstein coefficients of some emissions are calculated. The radiative lifetimes are determined for a number of vibrational levels of several states. The transitions between different Λ-S states are evaluated. Spectroscopic routines for observing these states are proposed. The spectroscopic parameters, vibrational levels, transition dipole moments, and transition probabilities reported in this paper can be considered to be very reliable and can be used as guidelines for detecting these states in an appropriate spectroscopy experiment, especially for the states that were very difficult to observe or were not detected in previous experiments.

Towards accurate ab initio predictions of the vibrational spectrum of methane

NASA Technical Reports Server (NTRS)

Schwenke, David W.

2002-01-01

We have carried out extensive ab initio calculations of the electronic structure of methane, and these results are used to compute vibrational energy levels. We include basis set extrapolations, core-valence correlation, relativistic effects, and Born-Oppenheimer breakdown terms in our calculations. Our ab initio predictions of the lowest lying levels are superb.

High-Level Radioactive Waste.

ERIC Educational Resources Information Center

Hayden, Howard C.

1995-01-01

Presents a method to calculate the amount of high-level radioactive waste by taking into consideration the following factors: the fission process that yields the waste, identification of the waste, the energy required to run a 1-GWe plant for one year, and the uranium mass required to produce that energy. Briefly discusses waste disposal and…

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

NASA Astrophysics Data System (ADS)

Tossell, J. A.

1997-04-01

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

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

Shirkov, Leonid; Makarewicz, Jan, E-mail: jama@amu.edu.pl

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowedmore » us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.« less

Energy level alignment at the interfaces between typical electrodes and nucleobases: Al/adenine/indium-tin-oxide and Al/thymine/indium-tin-oxide

NASA Astrophysics Data System (ADS)

Lee, Younjoo; Lee, Hyunbok; Park, Soohyung; Yi, Yeonjin

2012-12-01

We investigated the interfacial electronic structures of Al/adenine/indium-tin-oxide (ITO) and Al/thymine/ITO using in situ ultraviolet and x-ray photoemission spectroscopy and density functional theory calculations. Adenine shows both an interface dipole and level bending, whereas thymine shows only an interface dipole in contact with ITO. In addition, thymine possesses a larger ionization energy than adenine. These are understood with delocalized π states confirmed with theoretical calculations. For the interface between nucleobases and Al, both nucleobases show a prominent reduction of the electron injection barrier from Al to each base in accordance with a downward level shift.

Energy levels and radiative rates for transitions in B-like to F-like Kr ions (Kr XXXII XXVIII)

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Keenan, F. P.; Lawson, K. D.

2008-05-01

Energy levels, radiative rates, oscillator strengths, line strengths, and lifetimes have been calculated for transitions in B-like to F-like Kr ions, Kr XXXIII-XXVIII. For the calculations, the fully relativistic GRASP code has been adopted, and results are reported for all electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1), and magnetic quadrupole (M2) transitions among the lowest 125, 236, 272, 226, and 113 levels of Kr XXXII, Kr XXXI, Kr XXX, Kr XXIX, and Kr XXVIII, respectively, belonging to the n ⩽ 3 configurations. Comparisons are made with earlier available theoretical and experimental results, and some discrepancies have been noted and explained.

Energetics of Meloidogyne incognita on Resistant and Susceptible Alyceclover Genotypes

PubMed Central

Powers, L. E.; McSorley, R.

1993-01-01

To determine the energy cost of a population of Meloidogyne incognita on the roots of alyceclover, nematode biomass was estimated and equations in the literature were used to calculate energy budgets. Amounts of energy consumed, respired, or used in production of nematode biomass were calculated. Results suggested that severe infestations of root-knot nematodes can remove significant quantities of energy from their hosts. Over a 36-day period, a population of 2.6 females of M. incognita per root system removed less than 0.4 calories of energy from a resistant alyceclover plant but over 11 calories were removed by 28 females from a susceptible alyceclover. The calculations indicate that on the resistant alyceclover line, 53% of the energy assimilated by the root-knot population was allocated to respiration, with only 47% allocated to production, whereas on the susceptible line, 65% of the assimilated energy was allocated to production. Such energy demands by the parasite could result in significant reductions in yield quantity and quality at a field production level. PMID:19279766

Continuum and three-nucleon force effects on Be 9 energy levels

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

Langhammer, Joachim; Navrátil, Petr; Quaglioni, Sofia

2015-02-05

In this paper, we extend the recently proposed ab initio no-core shell model with continuum to include three-nucleon (3N) interactions beyond the few-body domain. The extended approach allows for the assessment of effects of continuum degrees of freedom as well as of the 3N force in ab initio calculations of structure and reaction observables of p- and lower-sd-shell nuclei. As a first application we concentrate on energy levels of the 9Be system for which all excited states lie above the n- 8Be threshold. For all energy levels, the inclusion of the continuum significantly improves the agreement with experiment, which wasmore » an issue in standard no-core shell model calculations. Furthermore, we find the proper treatment of the continuum indispensable for reliable statements about the quality of the adopted 3N interaction from chiral effective field theory. Finally, in particular, we find the 1/2 + resonance energy, which is of astrophysical interest, in good agreement with experiment.« less

Multi-configuration Dirac-Hartree-Fock (MCDHF) calculations for Ni XXV

NASA Astrophysics Data System (ADS)

Singh, Narendra; Aggarwal, Sunny

2018-03-01

We present accurate 165 fine-structure energy levels related to the configurations 1s22s2, 1s22p2, 1s2nƖn‧l‧ (n = 2, n‧ = 2, 3, 4, 5, Ɩ = s,p Ɩ‧ = s, p, d, f, g) of Ni XXV which may be useful ion for astrophysical and fusion plasma. For the calculations of energy levels and radiative rates, we have used the multiconfiguration Dirac-Hartree-Fock (MCDHF) method employed in GRASP2K code. The calculations are carried out in the active space approximation with the inclusion of the Breit interaction, the finite nuclear size effect, and quantum electrodynamic corrections. The transition wavelengths, transition probabilities, line strengths, and absorption oscillator strengths are reported for electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1), magnetic quadrupole (M2) transitions from the ground state. We have compared our calculated results with available theoretical and experimental data and good agreement is achieved. We predict new energy levels, oscillator strengths, line strengths and transition probabilities, where no other experimental or theoretical results are available. The present complete set of results should be of great help in line identification and the interpretation of spectra, as well as in the modelling and diagnostics of astrophysical and fusion plasmas.

Electron impact excitation of N IV: calculations with the DARC code and a comparison with ICFT results

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Keenan, F. P.; Lawson, K. D.

2016-10-01

There have been discussions in the recent literature regarding the accuracy of the available electron impact excitation rates (equivalently effective collision strengths Υ) for transitions in Be-like ions. In the present paper we demonstrate, once again, that earlier results for Υ are indeed overestimated (by up to four orders of magnitude), for over 40 per cent of transitions and over a wide range of temperatures. To do this we have performed two sets of calculations for N IV, with two different model sizes consisting of 166 and 238 fine-structure energy levels. As in our previous work, for the determination of atomic structure the GRASP (General-purpose Relativistic Atomic Structure Package) is adopted and for the scattering calculations (the standard and parallelised versions of) the Dirac Atomic R-matrix Code (DARC) are employed. Calculations for collision strengths and effective collision strengths have been performed over a wide range of energy (up to 45 Ryd) and temperature (up to 2.0 × 106 K), useful for applications in a variety of plasmas. Corresponding results for energy levels, lifetimes and A-values for all E1, E2, M1 and M2 transitions among 238 levels of N IV are also reported.

Relationship between electronic properties and drug activity of seven quinoxaline compounds: A DFT study

NASA Astrophysics Data System (ADS)

Behzadi, Hadi; Roonasi, Payman; Assle taghipour, Khatoon; van der Spoel, David; Manzetti, Sergio

2015-07-01

The quantum chemical calculations at the DFT/B3LYP level of theory were carried out on seven quinoxaline compounds, which have been synthesized as anti-Mycobacterium tuberculosis agents. Three conformers were optimized for each compound and the lowest energy structure was found and used in further calculations. The electronic properties including EHOMO, ELUMO and related parameters as well as electron density around oxygen and nitrogen atoms were calculated for each compound. The relationship between the calculated electronic parameters and biological activity of the studied compounds were investigated. Six similar quinoxaline derivatives with possible more drug activity were suggested based on the calculated electronic descriptors. A mechanism was proposed and discussed based on the calculated electronic parameters and bond dissociation energies.

Ab initio/GIAO-CCSD(T) study of structures, energies, and 13C NMR chemical shifts of C4H7(+) and C5H9(+) ions: relative stability and dynamic aspects of the cyclopropylcarbinyl vs bicyclobutonium ions.

PubMed

Olah, George A; Surya Prakash, G K; Rasul, Golam

2008-07-16

The structures and energies of the carbocations C 4H 7 (+) and C 5H 9 (+) were calculated using the ab initio method. The (13)C NMR chemical shifts of the carbocations were calculated using the GIAO-CCSD(T) method. The pisigma-delocalized bisected cyclopropylcarbinyl cation, 1 and nonclassical bicyclobutonium ion, 2 were found to be the minima for C 4H 7 (+) at the MP2/cc-pVTZ level. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level the structure 2 is 0.4 kcal/mol more stable than the structure 1. The (13)C NMR chemical shifts of 1 and 2 were calculated by the GIAO-CCSD(T) method. Based on relative energies and (13)C NMR chemical shift calculations, an equilibrium involving the 1 and 2 in superacid solutions is most likely responsible for the experimentally observed (13)C NMR chemical shifts, with the latter as the predominant equilibrating species. The alpha-methylcyclopropylcarbinyl cation, 4, and nonclassical bicyclobutonium ion, 5, were found to be the minima for C 5H 9 (+) at the MP2/cc-pVTZ level. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level ion 5 is 5.9 kcal/mol more stable than the structure 4. The calculated (13)C NMR chemical shifts of 5 agree rather well with the experimental values of C 5H 9 (+).

Atomic data and line intensities for the S V ion

NASA Astrophysics Data System (ADS)

Iorga, C.; Stancalie, V.

2017-05-01

The energy levels, oscillator strengths, spontaneous radiative decay rates, lifetimes and electron impact collision strengths have been obtained for the [ Ne ] 3s nl, [ Ne ] 3p nl, [ Ne ] 3d nl configurations belonging to S V ion, with n ≤ 7 and l ≤ 4, resulting in 567 fine-structure levels. The calculations have been performed within the fully relativistic Flexible Atomic Code (FAC, Gu, 2008) framework and the distorted wave approximation. To attain the desired accuracy for the levels energy, the valence-valence and valence-core correlations have been taken care of by including 96 configuration state functions (CSFs) in the model, reaching a total of 3147 fine-structure levels. Two separate calculations have been performed with the local central potential computed for two different average configurations. A third calculation is also performed without the addition of the core-excited states in the atomic model for completeness. The effects of slightly different mean configurations and valence-core correlations on the energy levels and decay rates are investigated. The collision data have been computed employing the relativistic distorted-wave method along with the atomic model containing the 96 CSFs and corresponding to the ground state mean configuration. The collision strengths corresponding to excitation from the first four fine-structure levels are given for five energy values of the scattered electron 2.65, 6.18, 11.02, 17.36, 25.43 Rydberg, plus an additional variable small energy value near the threshold. A collisional-radiative model has been employed to solve the rate equations for the populations of the 567 fine-structure levels, for a temperature of LogTE(K) = 5.2 corresponding to the maximum abundance of S V, and at densities 106-1016cm-3, assuming a Maxwellian electron energy distribution function and black body radiation of temperature 6000 K and dilution factor 0.35 for the photon distribution function. The main processes responsible for the level population variations are the electron-impact collisional excitation and the radiative decay along with their inverse processes. As a result, the level populations along with the spectral high-line intensity ratios are provided.

Energy levels, radiative rates, and lifetimes for transitions in W LVIII

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

Aggarwal, Kanti M., E-mail: K.Aggarwal@qub.ac.uk; Keenan, Francis P.

2014-11-15

Energy levels and radiative rates are reported for transitions in Cl-like W LVIII. Configuration interaction (CI) has been included among 44 configurations (generating 4978 levels) over a wide energy range up to 363 Ryd, and the general-purpose relativistic atomic structure package (GRASP) adopted for the calculations. Since no other results of comparable complexity are available, calculations have also been performed with the flexible atomic code (FAC), which help in assessing the accuracy of our results. Energies are listed for the lowest 400 levels (with energies up to ∼98 Ryd), which mainly belong to the 3s{sup 2}3p{sup 5}, 3s3p{sup 6}, 3s{supmore » 2}3p{sup 4}3d, 3s{sup 2}3p{sup 3}3d{sup 2}, 3s3p{sup 4}3d{sup 2}, 3s{sup 2}3p{sup 2}3d{sup 3}, and 3p{sup 6}3d configurations, and radiative rates are provided for four types of transitions, i.e. E1, E2, M1, and M2. Our energy levels are assessed to be accurate to better than 0.5%, whereas radiative rates (and lifetimes) should be accurate to better than 20% for a majority of the strong transitions.« less

High-Level, First-Principles, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO).

PubMed

Li, Jun; Carter, Stuart; Bowman, Joel M; Dawes, Richard; Xie, Daiqian; Guo, Hua

2014-07-03

The ro-vibrational spectrum of the simplest Criegee intermediate (CH2OO) has been determined quantum mechanically based on nine-dimensional potential energy and dipole surfaces for its ground electronic state. The potential energy surface is fitted to more than 50 000 high-level ab initio points with a root-mean-square error of 25 cm(-1), using a recently proposed permutation invariant polynomial neural network method. The calculated rotational constants, vibrational frequencies, and spectral intensities of CH2OO are in excellent agreement with experiment. The potential energy surface provides a valuable platform for studying highly excited vibrational and unimolecular reaction dynamics of this important molecule.

Analytic functions for potential energy curves, dipole moments, and transition dipole moments of LiRb molecule.

PubMed

You, Yang; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang; Wang, Li-Zhi

2016-01-15

The analytic potential energy functions (APEFs) of the X(1)Σ(+), 2(1)Σ(+), a(3)Σ(+), and 2(3)Σ(+) states of the LiRb molecule are obtained using Morse long-range potential energy function with damping function and nonlinear least-squares method. These calculations were based on the potential energy curves (PECs) calculated using the multi-reference configuration interaction (MRCI) method. The reliability of the APEFs is confirmed using the curves of their first and second derivatives. By using the obtained APEFs, the rotational and vibrational energy levels of the states are determined by solving the Schrödinger equation of nuclear movement. The spectroscopic parameters, which are deduced using Dunham expansion, and the obtained rotational and vibrational levels are compared with the reported theoretical and experimental values. The correlation effect of the electrons of the inner shell remarkably improves the results compared with the experimental spectroscopic parameters. For the first time, the APEFs for the dipole moments and transition dipole moments of the states have been determined based on the curves obtained from the MRCI calculations. Copyright © 2015 Elsevier B.V. All rights reserved.

New potential energy surface for the HCS{sup +}–He system and inelastic rate coefficients

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

Dubernet, Marie-Lise; Quintas-Sánchez, Ernesto; Tuckey, Philip

2015-07-28

A new high quality potential energy surface is calculated at a coupled-cluster single double triple level with an aug-cc-pV5Z basis set for the HCS{sup +}–He system. This potential energy surface is used in low energy quantum scattering calculations to provide a set of (de)-excitation cross sections and rate coefficients among the first 20 rotational levels of HCS{sup +} by He in the range of temperature from 5 K to 100 K. The paper discusses the impact of the new ab initio potential energy surface on the cross sections at low energy and provides a comparison with the HCO{sup +}–He system.more » The HCS{sup +}–He rate coefficients for the strongest transitions differ by factors of up to 2.5 from previous rate coefficients; thus, analysis of astrophysical spectra should be reconsidered with the new rate coefficients.« less

Positive parity low spin states of odd-mass tellurium isotopes

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

Yazar, Harun Resit

2006-11-15

In this work, we analyse the positive parity of states of odd-mass nucleus within the framework of interacting boson fermion model. The result of an IBFM-1 multilevel calculation with the lg{sub 9/2}, 2d{sub 5/2}, 2d{sub 3/2}, 3s{sub 1/2} and one level, 1h{sub 11/2} with negative parity, single particle orbits is reported for the positive parity states of the odd mass nucleus {sup 123-125}Te. Also, an IBM-1 calculation is presented for the low-lying states in the even-even {sup 124-126}Te core nucleus. The energy levels and B (E2) transition probabilities were calculated and compared with the experimental data. It was found thatmore » the calculated positive parity low spin state energy spectra of the odd-mass {sup 123-125}Te isotopes agree quite well with the experimental data.« less

[Research on the emission spectrum of NO molecule's γ-band system by corona discharge].

PubMed

Zhai, Xiao-dong; Ding, Yan-jun; Peng, Zhi-min; Luo, Rui

2012-05-01

The optical emission spectrum of the gamma-band system of NO molecule, A2 sigma+ --> X2 pi(r), has been analyzed and calculated based on the energy structure of NO molecule' doublet states. By employing the theory of diatomic molecular Spectra, some key parameters of equations for the radiative transition intensity were evaluated theoretically, including the potentials of the doublet states of NO molecule's upper and lower energy levels, the electronic transition moments calculated by using r-centroid approximation method, and the Einstein coefficient of different vibrational and rotational levels. The simulated spectrum of the gamma-band system was calculated as a function of different vibrational and rotational temperature. Compared to the theoretical spectroscopy, the measured results were achieved from corona discharge experiments of NO and N2. The vibrational and rotational temperatures were determined approximately by fitting the measured spectral intensities with the calculated ones.

High-precision R-branch transition frequencies in the ν2 fundamental band of H 3+ %A Perry, Adam J.; Hodges, James N.; Markus, Charles R.; Kocheril, G. Stephen; McCall, Benjamin J.

NASA Astrophysics Data System (ADS)

Perry, Adam J.; Hodges, James N.; Markus, Charles R.; Kocheril, G. Stephen; McCall, Benjamin J.

2015-11-01

The H3+ molecular ion has served as a long-standing benchmark for state-of-the-art ab initio calculations of molecular potentials and variational calculations of rovibrational energy levels. However, the accuracy of such calculations would not have been confirmed if not for the wealth of spectroscopic data that has been made available for this molecule. Recently, a new high-precision ion spectroscopy technique was demonstrated by Hodges et al., which led to the first highly accurate and precise (∼MHz) H3+ transition frequencies. As an extension of this work, we present ten additional R-branch transitions measured to similar precision as a next step toward the ultimate goal of producing a comprehensive high-precision survey of this molecule, from which rovibrational energy levels can be calculated.

Calculation of the vibrational spectra of betaine hydrochloride

NASA Astrophysics Data System (ADS)

Szafran, Miroslaw; Koput, Jacek

1997-02-01

The molecular geometries of betaine hydrochloride, BET·HCl, and free protonated betaine, BET·H +, were calculated with the 6-31G(d,p) basis set at the SCF, MP2 and DFT levels of theory. At the SCF level, the minimum energy corresponds to the ionic pair, B +Htctdot;A -, however, the equilibrium Otctdot;Cl distance is 0.14 Å shorter than the X-ray value. Inclusion of the correlation effects, both at the MP2 and DFT levels, predicts a minimum energy for the molecular complex, Btctdot;H-A, with the equilibrium Otctdot;Cl distance close to the experimental value. The frequencies and intensities of the vibrational bands of BET·HCl, BET·DCl and BET·H + were calculated at the SCF and DFT levels and compared with the solid IR spectra. All measured IR bands were interpreted in term of the calculated vibrational modes. The rms deviations between the experimental and calculated SCF frequencies were 21 and 29 cm -1 for BET·HCl and BET·DCl, respectively. The computed band intensities agree qualitatively with the experimental data. The coupling of the CO stretching and OH bending modes are discussed. The summation bands are probably enhanced in intensity by Fermi resonance with the fundamentals responsible for the main ν(OH) (ν(OD) absorption region.

Multielectron spectroscopy: energy levels of K n+ and Rb n+ ions (n = 2, 3, 4)

NASA Astrophysics Data System (ADS)

Khalal, M. A.; Soronen, J.; Jänkälä, K.; Huttula, S.-M.; Huttula, M.; Bizau, J.-M.; Cubaynes, D.; Guilbaud, S.; Ito, K.; Andric, L.; Feng, J.; Lablanquie, P.; Palaudoux, J.; Penent, F.

2017-11-01

A magnetic bottle time-of-flight spectrometer has been used to perform spectroscopy of K n+ and Rb n+ states with ionization degrees n of 2, 3 and 4. Energy levels are directly measured by detecting in coincidence the n electrons that are emitted as a result of single photon absorption. Experimental results are compared with the energies from the NIST atomic database and ab initio multiconfiguration Dirac-Fock calculations. Previously unidentified 3p 4(3P)3d 1 4D energy levels of K2+ are assigned.

Temperature dependent energy levels of methylammonium lead iodide perovskite

NASA Astrophysics Data System (ADS)

Foley, Benjamin J.; Marlowe, Daniel L.; Sun, Keye; Saidi, Wissam A.; Scudiero, Louis; Gupta, Mool C.; Choi, Joshua J.

2015-06-01

Temperature dependent energy levels of methylammonium lead iodide are investigated using a combination of ultraviolet photoemission spectroscopy and optical spectroscopy. Our results show that the valence band maximum and conduction band minimum shift down in energy by 110 meV and 77 meV as temperature increases from 28 °C to 85 °C. Density functional theory calculations using slab structures show that the decreased orbital splitting due to thermal expansion is a major contribution to the experimentally observed shift in energy levels. Our results have implications for solar cell performance under operating conditions with continued sunlight exposure and increased temperature.

Multi-level quantum mechanics theories and molecular mechanics study of the double-inversion mechanism of the F- + CH3I reaction in aqueous solution.

PubMed

Liu, Peng; Zhang, Jingxue; Wang, Dunyou

2017-06-07

A double-inversion mechanism of the F - + CH 3 I reaction was discovered in aqueous solution using combined multi-level quantum mechanics theories and molecular mechanics. The stationary points along the reaction path show very different structures to the ones in the gas phase due to the interactions between the solvent and solute, especially strong hydrogen bonds. An intermediate complex, a minimum on the potential of mean force, was found to serve as a connecting-link between the abstraction-induced inversion transition state and the Walden-inversion transition state. The potentials of mean force were calculated with both the DFT/MM and CCSD(T)/MM levels of theory. Our calculated free energy barrier of the abstraction-induced inversion is 69.5 kcal mol -1 at the CCSD(T)/MM level of theory, which agrees with the one at 72.9 kcal mol -1 calculated using the Born solvation model and gas-phase data; and our calculated free energy barrier of the Walden inversion is 24.2 kcal mol -1 , which agrees very well with the experimental value at 25.2 kcal mol -1 in aqueous solution. The calculations show that the aqueous solution makes significant contributions to the potentials of mean force and exerts a big impact on the molecular-level evolution along the reaction pathway.

Low-energy tautomers and conformers of neutral and protonated arginine.

PubMed

Rak, J; Skurski, P; Simons, J; Gutowski, M

2001-11-28

The relative stabilities of zwitterionic and canonical forms of neutral arginine and of its protonated derivative were studied by using ab initio electronic structure methods. Trial structures were first identified at the PM3 level of theory with use of a genetic algorithm to systematically vary geometrical parameters. Further geometry optimizations of these structures were performed at the MP2 and B3LYP levels of theory with basis sets of the 6-31++G** quality. The final energies were determined at the CCSD/6-31++G** level and corrected for thermal effects determined at the B3LYP level. Two new nonzwitterionic structures of the neutral were identified, and one of them is the lowest energy structure found so far. The five lowest energy structures of neutral arginine are all nonzwitterionic in nature and are clustered within a narrow energy range of 2.3 kcal/mol. The lowest energy zwitterion structure is less stable than the lowest nonzwitterion structure by 4.0 kcal/mol. For no level of theory is a zwitterion structure suggested to be the global minimum. The calculated proton affinity of 256.3 kcal/mol and gas-phase basicity of 247.8 kcal/mol of arginine are in reasonable agreement with the measured values of 251.2 and 240.6 kcal/mol, respectively. The calculated vibrational characteristics of the low-energy structures of neutral arginine provide an alternative interpretation of the IR-CRLAS spectrum (Chapo et al. J. Am. Chem. Soc. 1998, 120, 12956-12957).

Analysis of solar spectra in the middle ultraviolet and visible for atmospheric trace constituents measurements. [hydroxyl radicals

NASA Technical Reports Server (NTRS)

Goldman, A.

1980-01-01

Individual spectral line parameters including line positions, strengths, and intensities were generated for the sq Alpha Sigma - sq Chi Pi (0,0) band of OH, applicable to atmospheric and high temperatures. Energy levels and transition frequencies are calculated by numerically diagonalizing the Hamiltonian. Line strengths are calculated using the dipole matrix and eigenvectors derived from energy matrix diagonalization. The line strengths are compared to those calculated from previously published algebraic line strength formulas. Tables of line parameters are presented for 240 K and 4600 K.

Industrial Facility Combustion Energy Use

DOE Data Explorer

McMillan, Colin

2016-08-01

Facility-level industrial combustion energy use is calculated from greenhouse gas emissions data reported by large emitters (>25,000 metric tons CO2e per year) under the U.S. EPA's Greenhouse Gas Reporting Program (GHGRP, https://www.epa.gov/ghgreporting). The calculation applies EPA default emissions factors to reported fuel use by fuel type. Additional facility information is included with calculated combustion energy values, such as industry type (six-digit NAICS code), location (lat, long, zip code, county, and state), combustion unit type, and combustion unit name. Further identification of combustion energy use is provided by calculating energy end use (e.g., conventional boiler use, co-generation/CHP use, process heating, other facility support) by manufacturing NAICS code. Manufacturing facilities are matched by their NAICS code and reported fuel type with the proportion of combustion fuel energy for each end use category identified in the 2010 Energy Information Administration Manufacturing Energy Consumption Survey (MECS, http://www.eia.gov/consumption/manufacturing/data/2010/). MECS data are adjusted to account for data that were withheld or whose end use was unspecified following the procedure described in Fox, Don B., Daniel Sutter, and Jefferson W. Tester. 2011. The Thermal Spectrum of Low-Temperature Energy Use in the United States, NY: Cornell Energy Institute.

Spectrum and energy levels of six-times ionized yttrium (Y VII)

NASA Astrophysics Data System (ADS)

Reader, Joseph

2018-03-01

The spectrum of six-times ionized yttrium, Y VII, was photographed with a sliding-spark discharge on 10.7 m normal- and grazing-incidence spectrographs. The region of observation was 157-824 Å. The observations extend the known configurations 4s24p3, 4s4p4, 4p5, 4s24p25s, 4s24p26s to the nearly complete 4s24p24d configuration. Our results for 4s24p24d significantly revise results of Rahimullah et al (1978 Phys. Scr. 18 96); Ateqad et al (1984 J. Phys. B: At. Mol. Phys. 17 4617). A total of 168 lines and 56 energy levels are now known for this ion. The observed configurations were interpreted with Hartree-Fock calculations and least-squares fits of the energy parameters to the observed levels. Transition probabilities for all classified lines were calculated with the fitted parameters.

Coupled-cluster and explicitly correlated perturbation-theory calculations of the uracil anion.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej

2007-02-28

A valence-type anion of the canonical tautomer of uracil has been characterized using explicitly correlated second-order Moller-Plesset perturbation theory (RI-MP2-R12) in conjunction with conventional coupled-cluster theory with single, double, and perturbative triple excitations. At this level of electron-correlation treatment and after inclusion of a zero-point vibrational energy correction, determined in the harmonic approximation at the RI-MP2 level of theory, the valence anion is adiabatically stable with respect to the neutral molecule by 40 meV. The anion is characterized by a vertical detachment energy of 0.60 eV. To obtain accurate estimates of the vertical and adiabatic electron binding energies, a scheme was applied in which electronic energy contributions from various levels of theory were added, each of them extrapolated to the corresponding basis-set limit. The MP2 basis-set limits were also evaluated using an explicitly correlated approach, and the results of these calculations are in agreement with the extrapolated values. A remarkable feature of the valence anionic state is that the adiabatic electron binding energy is positive but smaller than the adiabatic electron binding energy of the dipole-bound state.

Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study

NASA Astrophysics Data System (ADS)

Kamarchik, E.; Rodrigo, C.; Bowman, J. M.; Reisler, H.; Krylov, A. I.

2012-02-01

The dissociation of the hydroxymethyl radical, CH2OH, and its isotopolog, CD2OH, following the excitation of high OH stretch overtones is studied by quasi-classical molecular dynamics calculations using a global potential energy surface (PES) fitted to ab initio calculations. The PES includes CH2OH and CH3O minima, dissociation products, and all relevant barriers. Its analysis shows that the transition states for OH bond fission and isomerization are both very close in energy to the excited vibrational levels reached in recent experiments and involve significant geometry changes relative to the CH2OH equilibrium structure. The energies of key stationary points are refined using high-level electronic structure calculations. Vibrational energies and wavefunctions are computed by coupled anharmonic vibrational calculations. They show that high OH-stretch overtones are mixed with other modes. Consequently, trajectory calculations carried out at energies about ˜3000 cm-1 above the barriers reveal that despite initial excitation of the OH stretch, the direct OH bond fission is relatively slow (10 ps) and a considerable fraction of the radicals undergoes isomerization to the methoxy radical. The computed dissociation energies are: D0(CH2OH → CH2O + H) = 10 188 cm-1, D0(CD2OH → CD2O + H) = 10 167 cm-1, D0(CD2OH → CHDO + D) = 10 787 cm-1. All are in excellent agreement with the experimental results. For CH2OH, the barriers for the direct OH bond fission and isomerization are: 14 205 and 13 839 cm-1, respectively.

Theoretical study of native point defects in strained-layer superlattice systems

NASA Astrophysics Data System (ADS)

Krishnamurthy, S.; Yu, Zhi Gang

2018-04-01

We developed a theoretical approach that employs first-principles Hamiltonians, tight-binding Hamiltonians, and Green's function techniques to obtain energy levels arising from native point defects (NPDs) in InAs-GaSb and InAs-InAs1-xSbx strained layer superlattice (SLS) systems. In InAs and GaSb regions, we considered four types of NPDs—anion vacancy, cation vacancy, anion anti-site, and cation anti-site—as well as isoelectronic substitution at anion sites (Sb at the As site and As at the Sb site). Additionally, we considered three types of defects—the cation at the second anion site, the second anion at the cation site, and second anion vacancy—in the InAs1-xSbx alloy region of the SLS. For a selected few designs, we studied NPDs both in the bulk region and near the interfaces of the SLS. We have considered 12 designs of InAs-GaSb systems and two designs of InAs-InAs0.7Sb0.3 systems lattice-matched to the GaSb substrate. The calculated defect levels not only agreed well with available measurements, but also revealed the connection between mid-gap levels and specific NPDs. We further calculated defect formation energies both in compounds and in all superlattices considered above. Since the absolute value of defect formation energy depends considerably on growth conditions, we evaluated the formation energies in SLS with respect to their value in the corresponding bulk or alloy. The calculated defect formation energies, together with defect energy level results, allow us to identify a few promising SLS designs for high-performing photodetectors.

Positron and electron energy bands in several ionic crystals using restricted Hartree-Fock method

NASA Astrophysics Data System (ADS)

Kunz, A. B.; Waber, J. T.

1981-08-01

Using a restricted Hartree-Fock formalism and suitably localized and symmetrized wave functions, both the positron and electron energy bands were calculated for NaF, MgO and NiO. The lowest positron state at Γ 1 lies above the vacuum level and negative work functions are predicted. Positron annihilation rates were calculated and found to be in good agreement with measured lifetimes.

Carbon Nanotube Field Emission Arrays

DTIC Science & Technology

2011-06-01

K , and M [14]. Using the tight binding energy model, the energy dispersion relations for graphene can be calculated for the triangle formed from...The corresponding reciprocal lattice vectors, b1 and b2, and Brillouin zone of graphene [14]. 19 graphene band structure is the six K ...points where the two bands are degenerate and the Fermi level passes. It has been shown through thorough calculations that at T = 0 K , the density

Density Functional Theory Calculations of Activation Energies for Non-radiative Carrier Capture by Deep Defect Levels in Semiconductors.

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

Modine, Normand Arthur; Wright, Alan F.; Lee, Stephen R.

Carrier recombination due to defects can have a major impact on device performance. The rate of defect-induced carrier recombination is determined by both defect levels and carrier capture cross-sections. Kohn-Sham density functional theory (DFT) has been widely and successfully used to predict defect levels in semiconductors and insulators, but only recently has work begun to focus on using DFT to determine carrier capture cross-sections. Lang and Henry worked out the fundamental theory of carrier-capture cross-sections in the 1970s and showed that, in most cases, room temperature carrier-capture cross-sections differ between defects primarily due to differences in the carrier capture activationmore » energies. Here, we present an approach to using DFT to calculate carrier capture activation energies that does not depend on perturbation theory or an assumed configuration coordinate, and we demonstrate this approach for the -3/-2 level of the Ga vacancy in wurtzite GaN.« less

The Effectiveness of the Component Impact Test Method for the Side Impact Injury Assessment of the Door Trim

NASA Astrophysics Data System (ADS)

Youn, Younghan; Koo, Jeong-Seo

The complete evaluation of the side vehicle structure and the occupant protection is only possible by means of the full scale side impact crash test. But, auto part manufacturers such as door trim makers can not conduct the test especially when the vehicle is under the developing process. The main objective of this study is to obtain the design guidelines by a simple component level impact test. The relationship between the target absorption energy and impactor speed were examined using the energy absorbed by the door trim. Since each different vehicle type required different energy levels on the door trim. A simple impact test method was developed to estimate abdominal injury by measuring reaction force of the impactor. The reaction force will be converted to a certain level of the energy by the proposed formula. The target of absorption energy for door trim only and the impact speed of simple impactor are derived theoretically based on the conservation of energy. With calculated speed of dummy and the effective mass of abdomen, the energy allocated in the abdomen area of door trim was calculated. The impactor speed can be calculated based on the equivalent energy of door trim absorbed during the full crash test. With the proposed design procedure for the door trim by a simple impact test method was demonstrated to evaluate the abdominal injury. This paper describes a study that was conducted to determine sensitivity of several design factors for reducing abdominal injury values using the matrix of orthogonal array method. In conclusion, with theoretical considerations and empirical test data, the main objective, standardization of door trim design using the simple impact test method was established.

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

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

First-principles calculation of electronic energy level alignment at electrochemical interfaces

NASA Astrophysics Data System (ADS)

Azar, Yavar T.; Payami, Mahmoud

2017-08-01

Energy level alignment at solid-solvent interfaces is an important step in determining the properties of electrochemical systems. The positions of conduction and valence band edges of a semiconductor are affected by its environment. In this study, using first-principles DFT calculation, we have determined the level shifts of the semiconductors TiO2 and ZnO at the interfaces with MeCN and DMF solvent molecules. The level shifts of semiconductor are obtained using the potential difference between the clean and exposed surfaces of asymmetric slabs. In this work, neglecting the effects of present ions in the electrolyte solution, we have shown that the solvent molecules give rise to an up-shift for the levels, and the amount of this shift varies with coverage. It is also shown that the shapes of density of states do not change sensibly near the gap. Molecular dynamics simulations of the interface have shown that at room temperatures the semiconductor surface is not fully covered by the solvent molecules, and one must use intermediate values in an static calculations.

Towards an Optimal Gradient-dependent Energy Functional of the PZ-SIC Form

DOE PAGES

Jónsson, Elvar Örn; Lehtola, Susi; Jónsson, Hannes

2015-06-01

Results of Perdew–Zunger self-interaction corrected (PZ-SIC) density functional theory calculations of the atomization energy of 35 molecules are compared to those of high-level quantum chemistry calculations. While the PBE functional, which is commonly used in calculations of condensed matter, is known to predict on average too high atomization energy (overbinding of the molecules), the application of PZ-SIC gives a large overcorrection and leads to significant underestimation of the atomization energy. The exchange enhancement factor that is optimal for the generalized gradient approximation within the Kohn-Sham (KS) approach may not be optimal for the self-interaction corrected functional. The PBEsol functional, wheremore » the exchange enhancement factor was optimized for solids, gives poor results for molecules in KS but turns out to work better than PBE in PZ-SIC calculations. The exchange enhancement is weaker in PBEsol and the functional is closer to the local density approximation. Furthermore, the drop in the exchange enhancement factor for increasing reduced gradient in the PW91 functional gives more accurate results than the plateaued enhancement in the PBE functional. A step towards an optimal exchange enhancement factor for a gradient dependent functional of the PZ-SIC form is taken by constructing an exchange enhancement factor that mimics PBEsol for small values of the reduced gradient, and PW91 for large values. The average atomization energy is then in closer agreement with the high-level quantum chemistry calculations, but the variance is still large, the F 2 molecule being a notable outlier.« less

Atomic Data and Spectral Line Intensities for Ne III

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Thomas, R. J.; Landi, E.; Fisher, Richard R. (Technical Monitor)

2001-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ne III. The configurations used are 2s(sup 2) 2p(sup 4),2s2p(sup 5),2s(sup 2) 2p(sup 3)3s, and 2s(sup 2)3p(sup 3)3d giving rise to 57 fine-structure levels in intermediate coupling. Collision strengths are calculated at five incident energies, 5, 10, 15, 20, and 25 Ry. Excitation rate coefficients are calculated by assuming a Maxwellian electron velocity distribution at an electron temperature of logT,(K)=5.0, corresponding to maximum abundance of Ne III. Using the excitation rate coefficients and the radiative transition rates, statistical equilibrium equations for level populations are solved at electron densities covering the range of 10(exp 8)-10(exp 14) per cubic centimeter. Relative spectral line intensities are calculated. Proton excitation rates between the lowest three levels have been included in the statistical equilibrium equations. The predicted Ne III line intensities are compared with SERTS rocket measurements of a solar active region and of a laboratory EUV light source.

Theoretical transition probabilities, oscillator strengths, and radiative lifetimes of levels in Pb IV

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

Alonso-Medina, A.; Colon, C., E-mail: cristobal.colon@upm.e; Porcher, P.

2011-01-15

Transition probabilities and oscillator strengths of 176 spectral lines with astrophysical interest arising from 5d{sup 10}ns (n = 7,8), 5d{sup 10}np (n = 6,7), 5d{sup 10}nd (n = 6,7), 5d{sup 10}5f, 5d{sup 10}5g, 5d{sup 10}nh (n = 6,7,8), 5d{sup 9}6s{sup 2}, and 5d{sup 9}6s6p configurations, and radiative lifetimes for 43 levels of Pb IV, have been calculated. These values were obtained in intermediate coupling (IC) and using relativistic Hartree-Fock calculations including core-polarization effects. For the IC calculations, we use the standard method of least-square fitting from experimental energy levels by means of the Cowan computer code. The inclusion in thesemore » calculations of the 5d{sup 10}7p and 5d{sup 10}5f configurations has facilitated a complete assignment of the energy levels in the Pb IV. Transition probabilities, oscillator strengths, and radiative lifetimes obtained are generally in good agreement with the experimental data.« less

Using a Nondirect Product Basis to Compute J > 0 Rovibrational States of H3+

NASA Astrophysics Data System (ADS)

Jaquet, Ralph; Carrington, Tucker

2013-10-01

We have used a Lanczos algorithm with a nondirect product basis to compute energy levels of H3+ with J values as large as 46. Energy levels computed on the potential surface of M. Pavanello, et al. (J. Chem. Phys. 2012, 136, 184303) agree well with previous calculations for low J values.

From Dimer to Crystal: Calculating the Cohesive Energy of Rare Gas Solids

ERIC Educational Resources Information Center

Halpern, Arthur M.

2012-01-01

An upper-level undergraduate project is described in which students perform high-level ab initio computational scans of the potential energy curves for Ne[subscript 2] and Ar[subscript 2] and obtain the respective Lennard-Jones (LJ) potential parameters [sigma] and [epsilon] for the dimers. Using this information, along with the summation of…

Prediction of the far field noise from wind energy farms

NASA Technical Reports Server (NTRS)

Shepherd, K. P.; Hubbard, H. H.

1986-01-01

The basic physical factors involved in making predictions of wind turbine noise and an approach which allows for differences in the machines, the wind energy farm configurations and propagation conditions are reviewed. Example calculations to illustrate the sensitivity of the radiated noise to such variables as machine size, spacing and numbers, and such atmosphere variables as absorption and wind direction are presented. It is found that calculated far field distances to particular sound level contours are greater for lower values of atmospheric absorption, for a larger total number of machines, for additional rows of machines and for more powerful machines. At short and intermediate distances, higher sound pressure levels are calculated for closer machine spacings, for more powerful machines, for longer row lengths and for closer row spacings.

Microscopic theoretical study of frequency dependent dielectric constant of heavy fermion systems

NASA Astrophysics Data System (ADS)

Shadangi, Keshab Chandra; Rout, G. C.

2017-05-01

The dielectric polarization and the dielectric constant plays a vital role in the deciding the properties of the Heavy Fermion Systems. In the present communication we consider the periodic Anderson's Model which consists of conduction electron kinetic energy, localized f-electron kinetic energy and the hybridization between the conduction and localized electrons, besides the Coulomb correlation energy. We calculate dielectric polarization which involves two particle Green's functions which are calculated by using Zubarev's Green's function technique. Using the equations of motion of the fermion electron operators. Finally, the temperature and frequency dependent dielectric constant is calculated from the dielectric polarization function. The charge susceptibility and dielectric constant are computed numerically for different physical parameters like the position (Ef) of the f-electron level with respect to fermi level, the strength of the hybridization (V) between the conduction and localized f-electrons, Coulomb correlation potential temperature and optical phonon wave vector (q). The results will be discussed in a reference to the experimental observations of the dielectric constants.

Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

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

Adam, Ahmad Y.; Jensen, Per, E-mail: jensen@uni-wuppertal.de; Yachmenev, Andrey

2015-12-28

We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH{sub 3} radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH{sub 3} in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in verymore » good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant’s equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.« less

Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on Lornoxicam by density functional theory

NASA Astrophysics Data System (ADS)

Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

2015-11-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of Lornoxicam 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 parameters, 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) and 6-31++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 Lornoxicam 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 Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis and the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like Entropy, Enthalpy, Specific heat capacity and zero vibrational energy have been calculated. Besides, molecular electrostatic potential (MEP) was investigated using theoretical calculations.

Energy expenditure and nutritional status of coal miners: A cross-sectional study.

PubMed

Bilici, Saniye; Saglam, Fatma; Beyhan, Yasemin; Barut-Uyar, Banugul; Dikmen, Derya; Goktas, Zeynep; Attar, A James; Mucka, Patrick; Uyar, M Fatih

2016-09-02

The objectives of this study were to assess the nutritional status, daily energy intake, and daily energy expenditure of coal miners in Turkey. A total of 135 healthy coal miners (aged 19-64 years) were evaluated. Heart rates were measured using Polar watches, and the total energy expenditure was calculated using physical activity level formula and Hiilloskorpi equation. The average body mass index of the participants was 25.7 ± 3.98 kg/m 2 , and the average energy intake was 3,973.7 ± 420.85 kcal. According to Dietary Reference Intakes, the energy and nutrient intakes of the miners were adequate, except for the intake of vitamin D. The coal miners were found to be at moderate (43.0%), heavy (41.5%), and very heavy (13.3%) activity levels. Calculations of the energy expenditure at work were found to be 2,189.8 ± 376.19 to 2,788.8 ± 359.89 kcal per day. Further studies have to be conducted for developing national standards for each occupation.

QM/MM free energy simulations: recent progress and challenges

PubMed Central

Lu, Xiya; Fang, Dong; Ito, Shingo; Okamoto, Yuko; Ovchinnikov, Victor

2016-01-01

Due to the higher computational cost relative to pure molecular mechanical (MM) simulations, hybrid quantum mechanical/molecular mechanical (QM/MM) free energy simulations particularly require a careful consideration of balancing computational cost and accuracy. Here we review several recent developments in free energy methods most relevant to QM/MM simulations and discuss several topics motivated by these developments using simple but informative examples that involve processes in water. For chemical reactions, we highlight the value of invoking enhanced sampling technique (e.g., replica-exchange) in umbrella sampling calculations and the value of including collective environmental variables (e.g., hydration level) in metadynamics simulations; we also illustrate the sensitivity of string calculations, especially free energy along the path, to various parameters in the computation. Alchemical free energy simulations with a specific thermodynamic cycle are used to probe the effect of including the first solvation shell into the QM region when computing solvation free energies. For cases where high-level QM/MM potential functions are needed, we analyze two different approaches: the QM/MM-MFEP method of Yang and co-workers and perturbative correction to low-level QM/MM free energy results. For the examples analyzed here, both approaches seem productive although care needs to be exercised when analyzing the perturbative corrections. PMID:27563170

Relative complexation energies for Li(+) ion in solution: molecular level solvation versus polarizable continuum model study.

PubMed

Eilmes, Andrzej; Kubisiak, Piotr

2010-01-21

Relative complexation energies for the lithium cation in acetonitrile and diethyl ether have been studied. Quantum-chemical calculations explicitly describing the solvation of Li(+) have been performed based on structures obtained from molecular dynamics simulations. The effect of an increasing number of solvent molecules beyond the first solvation shell has been found to consist in reduction of the differences in complexation energies for different coordination numbers. Explicit-solvation data have served as a benchmark to the results of polarizable continuum model (PCM) calculations. It has been demonstrated that the PCM approach can yield relative complexation energies comparable to the predictions based on molecular-level solvation, but at significantly lower computational cost. The best agreement between the explicit-solvation and the PCM results has been obtained when the van der Waals surface was adopted to build the molecular cavity.

Vibrational treatment of the formic acid double minimum case in valence coordinates

NASA Astrophysics Data System (ADS)

Richter, Falk; Carbonnière, P.

2018-02-01

One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm-1 for trans- and cis-HCOOH, respectively, have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calculated trans fundamental transition frequencies agree with experiment to within 5 cm-1. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm-1 relative to trans zero point energy.

Radiation heat transfer calculations for the uranium fuel-containment region of the nuclear light bulb engine.

NASA Technical Reports Server (NTRS)

Rodgers, R. J.; Latham, T. S.; Krascella, N. L.

1971-01-01

Calculation results are reviewed of the radiant heat transfer characteristics in the fuel and buffer gas regions of a nuclear light bulb engine based on the transfer of energy by thermal radiation from gaseous uranium fuel in a neon vortex, through an internally cooled transparent wall, to seeded hydrogen propellant. The results indicate that the fraction of UV energy incident on the transparent walls increases with increasing power level. For the reference engine power level of 4600 megw, it is necessary to employ space radiators to reject the UV radiated energy absorbed by the transparent walls. This UV energy can be blocked by employing nitric oxide and oxygen seed gases in the fuel and buffer gas regions. However, this results in increased UV absorption in the buffer gas which also requires space radiators to reject the heat load.

Theoretical study of γ-aminobutyric acid conformers: Intramolecular interactions and ionization energies

NASA Astrophysics Data System (ADS)

Wang, Ke-Dong; Wang, Mei-Ting; Meng, Ju

2014-10-01

Allowing for all combinations of internal single-bond rotamers, 1,296 unique trial structures of γ-Aminobutyric acid (GABA) are obtained. All of these structures are optimized at the M06-2X level of theory and a total of 68 local minimal conformers are found. The nine low-lying conformers are used for further studies. According to the calculated relative Gibbs free energies at M06-2X level of theory, we find that the dispersion is important for the relative energy of GABA. The intramolecular hydrogen bonds and hyperconjugative interaction and their effects on the conformational stability are studied. The results show that both of them have great influence on the conformers. The vertical ionization energies (VIE) are calculated and match the experimental data well. The results show that the neutral GABA in the gas phase is a multi-conformer system and at least four conformations exist.

Electron self-energy in a homogeneous magnetic field

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

Gepraegs, R.; Riffert, H.; Herold, H.

1994-05-15

A relativistic calculation of the electron self-energy in a strong homogeneous magnetic field is presented, and the final expressions are calculated numerically for the Landau levels [ital N]=0,1,2,3 and both spin projections ([sigma]=[plus minus]1). For a given [ital N][gt]0 the energy of the spin-up state ([sigma]=+1) increases monotonically, but the spin-down ([sigma]=[minus]1) energy is negative for small fields, shows a minimum, and then increases for large fields; a crossing of levels appears for [ital N][gt]0. The total decay rates for these states are also obtained, as well as the spin-flip transition probability for ([ital N]=1, [sigma]=+1)[r arrow]([ital N]=1, [sigma]=[minus]1). Itmore » turns out that this transition rate is extremely small compared to the usual cyclotron emission rates.« less

77 FR 63324 - Notice of Certain Operating Cost Adjustment Factors for 2013

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-16

...: Energy Information Agency, Natural Gas, Residential Energy Price, 2010-2011 annual prices in dollars per.... The best current price data sources for the nine cost categories were used in calculating annual change factors. State-level data for fuel oil, electricity, and natural gas from Department of Energy...

Poster: "Energy Search."

ERIC Educational Resources Information Center

Social Education, 1982

1982-01-01

Contains a poster dealing with energy uses for use in secondary-level classes. On the reverse side of the poster, there is a discussion of alternative energy resources. Activities in which students calculate the operating costs of solar-powered cars and the size of solar collectors needed to heat water are included. (AM)

Infiltration modeling guidelines for commercial building energy analysis

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

Gowri, Krishnan; Winiarski, David W.; Jarnagin, Ronald E.

This report presents a methodology for modeling air infiltration in EnergyPlus to account for envelope air barrier characteristics. Based on a review of various infiltration modeling options available in EnergyPlus and sensitivity analysis, the linear wind velocity coefficient based on DOE-2 infiltration model is recommended. The methodology described in this report can be used to calculate the EnergyPlus infiltration input for any given building level infiltration rate specified at known pressure difference. The sensitivity analysis shows that EnergyPlus calculates the wind speed based on zone altitude, and the linear wind velocity coefficient represents the variation in infiltration heat loss consistentmore » with building location and weather data.« less

Energy control strategy for a hybrid electric vehicle

DOEpatents

Phillips, Anthony Mark; Blankenship, John Richard; Bailey, Kathleen Ellen; Jankovic, Miroslava

2002-08-27

An energy control strategy (10) for a hybrid electric vehicle that controls an electric motor during bleed and charge modes of operation. The control strategy (10) establishes (12) a value of the power level at which the battery is to be charged. The power level is used to calculate (14) the torque to be commanded to the electric motor. The strategy (10) of the present invention identifies a transition region (22) for the electric motor's operation that is bounded by upper and lower speed limits. According to the present invention, the desired torque is calculated by applying equations to the regions before, during and after the transition region (22), the equations being a function of the power level and the predetermined limits and boundaries.

Energy control strategy for a hybrid electric vehicle

DOEpatents

Phillips, Anthony Mark; Blankenship, John Richard; Bailey, Kathleen Ellen; Jankovic, Miroslava

2002-01-01

An energy control strategy (10) for a hybrid electric vehicle that controls an electric motor during bleed and charge modes of operation. The control strategy (10) establishes (12) a value of the power level at which the battery is to be charged. The power level is used to calculate (14) the torque to be commanded to the electric motor. The strategy (10) of the present invention identifies a transition region (22) for the electric motor's operation that is bounded by upper and lower speed limits. According to the present invention, the desired torque is calculated by applying equations to the regions before, during and after the transition region (22), the equations being a function of the power level and the predetermined limits and boundaries.

Radiative rates and electron impact excitation rate coefficients for Ne-like selenium, Se XXV

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

Wang, K.; Chen, C.Y., E-mail: chychen@fudan.edu.cn; Huang, M.

2011-07-15

In this article we report calculations of energy levels, radiative rates, electron impact collision strengths, and effective collision strengths for transitions among the 241 fine-structure levels arising from 2l{sup 8} and 2l{sup 7}n{sup '}l{sup '} (n{sup '{<=}}6 and l{sup '{<=}}n{sup '}-1) configurations of Ne-like Se XXV using the Flexible Atomic Code. Energy levels and radiative rates are calculated within the relativistic configuration-interaction method. Direct excitation collision strengths are calculated using the relativistic distorted-wave approximation and high-energy collision strengths are obtained in the relativistic plane-wave approximation. Resonance contributions through the relevant Na-like doubly-excited configurations 2l{sup 7}n'l'n''l'' (3{<=}n'{<=}7, l'{<=}n'-1, n'{<=}n''{<=}50, and l''{<=}8)more » are explicitly taken into account via the independent-process and isolated-resonance approximation using distorted waves. Resonant stabilizing transitions and possibly important radiative decays from the resonances toward low-lying autoionizing levels are considered. In addition, the resonance contributions from Na-like 2l{sup 6}3l'3l'''n''' (n'''=3-6) configurations are included and found to be predominant for many transitions among the singly-excited states in Ne-like Se XXV. We present the radiative rates, oscillator strengths, and line strengths for all electric dipole, magnetic dipole, electric quadrupole, magnetic quadrupole, electric octopole, and magnetic octopole transitions among the 241 levels. The effective collision strengths are reported for all 28920 transitions among the 241 levels over a wide temperature range up to 10 keV. To assess the reliability and accuracy of the present collisional data, we have performed a 27-state close-coupling calculation, employing the Dirac R-matrix theory. The results from the close-coupling calculation and the independent-process calculation for the identical target states are found to be in good agreement. - Highlights: {yields} Radiative and collisional atomic data are presented for the lowest 241 fine-structure levels in Ne-like Se. {yields} Calculations are performed using the FAC package. {yields} Resonances enhance significantly a large amount of transitions. {yields} Radiative damping effects are significant for many transitions. {yields} Close-coupling effects are small in Ne-like Se.« less

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

PubMed

Lee, Edmond P F; Wright, Timothy G

2005-10-08

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

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Ga XXX, Ge XXXI, As XXXII, Se XXXIII and Br XXXIV

NASA Astrophysics Data System (ADS)

Aggarwal, Kanti M.; Keenan, Francis P.

2013-04-01

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in He-like Ga XXX, Ge XXXI, As XXXII, Se XXXIII and Br XXXIV. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths, and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels of each ion. Additionally, theoretical lifetimes are provided for all 49 levels of the above five ions. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 108 K. Comparisons are made with similar data obtained using the flexible atomic code (fac) to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, particularly for some forbidden transitions, are also discussed. Finally, discrepancies between the present results for effective collision strengths with the darc code and earlier semi-relativistic R-matrix data are noted over a wide range of electron temperatures for many transitions in all ions.

Excitons in coupled type-II double quantum wells under electric and magnetic fields: InAs/AlSb/GaSb

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

Lyo, S. K., E-mail: sklyo@uci.edu; Pan, W.

2015-11-21

We calculate the wave functions and the energy levels of an exciton in double quantum wells under electric (F) and magnetic (B) fields along the growth axis. The result is employed to study the energy levels, the binding energy, and the boundary on the F–B plane of the phase between the indirect exciton ground state and the semiconductor ground state for several typical structures of the type-II quasi-two-dimensional quantum wells such as InAs/AlSb/GaSb. The inter-well inter-band radiative transition rates are calculated for exciton creation and recombination. We find that the rates are modulated over several orders of magnitude by themore » electric and magnetic fields.« less

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

DOE PAGES

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

2018-03-13

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

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

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Ab initio molecular orbital calculations on HBr - 2 Geometry, frequencies, and enthalpy changes

NASA Astrophysics Data System (ADS)

Ikuta, Shigeru; Saitoh, Toshikazu; Nomura, Okio

1990-08-01

HBr-2 has D∞h symmetry at both the second-order (MP2) and third-order (MP3) Møller-Plesset perturbation levels of theory with the extended basis sets, whereas the Hartree-Fock level of theory predicts that it has C∞v symmetry. A potential energy map is calculated with the MP2 method as a function of two parameters, i.e., the distance of two Br atoms and the displacement of H from the center of them. Two-dimensional vibration analysis is performed by using this potential energy map. The calculated ν1 is 200 cm-1 and the ν3 is 837 cm-1 in HBr-2, and those in DBr-2 are 199 and 569 cm-1, respectively. Thus the ratio of the asymmetric vibration (ν3)H/(ν3)D is 1.47, being somewhat greater than the value of √2 expected for a harmonic oscillator. The enthalpy changes (ΔH°) in the reaction of Br- with an HBr molecule are determined by both the MP3 total energy changes and the thermal energy changes between the reactants and the product. The calculated enthalpy change of -21.2 kcal/mol is in good agreement with the experimental one (-21 kcal/mol) recently observed by Caldwell and Kebarle. These calculated data on HBr-2, which will provide us with a useful guide for future measurements of gas-phase vibrational spectra, are compared with those on HCl-2 and HF-2.

Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex

NASA Astrophysics Data System (ADS)

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C.

2017-08-01

We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O2-O2, relevant for the theoretical description of collision-induced absorption in the forbidden X3Σg- → a1Δg and X3Σg- → b1Σg+ bands at 7883 cm-1 and 13 122 cm-1, respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O2-O2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex.

PubMed

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C

2017-08-28

We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O 2 -O 2 , relevant for the theoretical description of collision-induced absorption in the forbidden X 3 Σ g -  → a 1 Δ g and X 3 Σ g -  → b 1 Σ g + bands at 7883 cm -1 and 13 122 cm -1 , respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O 2 -O 2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

Vertical distribution of vibrational energy of molecular nitrogen in a stable auroral red arc and its effect on ionospheric electron densities. Ph.D. Thesis - Catholic Univ. of Am.

NASA Technical Reports Server (NTRS)

Newton, G. P.

1973-01-01

Previous solutions of the problem of the distribution of vibrationally excited molecular nitrogen in the thermosphere have either assumed a Boltzmann distribution and considered diffusion as one of the loss processes or solved for the energy level populations and neglected diffusion. Both of the previous approaches are combined by solving the time dependent continuity equations, including the diffusion process, for the first six energy levels of molecular nitrogen for conditions in the thermosphere corresponding to a stable auroral red arc. The primary source of molecular nitrogen excitation was subexcitation, and inelastic collisions between thermal electrons and molecular nitrogen. The reaction rates for this process were calculated from published cross section calculations. The loss processes for vibrational energy were electron and atomic oxygen quenching and vibrational energy exchange. The coupled sets of nonlinear, partial differential equations were solved numerically by employing finite difference equations.

Energy Levels in Quantum Wells.

NASA Astrophysics Data System (ADS)

Zang, Jan Xin

Normalized analytical equations for eigenstates of an arbitrary one-dimensional configuration of square potentials in a well have been derived. The general formulation is used to evaluate the energy levels of a particle in a very deep potential well containing seven internal barriers. The configuration can be considered as a finite superlattice sample or as a simplified model for a sample with only several atom layers. The results are shown in graphical forms as functions of the height and width of the potential barriers and as functions of the ratio of the effective mass in barrier to the mass in well. The formation of energy bands and surface eigenstates from eigenstates of a deep single well, the coming close of two energy bands and a surface state which are separate ordinarily, and mixing of the wave function of a surface state with the bulk energy bands are seen. Then the normalized derivation is extended to study the effect of a uniform electric field applied across a one-dimensional well containing an internal configuration of square potentials The general formulation is used to calculate the electric field dependence of the energy levels of a deep well with five internal barriers. Typical results are shown in graphical forms as functions of the barrier height, barrier width, barrier effective mass and the field strength. The formation of Stark ladders and surface states from the eigenstates of a single deep well in an electric field, the localization process of wave functions with changing barrier height, width, and field strength and their anticrossing behaviors are seen. The energy levels of a hydrogenic impurity in a uniform medium and in a uniform magnetic field are calculated with variational methods. The energy eigenvalues for the eigenstates with major quantum number less than or equal to 3 are obtained. The results are consistent with previous results. Furthermore, the energy levels of a hydrogenic impurity at the bottom of a one-dimensional parabolic quantum well with a magnetic field normal to the plane of the well are calculated with the finite-basis-set variational method. The limit of small radial distance and the limit of great radial distance are considered to choose a set of proper basis functions. It is found that the energy levels increase with increasing parabolic parameter alpha and increase with increasing normalized magnetic field strength gamma except those levels with magnetic quantum number m < 0 at small gamma.

Reduction of the virtual space for coupled-cluster excitation energies of large molecules and embedded systems

PubMed Central

Send, Robert; Kaila, Ville R. I.; Sundholm, Dage

2011-01-01

We investigate how the reduction of the virtual space affects coupled-cluster excitation energies at the approximate singles and doubles coupled-cluster level (CC2). In this reduced-virtual-space (RVS) approach, all virtual orbitals above a certain energy threshold are omitted in the correlation calculation. The effects of the RVS approach are assessed by calculations on the two lowest excitation energies of 11 biochromophores using different sizes of the virtual space. Our set of biochromophores consists of common model systems for the chromophores of the photoactive yellow protein, the green fluorescent protein, and rhodopsin. The RVS calculations show that most of the high-lying virtual orbitals can be neglected without significantly affecting the accuracy of the obtained excitation energies. Omitting all virtual orbitals above 50 eV in the correlation calculation introduces errors in the excitation energies that are smaller than 0.1 eV . By using a RVS energy threshold of 50 eV , the CC2 calculations using triple-ζ basis sets (TZVP) on protonated Schiff base retinal are accelerated by a factor of 6. We demonstrate the applicability of the RVS approach by performing CC2∕TZVP calculations on the lowest singlet excitation energy of a rhodopsin model consisting of 165 atoms using RVS thresholds between 20 eV and 120 eV. The calculations on the rhodopsin model show that the RVS errors determined in the gas-phase are a very good approximation to the RVS errors in the protein environment. The RVS approach thus renders purely quantum mechanical treatments of chromophores in protein environments feasible and offers an ab initio alternative to quantum mechanics∕molecular mechanics separation schemes. PMID:21663351

Reduction of the virtual space for coupled-cluster excitation energies of large molecules and embedded systems.

PubMed

Send, Robert; Kaila, Ville R I; Sundholm, Dage

2011-06-07

We investigate how the reduction of the virtual space affects coupled-cluster excitation energies at the approximate singles and doubles coupled-cluster level (CC2). In this reduced-virtual-space (RVS) approach, all virtual orbitals above a certain energy threshold are omitted in the correlation calculation. The effects of the RVS approach are assessed by calculations on the two lowest excitation energies of 11 biochromophores using different sizes of the virtual space. Our set of biochromophores consists of common model systems for the chromophores of the photoactive yellow protein, the green fluorescent protein, and rhodopsin. The RVS calculations show that most of the high-lying virtual orbitals can be neglected without significantly affecting the accuracy of the obtained excitation energies. Omitting all virtual orbitals above 50 eV in the correlation calculation introduces errors in the excitation energies that are smaller than 0.1 eV. By using a RVS energy threshold of 50 eV, the CC2 calculations using triple-ζ basis sets (TZVP) on protonated Schiff base retinal are accelerated by a factor of 6. We demonstrate the applicability of the RVS approach by performing CC2/TZVP calculations on the lowest singlet excitation energy of a rhodopsin model consisting of 165 atoms using RVS thresholds between 20 eV and 120 eV. The calculations on the rhodopsin model show that the RVS errors determined in the gas-phase are a very good approximation to the RVS errors in the protein environment. The RVS approach thus renders purely quantum mechanical treatments of chromophores in protein environments feasible and offers an ab initio alternative to quantum mechanics/molecular mechanics separation schemes. © 2011 American Institute of Physics

Investigations of Reactive Processes at Temperatures Relevant to the Hypersonic Flight Regime

DTIC Science & Technology

2014-10-31

molecule is constructed based on high- level ab-initio calculations and interpolated using the reproducible kernel Hilbert space (RKHS) method and...a potential energy surface (PES) for the ground state of the NO2 molecule is constructed based on high- level ab initio calculations and interpolated...between O(3P) and NO(2Π) at higher temperatures relevant to the hypersonic flight regime of reentering space- crafts. At a more fundamental level , we

Energy levels, oscillator strengths, line strengths, and transition probabilities in Si-like ions of La XLIII, Er LIV, Tm LV, and Yb LVI

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

Chen, Zhan-Bin, E-mail: chenzb008@qq.com; Ma, Kun; Wang, Hong-Jian

2017-01-15

Detailed calculations using the multi-configuration Dirac–Fock (MCDF) method are carried out for the lowest 64 fine-structure levels of the 3s{sup 2}3p{sup 2}, 3s{sup 2}3p3d, 3s3p{sup 3}, 3s3p{sup 2}3d, 3s{sup 2}3d{sup 2}, and 3p{sup 4} configurations in Si-like ions of La XLIII, Er LIV, Tm LV, and Yb LVI. Energies, oscillator strengths, wavelengths, line strengths, and radiative electric dipole transition rates are given for all ions. A parallel calculation using the many-body perturbation theory (MBPT) method is also carried out to assess the present energy levels accuracy. Comparisons are performed between these two sets of energy levels, as well as withmore » other available results, showing that they are in good agreement with each other within 0.5%. These high accuracy results can be used to the modeling and the interpretation of astrophysical objects and fusion plasmas. - Highlights: • Energy levels and E1 transition rates of Si-like ions are presented. • Breit interaction and Quantum Electrodynamics effects are discussed. • Present results should be useful in the astrophysical application and plasma modeling.« less

Improving hydropower choices via an online and open access tool

PubMed Central

Vilela, Thais; Reid, John

2017-01-01

This paper describes and validates the HydroCalculator Tool developed by Conservation Strategy Fund. The HydroCalculator Tool allows researchers, policy-makers and citizens to easily assess hydropower feasibility, by calculating traditional financial indicators, such as the levelized cost of energy, as well as greenhouse gas emissions and the economic net present value including emissions costs. Currently, people other than project developers have limited or no access to such information, which stifles informed public debate on electric energy options. Within this context, the use of the HydroCalculator Tool may contribute to the debate, by facilitating access to information. To validate the tool’s greenhouse gas calculations, we replicate two peer-reviewed articles that estimate greenhouse gas emissions from different hydropower plants in the Amazon basin. The estimates calculated by the HydroCalculator Tool are similar to the ones found in both peer-reviewed articles. The results show that hydropower plants can lead to greenhouse gas emissions and that, in some cases, these emissions can be larger than those of alternative energy sources producing the same amount of electricity. PMID:28650968

Improving hydropower choices via an online and open access tool.

PubMed

Vilela, Thais; Reid, John

2017-01-01

This paper describes and validates the HydroCalculator Tool developed by Conservation Strategy Fund. The HydroCalculator Tool allows researchers, policy-makers and citizens to easily assess hydropower feasibility, by calculating traditional financial indicators, such as the levelized cost of energy, as well as greenhouse gas emissions and the economic net present value including emissions costs. Currently, people other than project developers have limited or no access to such information, which stifles informed public debate on electric energy options. Within this context, the use of the HydroCalculator Tool may contribute to the debate, by facilitating access to information. To validate the tool's greenhouse gas calculations, we replicate two peer-reviewed articles that estimate greenhouse gas emissions from different hydropower plants in the Amazon basin. The estimates calculated by the HydroCalculator Tool are similar to the ones found in both peer-reviewed articles. The results show that hydropower plants can lead to greenhouse gas emissions and that, in some cases, these emissions can be larger than those of alternative energy sources producing the same amount of electricity.

Thermal effects and antibacterial properties of energy levels required to sterilize stained root canals with an Nd:YAG laser.

PubMed

Ramsköld, L O; Fong, C D; Strömberg, T

1997-02-01

Thermal effects and antibacterial properties of an Nd:YAG laser were studied to establish clinically safe levels of energy to deliver into the root canal and to determine the energy level needed to sterilize infected root canals. The results indicate that lasing cycles of 3 J-s for 15 s followed by a 15-s recovery interval can be continued for prolonged periods without risk of thermal damage to surrounding tissues. In vitro lasing of root canals inoculated with dark stained bacteria showed that two such lasing cycles sterilized only two out of eight canals, whereas when four cycles were used seven out of eight canals were sterilized. Guidelines for energy levels in endodontic Nd:YAG laser work are discussed, and base data for calculating appropriate energy levels are given.

Interaction of sodium atoms with stacking faults in silicon with different Fermi levels

NASA Astrophysics Data System (ADS)

Ohno, Yutaka; Morito, Haruhiko; Kutsukake, Kentaro; Yonenaga, Ichiro; Yokoi, Tatsuya; Nakamura, Atsutomo; Matsunaga, Katsuyuki

2018-06-01

Variation in the formation energy of stacking faults (SFs) with the contamination of Na atoms was examined in Si crystals with different Fermi levels. Na atoms agglomerated at SFs under an electronic interaction, reducing the SF formation energy. The energy decreased with the decrease of the Fermi level: it was reduced by more than 10 mJ/m2 in p-type Si, whereas it was barely reduced in n-type Si. Owing to the energy reduction, Na atoms agglomerating at SFs in p-type Si are stable compared with those in n-type Si, and this hypothesis was supported by ab initio calculations.

Extended wave-packet model to calculate energy-loss moments of protons in matter

NASA Astrophysics Data System (ADS)

Archubi, C. D.; Arista, N. R.

2017-12-01

In this work we introduce modifications to the wave-packet method proposed by Kaneko to calculate the energy-loss moments of a projectile traversing a target which is represented in terms of Gaussian functions for the momentum distributions of electrons in the atomic shells. These modifications are introduced using the Levine and Louie technique to take into account the energy gaps corresponding to the different atomic levels of the target. We use the extended wave-packet model to evaluate the stopping power, the energy straggling, the inverse mean free path, and the ionization cross sections for protons in several targets, obtaining good agreements for all these quantities on an extensive energy range that covers low-, intermediate-, and high-energy regions. The extended wave-packet model proposed here provides a method to calculate in a very straightforward way all the significant terms of the inelastic interaction of light ions with any element of the periodic table.

Energy dissipation dataset for reversible logic gates in quantum dot-cellular automata.

PubMed

Bahar, Ali Newaz; Rahman, Mohammad Maksudur; Nahid, Nur Mohammad; Hassan, Md Kamrul

2017-02-01

This paper presents an energy dissipation dataset of different reversible logic gates in quantum-dot cellular automata. The proposed circuits have been designed and verified using QCADesigner simulator. Besides, the energy dissipation has been calculated under three different tunneling energy level at temperature T =2 K. For estimating the energy dissipation of proposed gates; QCAPro tool has been employed.

Impact behaviour of Napier/polyester composites under different energy levels

NASA Astrophysics Data System (ADS)

Fahmi, I.; Majid, M. S. Abdul; Afendi, M.; Haslan, M.; Helmi E., A.; M. Haameem J., A.

2016-07-01

The effects of different energy levels on the impact behaviour of Napier fibre/polyester reinforced composites were investigated. Napier fibre was extracted using traditional water retting process to be utilized as reinforcing materials in polyester composite laminates. 25% fibre loading composite laminates were prepared and impacted at three different energy levels; 2.5,5 and 7.5 J using an instrumented drop weight impact testing machine (IMATEK IM10). The outcomes show that peak force and contact time increase with increased impact load. The energy absorption was then calculated from the force displacement curve. The results indicated that the energy absorption decreases with increasing energy levels of the impact. Impacted specimens were observed visually for fragmentation fracture using an optical camera to identify the failure mechanisms. Fracture fragmentation pattern from permanent dent to perforation with radial and circumferential was observed.

Solution of the Schrodinger Equation for One-Dimensional Anharmonic Potentials: An Undergraduate Computational Experiment

ERIC Educational Resources Information Center

Beddard, Godfrey S.

2011-01-01

A method of solving the Schrodinger equation using a basis set expansion is described and used to calculate energy levels and wavefunctions of the hindered rotation of ethane and the ring puckering of cyclopentene. The calculations were performed using a computer algebra package and the calculations are straightforward enough for undergraduates to…

Accurate potential energy surface for the 1(2)A' state of NH(2): scaling of external correlation versus extrapolation to the complete basis set limit.

PubMed

Li, Y Q; Varandas, A J C

2010-09-16

An accurate single-sheeted double many-body expansion potential energy surface is reported for the title system which is suitable for dynamics and kinetics studies of the reactions of N(2D) + H2(X1Sigmag+) NH(a1Delta) + H(2S) and their isotopomeric variants. It is obtained by fitting ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pVQZ basis set, after slightly correcting semiempirically the dynamical correlation using the double many-body expansion-scaled external correlation method. The function so obtained is compared in detail with a potential energy surface of the same family obtained by extrapolating the calculated raw energies to the complete basis set limit. The topographical features of the novel global potential energy surface are examined in detail and found to be in general good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. The novel function has been built so as to become degenerate at linear geometries with the ground-state potential energy surface of A'' symmetry reported by our group, where both form a Renner-Teller pair.

Rotationally inelastic scattering of ND3 with H2 as a probe of the intermolecular potential energy surface

NASA Astrophysics Data System (ADS)

Tkáč, Ondřej; Saha, Ashim K.; Loreau, Jérôme; Ma, Qianli; Dagdigian, Paul J.; Parker, David H.; van der Avoird, Ad; Orr-Ewing, Andrew J.

2015-12-01

Differential cross sections (DCSs) are reported for rotationally inelastic scattering of ND3 with H2, measured using a crossed molecular beam apparatus with velocity map imaging (VMI). ND3 molecules were quantum-state selected in the ground electronic and vibrational levels and, optionally, in the j±k = 11- rotation-inversion level prior to collisions. Inelastic scattering of state-selected ND3 with H2 was measured at the mean collision energy of 580 cm-1 by resonance-enhanced multiphoton ionisation spectroscopy and VMI of ND3 in selected single final j'±k' levels. Comparison of experimental DCSs with close-coupling quantum-mechanical scattering calculations serves as a test of a recently reported ab initio potential energy surface. Calculated integral cross sections reveal the propensities for scattering into various final j'±k' levels of ND3 and differences between scattering by ortho and para H2. Integral and differential cross sections are also computed at a mean collision energy of 430 cm-1 and compared to our recent results for inelastic scattering of state-selected ND3 with He.

Theoretical Study of Electronic Structure and Thermoelectric Properties of Doped CuAlO2

NASA Astrophysics Data System (ADS)

Poopanya, P.; Yangthaisong, A.; Rattanapun, C.; Wichainchai, A.

2011-05-01

The doping level dependence of thermoelectric properties of delafossite CuAlO2 has been investigated in the constant scattering time ( τ) approximation, starting from the first principles of electronic structure. In particular, the lattice parameters and the energy band structure were calculated using the total energy plane-wave pseudopotential method. It was found that the lattice parameters of CuAlO2 are a = 2.802 Å and c = 16.704 Å, and the internal parameter is u = 0.1097. CuAlO2 has an indirect band gap of 2.17 eV and a direct gap of 3.31 eV. The calculated energy band structures were then used to calculate the electrical transport coefficients of CuAlO2. By considering the effects of doping level and temperature, it was found that the Seebeck coefficient S( T) increases with increasing acceptor doping ( A d) level. The values of S( T) in our experiments correspond to an A d level at 0.262 eV, which is identified as the Fermi level of CuAlO2. Based on our experimental Seebeck coefficient and the electrical conductivity, the constant relaxation time is estimated to be 1 × 10-16 s. The power factor is large for a low A d level and increases with temperature. It is suggested that delafossite CuAlO2 can be considered as a promising thermoelectric oxide material at high doping and high temperature.

Quantum close coupling calculation of transport and relaxation properties for Hg-H2 system

NASA Astrophysics Data System (ADS)

Nemati-Kande, Ebrahim; Maghari, Ali

2016-11-01

Quantum mechanical close coupling calculation of the state-to-state transport and relaxation cross sections have been done for Hg-H2 molecular system using a high-level ab initio potential energy surface. Rotationally averaged cross sections were also calculated to obtain the energy dependent Senftleben-Beenakker cross sections at the energy range of 0.005-25,000 cm-1. Boltzmann averaging of the energy dependent Senftleben-Beenakker cross sections showed the temperature dependency over a wide temperature range of 50-2500 K. Interaction viscosity and diffusion coefficients were also calculated using close coupling cross sections and full classical Mason-Monchick approximation. The results were compared with each other and with the available experimental data. It was found that Mason-Monchick approximation for viscosity is more reliable than diffusion coefficient. Furthermore, from the comparison of the experimental diffusion coefficients with the result of the close coupling and Mason-Monchick approximation, it was found that the Hg-H2 potential energy surface used in this work can reliably predict diffusion coefficient data.

Ab initio intermolecular potential energy surface for the CO2—N2 system and related thermophysical properties

NASA Astrophysics Data System (ADS)

Crusius, Johann-Philipp; Hellmann, Robert; Castro-Palacio, Juan Carlos; Vesovic, Velisa

2018-06-01

A four-dimensional potential energy surface (PES) for the interaction between a rigid carbon dioxide molecule and a rigid nitrogen molecule was constructed based on quantum-chemical ab initio calculations up to the coupled-cluster level with single, double, and perturbative triple excitations. Interaction energies for a total of 1893 points on the PES were calculated using the counterpoise-corrected supermolecular approach and basis sets of up to quintuple-zeta quality with bond functions. The interaction energies were extrapolated to the complete basis set limit, and an analytical site-site potential function with seven sites for carbon dioxide and five sites for nitrogen was fitted to the interaction energies. The CO2—N2 cross second virial coefficient as well as the dilute gas shear viscosity, thermal conductivity, and binary diffusion coefficient of CO2—N2 mixtures were calculated for temperatures up to 2000 K to validate the PES and to provide reliable reference values for these important properties. The calculated values are in very good agreement with the best experimental data.

Nonlinear optical susceptibilities in the diffusion modified AlxGa1-xN/GaN single quantum well

NASA Astrophysics Data System (ADS)

Das, T.; Panda, S.; Panda, B. K.

2018-05-01

Under thermal treatment of the post growth AlGaN/GaN single quantum well, the diffusion of Al and Ga atoms across the interface is expected to form the diffusion modified quantum well with diffusion length as a quantitative parameter for diffusion. The modification of confining potential and position-dependent effective mass in the quantum well due to diffusion is calculated taking the Fick's law. The built-in electric field which arises from spontaneous and piezoelectric polarizations in the wurtzite structure is included in the effective mass equation. The electronic states are calculated from the effective mass equation using the finite difference method for several diffusion lengths. Since the effective well width decreases with increasing diffusion length, the energy levels increase with it. The intersubband energy spacing in the conduction band decreases with diffusion length due to built-in electric field and reduction of effective well width. The linear susceptibility for first-order and the nonlinear second-order and third-order susceptibilities are calculated using the compact density matrix approach taking only two levels. The calculated susceptibilities are red shifted with increase in diffusion lengths due to decrease in intersubband energy spacing.

Reductive half-reaction of aldehyde oxidoreductase toward acetaldehyde: Ab initio and free energy quantum mechanical/molecular mechanical calculations.

PubMed

Dieterich, Johannes M; Werner, Hans-Joachim; Mata, Ricardo A; Metz, Sebastian; Thiel, Walter

2010-01-21

Energy and free energy barriers for acetaldehyde conversion in aldehyde oxidoreductase are determined for three reaction pathways using quantum mechanical/molecular mechanical (QM/MM) calculations on the solvated enzyme. Ab initio single-point QM/MM energies are obtained at the stationary points optimized at the DFT(B3LYP)/MM level. These ab initio calculations employ local correlation treatments [LMP2 and LCCSD(T0)] in combination with augmented triple- and quadruple-zeta basis sets, and the final coupled cluster results include MP2-based corrections for basis set incompleteness and for the domain approximation. Free energy perturbation (FEP) theory is used to generate free energy profiles at the DFT(B3LYP)/MM level for the most important reaction steps by sampling along the corresponding reaction paths using molecular dynamics. The ab initio and FEP QM/MM results are combined to derive improved estimates of the free energy barriers, which differ from the corresponding DFT(B3LYP)/MM energy barriers by about 3 kcal mol(-1). The present results confirm the qualitative mechanistic conclusions from a previous DFT(B3LYP)/MM study. Most favorable is a three-step Lewis base catalyzed mechanism with an initial proton transfer from the cofactor to the Glu869 residue, a subsequent nucleophilic attack that yields a tetrahedral intermediate (IM2), and a final rate-limiting hydride transfer. The competing metal center activated pathway has the same final step but needs to overcome a higher barrier in the initial step on the route to IM2. The concerted mechanism has the highest free energy barrier and can be ruled out. While confirming the qualitative mechanistic scenario proposed previously on the basis of DFT(B3LYP)/MM energy profiles, the present ab initio and FEP QM/MM calculations provide corrections to the barriers that are important when aiming at high accuracy.

A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H2

NASA Astrophysics Data System (ADS)

Denis-Alpizar, Otoniel; Kalugina, Yulia; Stoecklin, Thierry; Vera, Mario Hernández; Lique, François

2013-12-01

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H2. Ab initio calculations of the HCN-H2 van der Waals complex, considering both molecules as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN-H2 with the nitrogen pointing towards H2 at an intermolecular separation of 7.20 a0. The corresponding well depth is -195.20 cm-1. A secondary minimum of -183.59 cm-1 was found for a T-shape configuration with the H of HCN pointing to the center of mass of H2. We also determine the rovibrational energy levels of the HCN-para-H2 and HCN-ortho-H2 complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm-1 and 60.26 cm-1, respectively. The calculated ro-vibrational transitions in the HCN-H2 complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.

Towards designing polymers for photovoltaic applications: A DFT and experimental study of polyazomethines with various chemical structures

NASA Astrophysics Data System (ADS)

Wojtkiewicz, Jacek; Iwan, Agnieszka; Pilch, Marek; Boharewicz, Bartosz; Wójcik, Kamil; Tazbir, Igor; Kaminska, Maria

2017-06-01

Theoretical studies of polyazomethines (PAZs) with various chemical structures designated for photovoltaic applications are presented. PAZ energy levels and optical properties were calculated within density-functional theory (DFT and TDDFT) framework for 28 oligomers (monomer, dimer and trimer) of PAZs. The correlations between chemical structure of PAZ and location of its highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels were examined. It turned out that the presence of triaminophenylene, dimethoxydiphenylene and fluorine group raises the orbital energies. As a consequence, it is a factor which improves the photovoltaic efficiency of solar cell built on the base of the corresponding PAZ and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). On the contrary, quinone, 1,3,5-triazine and perfluorophenylene groups lower orbital energies and have negative influence on the photovoltaic efficiency. Moreover, calculations for methyl, ethyl and butyl analogs of P3HT as well as polythiophenes were performed and compared with the results obtained for PAZs. In addition experimental data are presented, which cover optical, electrochemical and electrical transport properties of the studied PAZs, allowing to determine HOMO and LUMO energies of the polymers and their conductivity. Finally, comparison between calculated and experimental results were made and discussed.

Collisional Quenching of Highly-Excited H2 due to H2 Collisions

NASA Astrophysics Data System (ADS)

Wan, Yier; Yang, Benhui H.; Stancil, Phillip C.; Naduvalath, Balakrishnan; Forrey, Robert C.; This work was partially support by Hubble grant HST-AT-13899. We thank Kyle Walkerassistance with vrrmm.

2017-06-01

Collision-induced energy transfer involving H2 molecules are of significant interest, since H2 is the most abundant molecular species in the universe. Collisional de-excitation rate coefficients of the H2-H2 system are necessary to produce accurate models of astrophysical environments. However, accurate calculations of collisional energy transfer are still a challenging problem, especially for highly-excited H2 because a large number of levels must be included in the calculation.Currently, most data are limited to initial rotational levels j up to 8 or initial vibrational levels up to 3. The vast majority of these results involve some form of a reduced-dimensional approach which may be of questionable accuracy. A reliable and accurate four-dimensional PES computed by Patkowski et al. is used in this work along with two quantum scattering programs (MOLSCAT and vrrmm). Another accurate full-dimensional PES has been reported for the H2-H2 system by Hinde.Not all transitions will be explicitly calculated. A zero-energy scaling technique (ZEST) is used to estimate some intermediate transitions from calculated rate coefficients. New inelastic quenching cross section for para-H2+para-H2 collisions with initial level j= 10, 12, 14, 18, 24 are calculated. Calculations for other de-excitation transitions from higher initial levels and collisions involving other spin isomer of hydrogen, ortho-H2+para-H2, ortho-H2+ortho-H2 and para-H2+ortho-H2 are in progress. The coupled- states approximation is also applied to obtain cross sections at high energy.K. Patkowski, et al., J. Chem. Phys. 129, 094304 (2008).J. M. Hutson and S. Green, MOLSCAT Computer code, v14 (1994).K. Walker, 2013, VRRMM: Vibrational/Rotational Rich Man’s MOLSCAT v3.1.K. Walker, Song, L., Yang, B. H.,et al. 2015, ApJ, \\811,27.S. Green, J. Chem. Phys. 62, 2271 (1975).Flower, D. R., Roueff, E. 1998, J. Phys. B, 31, 2935.T. -G. Lee, N. Balakrishnan, R. C. Forrey, P. C. Stancil, G. Shaw, D. R. Schultz, and G. J. Ferland. 2008, ApJ, 689, 1105-1111.P. Diep and J. K. Johnson, J. Chem. Phys. 112, 4465 (2000).R. J. Hinde, J. Chem. Phys. 128, 154308 (2008).R. V. Krems, TwoBC, Univ. British Columbia, Vancouver, CA (2006).

Interface effects on calculated defect levels for oxide defects

NASA Astrophysics Data System (ADS)

Edwards, Arthur; Barnaby, Hugh; Schultz, Peter; Pineda, Andrew

2014-03-01

Density functional theory (DFT) has had impressive recent success predicting defect levels in insulators and semiconductors [Schultz and von Lillienfeld, 2009]. Such success requires care in accounting for long-range electrostatic effects. Recently, Komsa and Pasquarello have started to address this problem in systems with interfaces. We report a multiscale technique for calculating electrostatic energies for charged defects in oxide of the metal-oxide-silicon (MOS) system, but where account is taken of substrate doping density, oxide thickness, and gate bias. We use device modeling to calculate electric fields for a point charge a fixed distance from the interface, and used the field to numerically calculate the long-range electrostatic interactions. We find, for example, that defect levels in the oxide do depend on both the magnitude and the polarity the substrate doping density. Furthermore, below 20 Å, oxide thickness also has significant effects. So, transferring results directly from bulk calculations leads to inaccuracies up to 0.5 eV- half of the silicon band gap. We will present trends in defect levels as a function of device parameters. We show that these results explain previous experimental results, and we comment on their potential impact on models for NBTI. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the United States Department of Energy's National Nuclear Security Administration under co.

Density Functional Theory Calculations of Activation Energies for Carrier Capture by Defects in Semiconductors

NASA Astrophysics Data System (ADS)

Modine, Normand; Wright, Alan; Lee, Stephen

2015-03-01

Carrier recombination due to defects can have a major impact on device performance. The rate of defect-induced recombination is determined by both defect levels and carrier capture cross-sections. Density functional theory (DFT) has been widely and successfully used to predict defect levels, but only recently has work begun to focus on using DFT to determine carrier capture cross-sections. Lang and Henry worked out the fundamental theory of carrier-capture by multiphonon emission in the 1970s and showed that, above the Debye temperature, carrier-capture cross-sections differ between defects primarily due to differences in their carrier capture activation energies. We present an approach to using DFT to calculate carrier capture activation energies that does not depend on an assumed configuration coordinate and that fully accounts for anharmonic effects, which can substantially modify carrier activation energies. We demonstrate our approach for the -3/-2 level of the Ga vacancy in wurtzite GaN. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Connecting Interface Structure to Energy Level Alignment at Aqueous Semiconductor Interfaces

NASA Astrophysics Data System (ADS)

Hybertsen, Mark

Understanding structure-function relationships at aqueous semiconductor interfaces presents fundamental challenges, including the discovery of the key interface structure motifs themselves. Important examples include the alignment of electrochemical redox levels with the semiconductor band edges and the identification of catalytic active sites. We have developed a multistep approach, initially demonstrated for GaN, ZnO and their alloys, motivated by measured high efficiency for photocatalytic water oxidation. The interface structure is simulated using ab initio molecular dynamics (AIMD). The calculated, average interface dipole is combined with the GW approach from many-body perturbation theory to calculate the energy level alignment between the semiconductor band edges and the centroid of the occupied 1b1 energy level of water and thus, the electrochemical levels. Cluster models are used to study reaction pathways. The emergent interface motif is the full (GaN) or partial (ZnO) dissociated interface water layer. Here I will focus on the aqueous interfaces to the stable TiO2 anatase (101) and rutile (110) facets. The AIMD calculations reveal interface water dissociation and reassociation processes through distinct pathways: one direct at the interface and the other via a spectator water molecule from the hydration layer. Comparisons between the two interfaces shows that the energy landscape for these pathways depends on the local hydrogen bonding patterns and the interplay with the interface template. Combined results from different initial conditions and AIMD temperatures demonstrate a partially dissociated interface water layer in both cases. Specifically for rutile, structure and the GW-based analysis of the interface energy level alignment agree with experiment. Finally, hole localization at different interface structure motifs will be discussed. Work performed in collaboration with J. Lyons, N. Kharche, M. Ertem and J. Muckerman, done in part at the CFN, which is a U.S. DOE Office of Science Facility, at BNL under Contract No. DE-SC0012704 and with resources from NERSC under Contract No. DE-AC02-05CH11231.

Structural and vibrational studies on 1-(5-methyl-[1,3,4] thiadiazol-2-yl)-pyrolidin-2-ol

NASA Astrophysics Data System (ADS)

Ramesh Babu, N.; Saleem, H.; Subashchandrabose, S.; Padusha, M. Syed Ali; Bharanidharan, S.

2016-01-01

FT-Raman and FT-IR spectra were recorded for1-(5-methyl-[1,3,4]thiadiazol-2-yl)-pyrolidin-2-ol (MTPN) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, IR and the Raman scattering intensities were computed using DFT/6-311++G (d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the IR and Raman spectra, based on the TED of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated. The intra-molecular charge transfer was calculated by means of NBO. Hyperconjugative interaction energy was more during the π-π∗ transition. Energy gap of the molecule has been found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable.

A gauge-independent zeroth-order regular approximation to the exact relativistic Hamiltonian—Formulation and applications

NASA Astrophysics Data System (ADS)

Filatov, Michael; Cremer, Dieter

2005-01-01

A simple modification of the zeroth-order regular approximation (ZORA) in relativistic theory is suggested to suppress its erroneous gauge dependence to a high level of approximation. The method, coined gauge-independent ZORA (ZORA-GI), can be easily installed in any existing nonrelativistic quantum chemical package by programming simple one-electron matrix elements for the quasirelativistic Hamiltonian. Results of benchmark calculations obtained with ZORA-GI at the Hartree-Fock (HF) and second-order Møller-Plesset perturbation theory (MP2) level for dihalogens X2 (X=F,Cl,Br,I,At) are in good agreement with the results of four-component relativistic calculations (HF level) and experimental data (MP2 level). ZORA-GI calculations based on MP2 or coupled-cluster theory with single and double perturbations and a perturbative inclusion of triple excitations [CCSD(T)] lead to accurate atomization energies and molecular geometries for the tetroxides of group VIII elements. With ZORA-GI/CCSD(T), an improved estimate for the atomization energy of hassium (Z=108) tetroxide is obtained.

Einstein coefficients and oscillator strengths for low lying state of CO molecules

NASA Astrophysics Data System (ADS)

Swer, S.; Syiemiong, A.; Ram, M.; Jha, A. K.; Saxena, A.

2018-04-01

Einstein Coefficients and Oscillator Strengths for different state of CO molecule have been calculated using LEROY'S LEVEL program and MOLCAS ab initio code. Using the wave function derived from Morse potential and transition dipole moment obtained from ab initio calculation, The potential energy functions were computed for these states using the spectroscopic constants. The Morse potential of these states and electronic transition dipole moment of the transition calculated in a recent ab initio study have been used in LEVEL program to produce transition dipole matrix element for a large number of bands. Einstein Coefficients have also been used to compute the radiative lifetimes of several vibrational levels and the calculated values are compared with other theoretical results and experimental values.

The CO 2 with dimethylamine reaction: ab initio predicted vibrational spectra

NASA Astrophysics Data System (ADS)

Jamróz, M. H.; Dobrowolski, J. Cz.; Borowiak, M. A.

1999-05-01

The IR spectra of CO 2, dimethylamine (DMA), (DMA) 2 dimers, DMA⋯CO 2 (2 : 1) complex, dimethylcarbamic acid (DMCA), DMCA⋯DMA (1 : 1) complex, DMCA -, and DMA(H) + were calculated at the B3PW91/6-31G** level. Potential energy distribution (PED) was calculated for predicted spectra to form basis for elucidation of experimental IR data. The stabilisation energy of the studied complexes was corrected by counterpoise method.

Location of protons in N-H···N hydrogen-bonded systems: a theoretical study on intramolecular pyridine-dihydropyridine and pyridine-pyridinium pairs.

PubMed

Mori, Yukie; Takano, Keiko

2012-08-21

Two-dimensional potential energy surfaces (PESs) were calculated for the degenerate intramolecular proton transfer (PT) in two N-H···N hydrogen-bonded systems, (Z)-2-(2-pyridylmethylidene)-1,2-dihydropyridine (1) and monoprotonated di(2-pyridyl) ether (2), at the MP2/cc-pVDZ level of theory. The calculated PES had two minima in both cases. The energy barrier in 1 was higher than the zero-point energy (ZPE) level, while that in 2 was close to the ZPE. Vibrational wavefunctions were obtained by solving time-independent Schrödinger equations with the calculated PESs. The maximum points of the probability density were shifted from the energy minima towards the region where the covalent N-H bond was elongated and the N···N distance shortened. The effects of a polar solvent on the PES were investigated with the continuum or cluster models in such a way that the solute-solvent electrostatic interactions could be taken into account under non-equilibrated conditions. A solvated contact ion-pair was modelled by a cluster consisting of one cation 2, one chloride ion and 26 molecules of acetonitrile. The calculation with this model suggested that the bridging proton is localised in the deeper well due to the significant asymmetry of the PES and the high potential barrier.

Proposed software system for atomic-structure calculation

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

Fischer, C.F.

1981-07-01

Atomic structure calculations are understood well enough that, at a routine level, an atomic structure software package can be developed. At the Atomic Physics Conference in Riga, 1978 L.V. Chernysheva and M.Y. Amusia of Leningrad University, presented a paper on Software for Atomic Calculations. Their system, called ATOM is based on the Hartree-Fock approximation and correlation is included within the framework of RPAE. Energy level calculations, transition probabilities, photo-ionization cross-sections, electron scattering cross-sections are some of the physical properties that can be evaluated by their system. The MCHF method, together with CI techniques and the Breit-Pauli approximation also provides amore » sound theoretical basis for atomic structure calculations.« less

Critically Evaluated Energy Levels, Spectral Lines, Transition Probabilities, and Intensities of Singly Ionized Vanadium (V II)

NASA Astrophysics Data System (ADS)

Saloman, Edward B.; Kramida, Alexander

2017-08-01

The energy levels, observed spectral lines, and transition probabilities of singly ionized vanadium, V II, have been compiled. The experimentally derived energy levels belong to the configurations 3d 4, 3d 3 ns (n = 4, 5, 6), 3d 3 np, and 3d 3 nd (n = 4, 5), 3d 34f, 3d 24s 2, and 3d 24s4p. Also included are values for some forbidden lines that may be of interest to the astrophysical community. Experimental Landé g-factors and leading percentages for the levels are included when available, as well as Ritz wavelengths calculated from the energy levels. Wavelengths and transition probabilities are reported for 3568 and 1896 transitions, respectively. From the list of observed wavelengths, 407 energy levels are determined. The observed intensities, normalized to a common scale, are provided. From the newly optimized energy levels, a revised value for the ionization energy is derived, 118,030(60) cm-1, corresponding to 14.634(7) eV. This is 130 cm-1 higher than the previously recommended value from Iglesias et al.

Core excitations across the neutron shell gap in 207Tl

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

Wilson, E.; Podolyák, Zs.; Grawe, H.

2015-05-05

The single closed-neutron-shell, one proton–hole nucleus 207Tl was populated in deep-inelastic collisions of a 208Pb beam with a 208Pb target. The yrast and near-yrast level scheme has been established up to high excitation energy, comprising an octupole phonon state and a large number of core excited states. Based on shell-model calculations, all observed single core excitations were established to arise from the breaking of the N=126 neutron core. While the shell-model calculations correctly predict the ordering of these states, their energies are compressed at high spins. It is concluded that this compression is an intrinsic feature of shell-model calculations usingmore » two-body matrix elements developed for the description of two-body states, and that multiple core excitations need to be considered in order to accurately calculate the energy spacings of the predominantly three-quasiparticle states.« less

Dynamic Jahn-Teller effect: Calculation of fine structure spectrum, isotope shift and Zeeman behavior at deep center Ni2+ in CdS

NASA Astrophysics Data System (ADS)

Schoepp, Juergen

The internal transition of the deep center Ni2+ in II to IV semiconductor cadmium sulfide is examined with reference to crystal field theory. An algorithm was developed for calculation, in a basis fitted to trigonal symmetry, of fine structure operator matrix which is made of the sum of operators from spin trajectory coupling, trigonal field and electron phonon coupling. The dependence of energy level on the mass was calculated in order to examine the isotropy effect at Ni2+ transition. The mass dependence of phonon energy was estimated in an atomic cluster by using a valence force model from Keating for elastic energy. The Zeeman behavior of Ni2+ transition was examined for magnetic fields; the Zeeman operator was added to the fine structure operator and the resulting matrix was diagonalized. It is noticed that calculations are quantitatively and qualitatively in agreement with experiments.

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

Gifford, Jason S.; Grace, Robert C.; Rickerson, Wilson H.

This report serves as a resource for policymakers who wish to learn more about levelized cost of energy (LCOE) calculations, including cost-based incentives. The report identifies key renewable energy cost modeling options, highlights the policy implications of choosing one approach over the other, and presents recommendations on the optimal characteristics of a model to calculate rates for cost-based incentives, FITs, or similar policies. These recommendations shaped the design of NREL's Cost of Renewable Energy Spreadsheet Tool (CREST), which is used by state policymakers, regulators, utilities, developers, and other stakeholders to assist with analyses of policy and renewable energy incentive paymentmore » structures. Authored by Jason S. Gifford and Robert C. Grace of Sustainable Energy Advantage LLC and Wilson H. Rickerson of Meister Consultants Group, Inc.« less

A Theoretical Study on N'-[(Z)-(4-Methylphenyl)Methylidene]-4-Nitrobenzohydrazide (NMPMN)

NASA Astrophysics Data System (ADS)

Okur, Muhammet; Albayrak, Nazmiye; Tamer, Ömer; Avcı, Davut; Atalay, Yusuf

2018-05-01

Quantum mechanical calculations of ground state energy, vibration wavenumbers, and electronic absorption wavelengths of N'-[(Z)-(4-methylphenyl)methylidene]-4-nitrobenzohydrazide with C15H13N3O3 empirical formula was performed by using Gaussian 09 program. Becke's three-parameter exchange functional in conjunction with the Lee-Yang-Parr correlation functional and Heyd-Scuseria-Ernzerhof functional levels of density functional theory (DFT) with the 6-311++G(d,p) basis set were used in the performing of above mentioned calculations. The highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energies have been also calculated at the same levels. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Nonlinear optical (NLO) behavior of the title molecule has been examined by the determining of electric dipole moment (μ), polarizability (α), and static first-order hyperpolarizability (β). Finally, molecular electrostatic potential (MEP) surface as well as Mulliken and NBO atomic charges were calculated by using Gaussian 09 program.

Sulfur mustard gas adsorption on ZnO fullerene-like nanocage: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Kazemi, Mohammad; Rad, Ali Shokuhi

2017-06-01

In the present study, we used density functional theory calculations (at B3LYP and ωB97XD Levels) to search on the adsorption of Sulfur mustard gas (defined as mustard gas) on the surface of fullerene-like ZnO nanocage as a semiconductor. We found three different configurations of adsorbed gas on the surface of this nanostructure semiconductor. The values of adsorption energy of mustard gas are calculated in the range of -144∼ -200 kJ/mol with enthalpies in the range of -132∼-195 kJ/mol and Gibbs free energies in the range of -88∼-144 kJ/mol (T = 298 K, based on ωB97XD level), which indicate exothermic and spontaneous chemisorption. For all geometries, we calculated geometry parameters by taking into account the charge analysis and frontier molecular orbital study. The result of this study can be a support for next studies to develop new nanomaterials as adsorbent/sensor for mustard gas.

Model for Cumulative Solar Heavy Ion Energy and LET Spectra

NASA Technical Reports Server (NTRS)

Xapsos, Mike; Barth, Janet; Stauffer, Craig; Jordan, Tom; Mewaldt, Richard

2007-01-01

A probabilistic model of cumulative solar heavy ion energy and lineary energy transfer (LET) spectra is developed for spacecraft design applications. Spectra are given as a function of confidence level, mission time period during solar maximum and shielding thickness. It is shown that long-term solar heavy ion fluxes exceed galactic cosmic ray fluxes during solar maximum for shielding levels of interest. Cumulative solar heavy ion fluences should therefore be accounted for in single event effects rate calculations and in the planning of space missions.

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

Nahar, Sultana N., E-mail: nahar@astronomy.ohio-state.edu

The atomic parameters–oscillator strengths, line strengths, radiative decay rates (A), and lifetimes–for fine structure transitions of electric dipole (E1) type for the astrophysically abundant ion Ne IV are presented. The results include 868 fine structure levels with n≤ 10, l≤ 9, and 1/2≤J≤ 19/2 of even and odd parities, and the corresponding 83,767 E1 transitions. The calculations were carried out using the relativistic Breit–Pauli R-matrix method in the close coupling approximation. The transitions have been identified spectroscopically using an algorithm based on quantum defect analysis and other criteria. The calculated energies agree with the 103 observed and identified energies to withinmore » 3% or better for most of the levels. Some larger differences are also noted. The A-values show good to fair agreement with the very limited number of available transitions in the table compiled by NIST, but show very good agreement with the latest published multi-configuration Hartree–Fock calculations. The present transitions should be useful for diagnostics as well as for precise and complete spectral modeling in the soft X-ray to infra-red regions of astrophysical and laboratory plasmas. -- Highlights: •The first application of BPRM method for accurate E1 transitions in Ne IV is reported. •Amount of atomic data (n going up to 10) is complete for most practical applications. •The calculated energies are in very good agreement with most observed levels. •Very good agreement of A-values and lifetimes with other relativistic calculations. •The results should provide precise nebular abundances, chemical evolution etc.« less

Vibrational spectroscopy investigation and density functional theory calculations on (E)-N‧-(4-methoxybenzylidene) benzohydrazide

NASA Astrophysics Data System (ADS)

Saleem, H.; Subashchandrabose, S.; Ramesh Babu, N.; Syed Ali Padusha, M.

2015-05-01

The FT-IR, FT-Raman and UV-Vis spectra of the Schiff base compound (E)-N‧-(4-methoxybenzylidene) benzohydrazide (MBBH) have been recorded and analyzed. The optimized geometrical parameters were calculated. The complete vibrational assignments were performed on the basis of TED of the vibrational modes, calculated with the help of SQM method. NBO analysis has been carried out to explore the hyperconjugative interactions and their second order stabilization energy within the molecule. The molecular orbitals (MO's) and its energy gap were studied. The first order hyperpolarizability (β0) and related properties (β, α0, Δα) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory.

Unraveling energy conversion modeling in the intrinsic persistent upconverted luminescence of solids: a study of native point defects in antiferromagnetic Er2O3.

PubMed

Huang, Bolong

2016-05-11

We investigated the mechanism of the intrinsic persistent luminescence of Er2O3 in the A-type lattice based on first-principles calculations. We found that the native point defects were engaged in mutual subtle interactions in the form of chemical reactions between different charge states. The release of energy related to lattice distortion facilitates the conversion of energy for electrons to be transported between the valence band and the trap levels or even between the deep trap levels so as to generate persistent luminescence. The defect transitions that take place along the zero-phonon line release energy to enable optical transitions, with the exact amount of negative effective correlation energy determined by the lattice distortions. Our calculations on the thermodynamic transition levels confirm that both the visible and NIR experimentally observed intrinsic persistent luminescence (phosphor or afterglow) are related to the thermodynamic transition levels of oxygen-related defects, and the thermodynamic transition levels within different charge states for these defects are independent of the chemical potentials of the given species. Lattice distortion defects such as anion Frenkel (a-Fr) pair defects play an important role in transporting O-related defects between different lattice sites. To obtain red persistent luminescence that matches the biological therapeutic window, it is suggested to increase the electron transition levels between high-coordinated O vacancies and related metastable a-Fr defects; a close-packed core-shell structure is required to quench low-coordinated O-related defects so as to reduce the green band luminescence. We further established a conversed chain reaction (CCR) model to interpret the energy conversion process of persistent luminescence in terms of the inter-reactions of native point defects between different charge states. It is advantageous to use the study of defect levels combined with formation energies to suggest limits to doping energy and explain photostimulated luminescence in terms of native point defects.

Dirac R-matrix calculations of photoionization cross sections of Ni XII and atomic structure data of Ni XIII

NASA Astrophysics Data System (ADS)

Nazir, R. T.; Bari, M. A.; Bilal, M.; Sardar, S.; Nasim, M. H.; Salahuddin, M.

2017-02-01

We performed R-matrix calculations for photoionization cross sections of the two ground state configuration 3s23p5 (^2P^o3/2,1/2) levels and 12 excited states of Ni XII using relativistic Dirac Atomic R-matrix Codes (DARC) across the photon energy range between the ionizations thresholds of the corresponding states and well above the thresholds of the last level of the Ni XIII target ion. Generally, a good agreement is obtained between our results and the earlier theoretical photoionization cross sections. Moreover, we have used two independent fully relativistic GRASP and FAC codes to calculate fine-structure energy levels, wavelengths, oscillator strengths, transitions rates among the lowest 48 levels belonging to the configuration (3s23p4, 3s3p5, 3p6, 3s23p33d) in Ni XIII. Additionally, radiative lifetimes of all the excited states of Ni XIII are presented. Our results of the atomic structure of Ni XIII show good agreement with other theoretical and experimental results available in the literature. A good agreement is found between our calculated lifetimes and the experimental ones. Our present results are useful for plasma diagnostic of fusion and astrophysical plasmas.

Energy levels and radiative rates for transitions in Co XI

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Keenan, F. P.; Msezane, A. Z.

2007-10-01

Aims: In this paper we report calculations for energy levels and radiative rates for transitions in Co xi. Methods: The General purpose Relativistic Atomic Structure Package (grasp) and the Flexible Atomic Code (fac) have been adopted for the calculations of energy levels and radiative rates. Results: Energies for the lowest 287 levels of Co xi, including those among the (1s^22s^22p^6) 3s^23p^5, 3s3p^6, 3s^23p^43d, 3s3p^53d, 3s^23p^33d^2, and 3s^23p^44s configurations, are reported. Additionally, radiative rates and oscillator strengths are reported for all electric dipole (E1) transitions with f ≥ 10-5 among these levels, and similar results for magnetic dipole (M1), electric quadrupole (E2), and magnetic quadrupole (M2) transitions are reported only for those with f≥10-8. Comparisons are made with the available results in the literature, and the accuracy of the present data is assessed. Finally, lifetimes for all excited levels are also listed, although measurements are presently available for only one of these. Tables 1 and 3-6 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/473/995

An Experimental and Quantum Chemical Study of the Electronic Spectrum of the HBCl Free Radical

NASA Astrophysics Data System (ADS)

Gharaibeh, Mohammed A.; Nagarajan, Ramya; Clouthier, Dennis J.; Tarroni, Ricardo

2012-06-01

The chloroborane (HBCl) free radical has a complex electronic spectrum in the visible that involves a transition from a bent ground state to a linear excited state, both of which are the Renner-Teller components of what would be a ^2π state at linearity. We have used the synchronous-scan LIF and single vibronic level emission techniques to untangle the many overlapping vibronic bands and assign upper state K quantum numbers for jet-cooled HBCl and DBCl. The radicals were produced in a pulsed electric discharge jet using a precursor mixture of boron trichloride (BCl_3) and hydrogen or deuterium in high-pressure argon. As an important aid to understanding the data, the ground and excited state high level ab initio potential energy surfaces (PES) have been calculated and the vibrational levels obtained variationally. The calculated ground state levels are in excellent agreement with the emission data validating the quality of the PES. Aside from an approximately 100 cm-1 shift in the upper state electronic term value, the calculated excited state vibrational energy levels and isotope shifts match the LIF data very well, allowing the observed bands to be assigned with confidence.

Cohesive Energies of Some Transition Metal Compounds Using Embedded Clusters

NASA Astrophysics Data System (ADS)

Press, Mehernosh Rustom

The molecular-clusters approach to electronic structure calculation is especially well-suited to the study of properties that depend primarily on the local environment of a system, especially those with no translational symmetry, e.g. systems with defects and structural deformations. The presence of the rest of the crystal environment can be accounted for approximately by embedding the cluster in a self-consistent crystal potential. This thesis makes a contribution in the area of investigating the capability of embedded molecular-clusters to yield reliable bulk structural properties. To this end, an algorithm for calculating the cohesive energies of clusters within the discrete-variational X(,(alpha)) LCAO-MO formulation is set up and verified on simple solids: Li, Na, Cu and LiF. We then use this formulation to study transition metal compounds, for which the interesting physics lies in local lattice defects, foreign impurities and structural deformations. In a self -consistent calculation of the lattice energies and stability of defect clusters in wustite, Fe(,1-x)O, corner-sharing aggregates of the 4:1 defect are identified as the most stable defect configurations due to efficient compensation of the cluster charge. The intercalation properties of layered-transition-metal-dichalcogenides continues to be a fertile experimental working area, backed by comparatively little theoretical study. We find that intercalation of ZrS(,2) with Na perturbs the valence energy level structure sufficiently to induce a more ionic Zr-S bond, a narrowing of the optical gap and filling of the lowest unoccupied host lattice orbitals with the electron donated by Na. Fe - intercalation in ZrS(,2) is accommodated via a strong Fe-S bond, impurity-like band levels in the optical gap of the host and hybridization-driven compression and lowering of the conduction band energy levels. The piezoelectric cuprous halides, CuCl and CuBr, exhibit a host of intriguing properties due to a filled and very active d('10) shell at the Fermi energy. A self-consistent calculation via energy minimization of the internal strain in these compounds shows both Cu-halide bonds to be very rigid with little charge delocalization under strain. Piezoelectric response is calculated in terms of effective charges and quadrupolar moments, e(,T) and (DELTA)Q.

High-spin level structure and Ground-state phase transition in the odd-mass 103-109Rh isotopes in the framework of exactly solvable sdg interacting boson-fermion model

NASA Astrophysics Data System (ADS)

Ghapanvari, M.; Ghorashi, A. H.; Ranjbar, Z.; Jafarizadeh, M. A.

2018-03-01

In this article, the negative-parity states in the odd-mass 103 - 109Rh isotopes in terms of the sd and sdg interacting-boson fermion models were studied. The transitional interacting boson-fermion model Hamiltonians in sd and sdg-IBFM versions based on affine SU (1 , 1) Lie Algebra were employed to describe the evolution from the spherical to deformed gamma unstable shapes along with the chain of Rh isotopes. In this method, sdg-IBFM Hamiltonian, which is a three level pairing Hamiltonian was determined easily via the exactly solvable method. Some observables of the shape phase transitions such as energy levels, the two neutron separation energies, signature splitting of the γ-vibrational band, the α-decay and double β--decay energies were calculated and examined for these isotopes. The present calculation correctly reproduces the spherical to gamma-soft phase transition in the Rh isotopes. Some comparisons were made with sd-IBFM.

Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory

NASA Astrophysics Data System (ADS)

Li, Jing; D'Avino, Gabriele; Duchemin, Ivan; Beljonne, David; Blase, Xavier

2018-01-01

We present a novel hybrid quantum/classical approach to the calculation of charged excitations in molecular solids based on the many-body Green's function G W formalism. Molecules described at the G W level are embedded into the crystalline environment modeled with an accurate classical polarizable scheme. This allows the calculation of electron addition and removal energies in the bulk and at crystal surfaces where charged excitations are probed in photoelectron experiments. By considering the paradigmatic case of pentacene and perfluoropentacene crystals, we discuss the different contributions from intermolecular interactions to electronic energy levels, distinguishing between polarization, which is accounted for combining quantum and classical polarizabilities, and crystal field effects, that can impact energy levels by up to ±0.6 eV. After introducing band dispersion, we achieve quantitative agreement (within 0.2 eV) on the ionization potential and electron affinity measured at pentacene and perfluoropentacene crystal surfaces characterized by standing molecules.

Measurements of continuum lowering in solid-density plasmas created from elements and compounds

DOE PAGES

Ciricosta, O.; Vinko, S. M.; Barbrel, B.; ...

2016-05-23

The effect of a dense plasma environment on the energy levels of an embedded ion is usually described in terms of the lowering of its continuum level. For strongly coupled plasmas, the phenomenon is intimately related to the equation of state; hence, an accurate treatment is crucial for most astrophysical and inertial-fusion applications, where the case of plasma mixtures is of particular interest. In this study, we present an experiment showing that the standard density-dependent analytical models are inadequate to describe solid-density plasmas at the temperatures studied, where the reduction of the binding energies for a given species is unaffectedmore » by the different plasma environment (ion density) in either the element or compounds of that species, and can be accurately estimated by calculations only involving the energy levels of an isolated neutral atom. Lastly, the results have implications for the standard approaches to the equation of state calculations.« less

Ro-vibronic transition intensities for triatomic molecules from the exact kinetic energy operator; electronic spectrum for the C̃ 1B2 ← X̃ 1A1 transition in SO2.

PubMed

Zak, Emil J; Tennyson, Jonathan

2017-09-07

A procedure for calculating ro-vibronic transition intensities for triatomic molecules within the Born-Oppenheimer approximation is reported. Ro-vibrational energy levels and wavefunctions are obtained with the DVR3D suite, which solves the nuclear motion problem with an exact kinetic energy operator. Absolute transition intensities are calculated both with the Franck-Condon approximation and with a full transition dipole moment surface. The theoretical scheme is tested on C̃  1 B 2  ← X̃  1 A 1 ro-vibronic transitions of SO 2 . Ab initio potential energy and dipole moment surfaces are generated for this purpose. The calculated ro-vibronic transition intensities and cross sections are compared with the available experimental and theoretical data.

A generalized force-modified potential energy surface (G-FMPES) for mechanochemical simulations

DOE PAGES

Subramanian, Gopinath; Mathew, Nithin; Leiding, Jeffery A.

2015-10-05

We describe the modifications that a spatially varying external load produces on a Born-Oppenheimer potential energy surface (PES) by calculating static quantities of interest. The effects of the external loads are exemplified using electronic structure calculations (at the HF/6-31G** level) of two different molecules: ethane and hexahydro-1,3,5-trinitro-s-triazine (RDX). The calculated transition states and The Hessian matrices of stationary points show that spatially varying external loads shift the stationary points and modify the curvature of the PES, thereby affecting the harmonic transition rates by altering both the energy barrier as well as the prefactor. The harmonic spectra of both molecules aremore » blue-shifted with increasing compressive “pressure.” Some stationary points on the RDX-PES disappear under application of the external load, indicating the merging of an energy minimum with a saddle point.« less

Calculating the free energy of transfer of small solutes into a model lipid membrane: Comparison between metadynamics and umbrella sampling

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

Bochicchio, Davide; Panizon, Emanuele; Ferrando, Riccardo

2015-10-14

We compare the performance of two well-established computational algorithms for the calculation of free-energy landscapes of biomolecular systems, umbrella sampling and metadynamics. We look at benchmark systems composed of polyethylene and polypropylene oligomers interacting with lipid (phosphatidylcholine) membranes, aiming at the calculation of the oligomer water-membrane free energy of transfer. We model our test systems at two different levels of description, united-atom and coarse-grained. We provide optimized parameters for the two methods at both resolutions. We devote special attention to the analysis of statistical errors in the two different methods and propose a general procedure for the error estimation inmore » metadynamics simulations. Metadynamics and umbrella sampling yield the same estimates for the water-membrane free energy profile, but metadynamics can be more efficient, providing lower statistical uncertainties within the same simulation time.« less

Similarity criteria in calculations of the energy characteristics of a cw oxygen - iodine laser

NASA Astrophysics Data System (ADS)

Mezhenin, A. V.; Azyazov, V. N.

2012-12-01

The calculated and experimental data on the energy efficiency of a cw oxygen - iodine laser (OIL) are analysed based on two similarity criteria, namely, on the ratio of the residence time of the gas mixture in the resonator to the characteristic time of extraction of the energy stored in singlet oxygen td and on the gain-to-loss ratio Π. It is shown that the simplified two-level laser model satisfactorily predicts the output characteristics of OILs with a stable resonator at τd <= 7. Efficient energy extraction from the OIL active medium is achieved in the case of τd = 5 - 7, Π = 4 - 8.

A coupled two-dimensional main chain torsional potential for protein dynamics: generation and implementation.

PubMed

Li, Yongxiu; Gao, Ya; Zhang, Xuqiang; Wang, Xingyu; Mou, Lirong; Duan, Lili; He, Xiao; Mei, Ye; Zhang, John Z H

2013-09-01

Main chain torsions of alanine dipeptide are parameterized into coupled 2-dimensional Fourier expansions based on quantum mechanical (QM) calculations at M06 2X/aug-cc-pvtz//HF/6-31G** level. Solvation effect is considered by employing polarizable continuum model. Utilization of the M06 2X functional leads to precise potential energy surface that is comparable to or even better than MP2 level, but with much less computational demand. Parameterization of the 2D expansions is against the full main chain torsion space instead of just a few low energy conformations. This procedure is similar to that for the development of AMBER03 force field, except unique weighting factor was assigned to all the grid points. To avoid inconsistency between quantum mechanical calculations and molecular modeling, the model peptide is further optimized at molecular mechanics level with main chain dihedral angles fixed before the calculation of the conformational energy on molecular mechanical level at each grid point, during which generalized Born model is employed. Difference in solvation models at quantum mechanics and molecular mechanics levels makes this parameterization procedure less straightforward. All force field parameters other than main chain torsions are taken from existing AMBER force field. With this new main chain torsion terms, we have studied the main chain dihedral distributions of ALA dipeptide and pentapeptide in aqueous solution. The results demonstrate that 2D main chain torsion is effective in delineating the energy variation associated with rotations along main chain dihedrals. This work is an implication for the necessity of more accurate description of main chain torsions in the future development of ab initio force field and it also raises a challenge to the development of quantum mechanical methods, especially the quantum mechanical solvation models.

Semiclassical approach to atomic decoherence by gravitational waves

NASA Astrophysics Data System (ADS)

Quiñones, D. A.; Varcoe, B. T. H.

2018-01-01

A new heuristic model of interaction of an atomic system with a gravitational wave (GW) is proposed. In it, the GW alters the local electromagnetic field of the atomic nucleus, as perceived by the electron, changing the state of the system. The spectral decomposition of the wave function is calculated, from which the energy is obtained. The results suggest a shift in the difference of the atomic energy levels, which will induce a small detuning to a resonant transition. The detuning increases with the quantum numbers of the levels, making the effect more prominent for Rydberg states. We performed calculations on the Rabi oscillations of atomic transitions, estimating how they would vary as a result of the proposed effect.

All the nonadiabatic (J=0) bound states of NO{sub 2}

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

Salzgeber, R.F.; Mandelshtam, V.A.; Schlier, C.

1999-02-01

We calculated all 3170 A{sub 1} and B{sub 2} (J=0) vibronic bound states of the coupled electronic ground ({tilde X}&hthinsp;{sup 2}A{sub 1}) and the first excited ({tilde A}&hthinsp;{sup 2}B{sub 2}) surfaces of NO{sub 2}, using a modification of the {ital ab initio} potentials of Leonardi {ital et al.} [J. Chem. Phys. {bold 105}, 9051 (1996)]. The calculation was performed by harmonic inversion of the Chebyshev correlation function generated from a DVR Hamiltonian in Radau coordinates. The rms error of the eigenenergies is about 2.5 cm{sup {minus}1}, corresponding to a relative error of 10{sup {minus}4} near the dissociation energy. The resultsmore » are compared with the adiabatic and diabatic levels calculated from the same surfaces, with experimental data, and with some approximations for the number of states function N(E). The experimental levels are reproduced fairly well up to an energy of 12&hthinsp;000 cm{sup {minus}1} above the potential minimum while the total number of bound levels agrees to within 2{percent} with that calculated from the phase space volume. {copyright} {ital 1999 American Institute of Physics.}« less

First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions.

PubMed

Valiev, R R; Cherepanov, V N; Baryshnikov, G V; Sundholm, D

2018-02-28

A method for calculating the rate constants for internal-conversion (k IC ) and intersystem-crossing (k ISC ) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of k IC and k ISC for a set of organic and organometallic compounds with experimentally known spectroscopic properties. The studied molecules were pyrromethene-567 dye, psoralene, hetero[8]circulenes, free-base porphyrin, naphthalene, and larger polyacenes. We also studied fac-Alq 3 and fac-Ir(ppy) 3 , which are important molecules in organic light emitting diodes (OLEDs). The excitation energies were calculated at the multi-configuration quasi-degenerate second-order perturbation theory (XMC-QDPT2) level, which is found to yield excitation energies in good agreement with experimental data. Spin-orbit coupling matrix elements, non-adiabatic coupling matrix elements, Huang-Rhys factors, and vibrational energies were calculated at the time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) levels. The computed fluorescence quantum yields for the pyrromethene-567 dye, psoralene, hetero[8]circulenes, fac-Alq 3 and fac-Ir(ppy) 3 agree well with experimental data, whereas for the free-base porphyrin, naphthalene, and the polyacenes, the obtained quantum yields significantly differ from the experimental values, because the FC and adiabatic approximations are not accurate for these molecules.

Collisional excitation of NH(X{sup 3}Σ{sup −}) by Ne: Potential energy surface, scattering calculations, and comparison with experiments

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

Bouhafs, Nezha; Lique, François, E-mail: francois.lique@univ-lehavre.fr

2015-11-14

We present a new three-dimensional potential energy surface (PES) for the NH(X{sup 3}Σ{sup −})–Ne van der Waals system, which explicitly takes into account the NH vibrational motion. Ab initio calculations of the NH–Ne PES were carried out using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations [RCCSD(T)]. The augmented correlation-consistent quadruple zeta (aug-cc-pVQZ) basis set was employed. Mid-bond functions were also included in order to improve the accuracy in the van der Waals well. Using this new PES, we have studied the collisional excitation of NH(X{sup 3}Σ{sup −}) by Ne. Close-coupling calculations ofmore » the collisional excitation cross sections of the fine-structure levels of NH by Ne are performed for energies up to 3000 cm{sup −1}, which yield, after thermal average, rate coefficients up to 350 K. The propensity rules between fine-structure levels are reported, and it is found that F-conserving cross sections are larger than F-changing cross sections even if the propensity rules are not as strong as for the NH–He system. The calculated rate coefficients are compared with available experimental measurements at room temperature and a fairly good agreement is found between experimental and theoretical data, confirming the good quality of the scattering calculations and also the accuracy of the potential energy surface used in this work.« less

Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation.

PubMed

Moix, Jeremy M; Ma, Jian; Cao, Jianshu

2015-03-07

A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters.

Energy compensation after sprint- and high-intensity interval training.

PubMed

Schubert, Matthew M; Palumbo, Elyse; Seay, Rebekah F; Spain, Katie K; Clarke, Holly E

2017-01-01

Many individuals lose less weight than expected in response to exercise interventions when considering the increased energy expenditure of exercise (ExEE). This is due to energy compensation in response to ExEE, which may include increases in energy intake (EI) and decreases in non-exercise physical activity (NEPA). We examined the degree of energy compensation in healthy young men and women in response to interval training. Data were examined from a prior study in which 24 participants (mean age, BMI, & VO2max = 28 yrs, 27.7 kg•m-2, and 32 mL∙kg-1∙min-1) completed either 4 weeks of sprint-interval training or high-intensity interval training. Energy compensation was calculated from changes in body composition (air displacement plethysmography) and exercise energy expenditure was calculated from mean heart rate based on the heart rate-VO2 relationship. Differences between high (≥ 100%) and low (< 100%) levels of energy compensation were assessed. Linear regressions were utilized to determine associations between energy compensation and ΔVO2max, ΔEI, ΔNEPA, and Δresting metabolic rate. Very large individual differences in energy compensation were noted. In comparison to individuals with low levels of compensation, individuals with high levels of energy compensation gained fat mass, lost fat-free mass, and had lower change scores for VO2max and NEPA. Linear regression results indicated that lower levels of energy compensation were associated with increases in ΔVO2max (p < 0.001) and ΔNEPA (p < 0.001). Considerable variation exists in response to short-term, low dose interval training. In agreement with prior work, increases in ΔVO2max and ΔNEPA were associated with lower energy compensation. Future studies should focus on identifying if a dose-response relationship for energy compensation exists in response to interval training, and what underlying mechanisms and participant traits contribute to the large variation between individuals.

Cyclotron resonance and interband optical transitions in HgTe/CdTe(0 1 3) quantum well heterostructures

NASA Astrophysics Data System (ADS)

Ikonnikov, A. V.; Zholudev, M. S.; Spirin, K. E.; Lastovkin, A. A.; Maremyanin, K. V.; Aleshkin, V. Ya; Gavrilenko, V. I.; Drachenko, O.; Helm, M.; Wosnitza, J.; Goiran, M.; Mikhailov, N. N.; Dvoretskii, S. A.; Teppe, F.; Diakonova, N.; Consejo, C.; Chenaud, B.; Knap, W.

2011-12-01

Cyclotron resonance spectra of 2D electrons in HgTe/CdxHg1-xTe (0 1 3) quantum well (QW) heterostructures with inverted band structure have been thoroughly studied in quasiclassical magnetic fields versus the electron concentration varied using the persistent photoconductivity effect. The cyclotron mass is shown to increase with QW width in contrast to QWs with normal band structure. The measured values of cyclotron mass are shown to be systematically less than those calculated using the 8 × 8 Kane model with conventional set of HgTe and CdTe material parameters. In quantizing pulsed magnetic fields (Landau level filling factor less than unity) up to 45 T, both intraband (CR) and interband magnetoabsorption have been studied at radiation wavelengths 14.8 and 11.4 µm for the first time. The results obtained are compared with the allowed transition energies between Landau levels in the valence and conduction bands calculated within the same model, the calculated energies being again systematically less (by 3-14%) than the observed optical transition energies.

Scattering resonances in bimolecular collisions between NO radicals and H2 challenge the theoretical gold standard

NASA Astrophysics Data System (ADS)

Vogels, Sjoerd N.; Karman, Tijs; Kłos, Jacek; Besemer, Matthieu; Onvlee, Jolijn; van der Avoird, Ad; Groenenboom, Gerrit C.; van de Meerakker, Sebastiaan Y. T.

2018-02-01

Over the last 25 years, the formalism known as coupled-cluster (CC) theory has emerged as the method of choice for the ab initio calculation of intermolecular interaction potentials. The implementation known as CCSD(T) is often referred to as the gold standard in quantum chemistry. It gives excellent agreement with experimental observations for a variety of energy-transfer processes in molecular collisions, and it is used to calibrate density functional theory. Here, we present measurements of low-energy collisions between NO radicals and H2 molecules with a resolution that challenges the most sophisticated quantum chemistry calculations at the CCSD(T) level. Using hitherto-unexplored anti-seeding techniques to reduce the collision energy in a crossed-beam inelastic-scattering experiment, a resonance structure near 14 cm-1 is clearly resolved in the state-to-state integral cross-section, and a unique resonance fingerprint is observed in the corresponding differential cross-section. This resonance structure discriminates between two NO-H2 potentials calculated at the CCSD(T) level and pushes the required accuracy beyond the gold standard.

Discriminating a deep gallium antisite defect from shallow acceptors in GaAs using supercell calculations

DOE PAGES

Schultz, Peter A.

2016-03-01

For the purposes of making reliable first-principles predictions of defect energies in semiconductors, it is crucial to distinguish between effective-mass-like defects, which cannot be treated accurately with existing supercell methods, and deep defects, for which density functional theory calculations can yield reliable predictions of defect energy levels. The gallium antisite defect GaAs is often associated with the 78/203 meV shallow double acceptor in Ga-rich gallium arsenide. Within a conceptual framework of level patterns, analyses of structure and spin stabilization can be used within a supercell approach to distinguish localized deep defect states from shallow acceptors such as B As. Thismore » systematic approach determines that the gallium antisite supercell results has signatures inconsistent with an effective mass state and cannot be the 78/203 shallow double acceptor. Lastly, the properties of the Ga antisite in GaAs are described, total energy calculations that explicitly map onto asymptotic discrete localized bulk states predict that the Ga antisite is a deep double acceptor and has at least one deep donor state.« less

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3

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

Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

Here, we report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C 2H 3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C 2H 3. All well converged 158 vibrational bands up to 3200 cm -1 are determined, together with a comparison to previous calculations and experimental results. Our results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from thatmore » of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C 2H 3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. Additionally, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C 2H 3 without the requirement of explicit wavefunctions.« less

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C2H3.

PubMed

Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

2017-06-14

We report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C 2 H 3 . The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C 2 H 3 . All well converged 158 vibrational bands up to 3200 cm -1 are determined, together with a comparison to previous calculations and experimental results. Results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from that of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C 2 H 3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. In addition, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C 2 H 3 without the requirement of explicit wavefunctions.

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3

DOE PAGES

Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

2017-06-12

Here, we report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C 2H 3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C 2H 3. All well converged 158 vibrational bands up to 3200 cm -1 are determined, together with a comparison to previous calculations and experimental results. Our results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from thatmore » of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C 2H 3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. Additionally, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C 2H 3 without the requirement of explicit wavefunctions.« less

DX-center transformation of Te donors in GaSb under hydrostatic pressure

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

Navarro-Contreras, H.; de Anda-Salazar, F.; Hsu, L.

1998-05-01

We have observed the transformation of Te shallow donors in GaSb into DX centers at hydrostatic pressures of 27.8{plus_minus}2.6kbar. The position of the Te DX energy level at zero pressure is calculated to lie 300{plus_minus}70meV above the conduction band at atmospheric pressure, consistent with the theory that in the III-V compounds the DX centers line up in energy with respect to the vacuum level within experimental error. This binding energy at zero pressure of the Te DX compares well with the value of 210 meV calculated from the cation-cation bonded DX-center model recently proposed by Park and Chadi. At pressuresmore » where the Te shallow donor into DX-center transformation has taken place we observe evidence of the existence of a bound phonon associated with the Te DX center. From its observed pressure dependence the LO optical phonon Gr{umlt u}neisen parameter is calculated to be {gamma}{sub LO}=0.93{plus_minus}0.09. {copyright} {ital 1998} {ital The American Physical Society}« less

Dual-level direct dynamics studies for the hydrogen abstraction reaction of 1,1-difluoroethane with O( 3P)

NASA Astrophysics Data System (ADS)

Liu, Jing-yao; Li, Ze-sheng; Dai, Zhen-wen; Zhang, Gang; Sun, Chia-chung

2004-01-01

We present dual-level direct dynamics calculations for the CH 3CHF 2 + O( 3P) hydrogen abstraction reaction in a wide temperature range, based on canonical variational transition-state theory including small curvature tunneling corrections. For this reaction, three distinct transition states, one for α-abstraction and two for β-abstraction, have been located. The potential energy surface information is obtained at the MP2(full)/6-311G(d,p) level of theory, and higher-level single-point calculations for the stationary points are preformed at several levels, namely QCISD(T)/6-311+G(3df,3pd), G2, and G3 using the MP2 geometries, as well as at the G3//MP4SDQ/6-311G(d,p) level. The energy profiles are further refined with the interpolated single-point energies method at the G3//MP2(full)/6-311G(d,p) level. The total rate constants match the experimental data reasonable well in the measured temperature range 1110-1340 K. It is shown that at low temperature α-abstraction may be the major reaction channel, while β-abstraction will have more contribution to the whole reaction rate as the temperature increases.

Impact of Complex-Valued Energy Function Singularities on the Behaviour of RAYLEIGH-SCHRöDINGER Perturbation Series. H_2CO Molecule Vibrational Energy Spectrum.

NASA Astrophysics Data System (ADS)

Duchko, Andrey; Bykov, Alexandr

2015-06-01

Nowadays the task of spectra processing is as relevant as ever in molecular spectroscopy. Nevertheless, existing techniques of vibrational energy levels and wave functions computation often come to a dead-lock. Application of standard quantum-mechanical approaches often faces inextricable difficulties. Variational method requires unimaginable computational performance. On the other hand perturbational approaches beat against divergent series. That's why this problem faces an urgent need in application of specific resummation techniques. In this research Rayleigh-Schrödinger perturbation theory is applied to vibrational energy levels calculation of excited vibrational states of H_2CO. It is known that perturbation series diverge in the case of anharmonic resonance coupling between vibrational states [1]. Nevertheless, application of advanced divergent series summation techniques makes it possible to calculate the value of energy with high precision (more than 10 true digits) even for highly excited states of the molecule [2]. For this purposes we have applied several summation techniques based on high-order Pade-Hermite approximations. Our research shows that series behaviour completely depends on the singularities of complex energy function inside unit circle. That's why choosing an approximation function modelling this singularities allows to calculate the sum of divergent series. Our calculations for formaldehyde molecule show that the efficiency of each summation technique depends on the resonant type. REFERENCES 1. J. Cizek, V. Spirko, and O. Bludsky, ON THE USE OF DIVERGENT SERIES IN VIBRATIONAL SPECTROSCOPY. TWO- AND THREE-DIMENSIONAL OSCILLATORS, J. Chem. Phys. 99, 7331 (1993). 2. A. V. Sergeev and D. Z. Goodson, SINGULARITY ANALYSIS OF FOURTH-ORDER MöLLER-PLESSET PERTURBATION THEORY, J. Chem. Phys. 124, 4111 (2006).

Adiabatic perturbation theory for atoms and molecules in the low-frequency regime

NASA Astrophysics Data System (ADS)

Martiskainen, Hanna; Moiseyev, Nimrod

2017-12-01

There is an increasing interest in the photoinduced dynamics in the low frequency, ω, regime. The multiphoton absorptions by molecules in strong laser fields depend on the polarization of the laser and on the molecular structure. The unique properties of the interaction of atoms and molecules with lasers in the low-frequency regime imply new concepts and directions in strong-field light-matter interactions. Here we represent a perturbational approach for the calculations of the quasi-energy spectrum in the low-frequency regime, which avoids the construction of the Floquet operator with extremely large number of Floquet channels. The zero-order Hamiltonian in our perturbational approach is the adiabatic Hamiltonian where the atoms/molecules are exposed to a dc electric field rather than to ac-field. This is in the spirit of the first step in the Corkum three-step model. The second-order perturbation correction terms are obtained when i ℏ ω ∂/∂ τ serves as a perturbation and τ is a dimensionless variable. The second-order adiabatic perturbation scheme is found to be an excellent approach for calculating the ac-field Floquet solutions in our test case studies of a simple one-dimensional time-periodic model Hamiltonian. It is straightforward to implement the perturbation approach presented here for calculating atomic and molecular energy shifts (positions) due to the interaction with low-frequency ac-fields using high-level electronic structure methods. This is enabled since standard quantum chemistry packages allow the calculations of atomic and molecular energy shifts due to the interaction with dc-fields. In addition to the shift of the energy positions, the energy widths (inverse lifetimes) can be obtained at the same level of theory. These energy shifts are functions of the laser parameters (low frequency, intensity, and polarization).

Kinetic study on the H + SiH4 abstraction reaction using an ab initio potential energy surface.

PubMed

Cao, Jianwei; Zhang, Zhijun; Zhang, Chunfang; Bian, Wensheng; Guo, Yin

2011-01-14

Variational transition state theory calculations with the correction of multidimensional tunneling are performed on a 12-dimensional ab initio potential energy surface for the H + SiH(4) abstraction reaction. The surface is constructed using a dual-level strategy. For the temperature range 200-1600 K, thermal rate constants are calculated and kinetic isotope effects for various isotopic species of the title reaction are investigated. The results are in very good agreement with available experimental data.

Developing Community-Focused Solutions using a Food-Energy-Water Calculator, with Initial Application to Western Kansas

NASA Astrophysics Data System (ADS)

Hill, M. C.; Pahwa, A.; Rogers, D.; Roundy, J. K.; Barron, R. W.

2017-12-01

Many agricultural areas are facing difficult circumstances. Kansas is one example, with problems that are typical. Past agricultural and hydrologic data document how irrigation in western Kansas has produced a multi-billion-dollar agricultural economy that is now threatened by pumping-induced declines in groundwater levels. Although reduced pumping could mitigate much of the threat and preserve much of Kansas' agricultural economy (albeit at a reduced level) in the long term, a primary disincentive for reducing pumping is the immediate economic impact of diminished irrigation. One alternative to continued unsustainable groundwater use is a water-energy tradeoff program that seeks to reduce pumping from the Ogallala aquifer to sustainable rates while maintaining local income levels. This program would allow development of the region's rich wind and solar energy resources in a way that focuses on local economic benefits, in exchange for water rights concessions from affected stakeholders. In considering this alternative, most citizens are currently unable to address a key question, "What could this mean for me?" Answering this question requires knowledge of agriculture, energy, water, economics, and drought probabilities, knowledge that is available at Kansas universities. This talk presents a joint University of Kansas - Kansas State University effort to address this need through development of the Food-Energy-Water Calculator. This talk will present the idea and discuss how the calculator would work. It is suggested that the framework created provides a powerful way to organize data and analysis results, and thus to seek solutions to difficult problems in many regions of the US and the world.

Quantum chemical determination of Young's modulus of lignin. Calculations on a beta-O-4' model compound.

PubMed

Elder, Thomas

2007-11-01

The calculation of Young's modulus of lignin has been examined by subjecting a dimeric model compound to strain, coupled with the determination of energy and stress. The computational results, derived from quantum chemical calculations, are in agreement with available experimental results. Changes in geometry indicate that modifications in dihedral angles occur in response to linear strain. At larger levels of strain, bond rupture is evidenced by abrupt changes in energy, structure, and charge. Based on the current calculations, the bond scission may be occurring through a homolytic reaction between aliphatic carbon atoms. These results may have implications in the reactivity of lignin especially when subjected to processing methods that place large mechanical forces on the structure.

In Pursuit of the Far-Infrared Spectrum of Cyanogen Iso-Thiocyanate Ncncs, Under the Influence of the Energy Level Dislocation due to Quantum Monodromy

NASA Astrophysics Data System (ADS)

Winnewisser, Manfred; Winnewisser, Brenda P.; Medvedev, Ivan R.; De Lucia, Frank, C.; Ross, Stephen C.; Koput, Jacek

2010-06-01

Quantum Monodromy has a strong impact on the ro-vibrational energy levels of chain molecules whose bending potential energy function has the form of the bottom of a champagne bottle (i.e. with a hump or punt) around the linear configuration. NCNCS is a particularly good example of such a molecule and clearly exhibits a distinctive monodromy-induced dislocation of the energy level pattern at the top of the potential energy hump. The generalized semi-rigid bender (GSRB) wave functions are used to show that the expectation values of any physical quantity which varies with the large amplitude bending coordinate will also have monodromy-induced dislocations. This includes the electric dipole moment components. High level ab initio calculations not only provided the molecular equilibrium structure of NCNCS, but also the electric dipole moment components μa and μb as functions of the large-amplitude bending coordinate. The calculated expectation values of these quantities indicate large ro-vibrational transition moments that will be discussed in pursuit of possible far-infrared bands. To our knowledge there is no NCNCS infrared spectrum reported in the literature. B. P. Winnewisser, M. Winnewisser, I. R. Medvedev, F. C. De Lucia, S. C. Ross and J. Koput, Phys. Chem. Chem. Phys., 2010, DOI:10.1039/B922023B.

Energy metabolism and nutritional status in hospitalized patients with lung cancer.

PubMed

Takemura, Yumi; Sasaki, Masaya; Goto, Kenichi; Takaoka, Azusa; Ohi, Akiko; Kurihara, Mika; Nakanishi, Naoko; Nakano, Yasutaka; Hanaoka, Jun

2016-09-01

This study aimed to investigate the energy metabolism of patients with lung cancer and the relationship between energy metabolism and proinflammatory cytokines. Twenty-eight patients with lung cancer and 18 healthy controls were enrolled in this study. The nutritional status upon admission was analyzed using nutritional screening tools and laboratory tests. The resting energy expenditure and respiratory quotient were measured using indirect calorimetry, and the predicted resting energy expenditure was calculated using the Harris-Benedict equation. Energy expenditure was increased in patients with advanced stage disease, and there were positive correlations between measured resting energy expenditure/body weight and interleukin-6 levels and between measured resting energy expenditure/predicted resting energy expenditure and interleukin-6 levels. There were significant relationships between body mass index and plasma leptin or acylated ghrelin levels. However, the level of appetite controlling hormones did not affect dietary intake. There was a negative correlation between plasma interleukin-6 levels and dietary intake, suggesting that interleukin-6 plays a role in reducing dietary intake. These results indicate that energy expenditure changes significantly with lung cancer stage and that plasma interleukin-6 levels affect energy metabolism and dietary intake. Thus, nutritional management that considers the changes in energy metabolism is important in patients with lung cancer.

Solar Energetic Proton Nowcast for Low Earth Orbits

NASA Astrophysics Data System (ADS)

Winter, L. M.; Quinn, R. A.

2013-12-01

Solar energetic proton flux levels above > 10 pfu can damage spacecraft and pose a hazard to astronauts as well as passengers and crew on polar commercial flights. While the GOES satellites provide real-time data of SEP levels in geosynchronous orbit, it is also important to determine the risk to objects in lower altitude orbits. To assess this risk in real-time, we created a web-based nowcast of SEP flux. The tool determines the current solar energetic proton flux level given input position (latitude, longitude, and altitude) and energy of the protons (e.g., > 10 MeV). The effective cutoff energy is calculated for the location and current geomagnetic storm level (i.e., the Kp value from SWPC) using the Shea & Smart (e.g., Smart et al. 1999abc, 2000) geomagnetic cutoff model, which uses a trajectory tracing technique through the Tsyganenko magnetospheric model for the geomagnetic field. With the cutoff energy and GOES proton flux measurements, a map of the current predicted proton flux level at the input energy is displayed along with the calculated integral spectrum for the input position. This operational tool is a powerful new diagnostic for assessing the risk to spacecraft from current solar proton levels, with easy to read color-coded maps generated for all GOES integral proton flux energies and a range of altitudes (1000 - 35000 km). The figures show example maps over a ';'quiet'' (03-26-13) and active (10-30-03) time, with high proton levels easily distinguishable at or above the NOAA warning level (yellow-orange-red). The tool also displays the current GOES integral spectrum and fit, and the estimated spectrum at a user-defined location and altitude.

Progress in calculating the potential energy surface of H3+.

PubMed

Adamowicz, Ludwik; Pavanello, Michele

2012-11-13

The most accurate electronic structure calculations are performed using wave function expansions in terms of basis functions explicitly dependent on the inter-electron distances. In our recent work, we use such basis functions to calculate a highly accurate potential energy surface (PES) for the H(3)(+) ion. The functions are explicitly correlated Gaussians, which include inter-electron distances in the exponent. Key to obtaining the high accuracy in the calculations has been the use of the analytical energy gradient determined with respect to the Gaussian exponential parameters in the minimization of the Rayleigh-Ritz variational energy functional. The effective elimination of linear dependences between the basis functions and the automatic adjustment of the positions of the Gaussian centres to the changing molecular geometry of the system are the keys to the success of the computational procedure. After adiabatic and relativistic corrections are added to the PES and with an effective accounting of the non-adiabatic effects in the calculation of the rotational/vibrational states, the experimental H(3)(+) rovibrational spectrum is reproduced at the 0.1 cm(-1) accuracy level up to 16,600 cm(-1) above the ground state.

The OH + D2 --> HOD + D angle-velocity distribution: quasi-classical trajectory calculations on the YZCL2 and WSLFH potential energy surfaces and comparison with experiments at ET = 0.28 eV.

PubMed

Sierra, José Daniel; Martínez, Rodrigo; Hernando, Jordi; González, Miguel

2009-12-28

The angle-velocity distribution (HOD) of the OH + D(2) reaction at a relative translational energy of 0.28 eV has been calculated using the quasi-classical trajectory (QCT) method on the two most recent potential energy surfaces available (YZCL2 and WSLFH PESs), widely extending a previous investigation of our group. Comparison with the high resolution experiments of Davis and co-workers (Science, 2000, 290, 958) shows that the structures (peaks) found in the relative translational energy distributions of products could not be satisfactorily reproduced in the calculations, probably due to the classical nature of the QCT method and the importance of quantum effects. The calculations, however, worked quite well for other properties. Overall, both surfaces led to similar results, although the YZCL2 surface is more accurate to describe the H(3)O PES, as derived from comparison with high level ab initio results. The differences observed in the QCT calculations were interpreted considering the somewhat larger anisotropy of the YZCL2 PES when compared with the WSLFH PES.

Nature and potency interactions of the hydrogen bond through the NBO analysis for charge transfer complex between 2-amino-4-hydroxy-6-methylpyrimidine and 2,3-pyrazinedicarboxylic acid

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Afroz, Ziya; Alam, Mohammad Jane; Bhat, Sheeraz Ahmad; Ahmad, Shabbir; Ahmad, Afaq

2018-05-01

The intermolecular interactions in complex formation between 2-amino-4-hydroxy-6-methylpyrimidine (AHMP) and 2,3-pyrazinedicarboxylicacid (PDCA) have been explored using density functional theory calculations. The isolated 1:1 molecular geometry of proton transfer (PT) complex between AHMP and PDCA has been optimized on a counterpoise corrected potential energy surface (PES) at DFT-B3LYP/6-31G(d,p) level of theory in the gaseous phase. Further, the formation of hydrogen bonded charge transfer (HBCT) complex between PDCA and AHMP has been also discussed. PT energy barrier between two extremes is calculated using potential energy surface (PES) scan by varying bond length. The intermolecular interactions have been analyzed from theoretical perspective of natural bond orbital (NBO) analysis. In addition, the interaction energy between molecular fragments involved in the complex formation has been also computed by counterpoise procedure at same level of theory.

Theoretical calculations of rotationally inelastic collisions of He with NaK(A (1)Σ(+)): Transfer of population, orientation, and alignment.

PubMed

Malenda, R F; Price, T J; Stevens, J; Uppalapati, S L; Fragale, A; Weiser, P M; Kuczala, A; Talbi, D; Hickman, A P

2015-06-14

We have performed extensive calculations to investigate thermal energy, rotationally inelastic collisions of NaK (A(1)Σ(+)) with He. We determined a potential energy surface using a multi-reference configuration interaction wave function as implemented by the GAMESS electronic structure code, and we have performed coupled channel scattering calculations using the Arthurs and Dalgarno formalism. We also calculate the Grawert coefficients B(λ)(j, j') for each j → j' transition. These coefficients are used to determine the probability that orientation and alignment are preserved in collisions taking place in a cell environment. The calculations include all rotational levels with j or j' between 0 and 50, and total (translational and rotational) energies in the range 0.0002-0.0025 a.u. (∼44-550 cm(-1)). The calculated cross sections for transitions with even values of Δj tend to be larger than those for transitions with odd Δj, in agreement with the recent experiments of Wolfe et al. (J. Chem. Phys. 134, 174301 (2011)). The calculations of the energy dependence of the cross sections and the calculations of the fraction of orientation and alignment preserved in collisions also exhibit distinctly different behaviors for odd and even values of Δj. The calculations also indicate that the average fraction of orientation or alignment preserved in a transition becomes larger as j increases. We interpret this behavior using the semiclassical model of Derouard, which also leads to a simple way of visualizing the distribution of the angles between the initial and final angular momentum vectors j and j'. Finally, we compare the exact quantum results for j → j' transitions with results based on the simpler, energy sudden approximation. That approximation is shown to be quite accurate.

OH{sup +} in astrophysical media: state-to-state formation rates, Einstein coefficients and inelastic collision rates with He

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

Gómez-Carrasco, Susana; Godard, Benjamin; Lique, François

The rate constants required to model the OH{sup +} observations in different regions of the interstellar medium have been determined using state of the art quantum methods. First, state-to-state rate constants for the H{sub 2}(v = 0, J = 0, 1) + O{sup +}({sup 4} S) → H + OH{sup +}(X {sup 3}Σ{sup –}, v', N) reaction have been obtained using a quantum wave packet method. The calculations have been compared with time-independent results to assess the accuracy of reaction probabilities at collision energies of about 1 meV. The good agreement between the simulations and the existing experimental cross sectionsmore » in the 0.01-1 eV energy range shows the quality of the results. The calculated state-to-state rate constants have been fitted to an analytical form. Second, the Einstein coefficients of OH{sup +} have been obtained for all astronomically significant rovibrational bands involving the X {sup 3}Σ{sup –} and/or A {sup 3}Π electronic states. For this purpose, the potential energy curves and electric dipole transition moments for seven electronic states of OH{sup +} are calculated with ab initio methods at the highest level, including spin-orbit terms, and the rovibrational levels have been calculated including the empirical spin-rotation and spin-spin terms. Third, the state-to-state rate constants for inelastic collisions between He and OH{sup +}(X {sup 3}Σ{sup –}) have been calculated using a time-independent close coupling method on a new potential energy surface. All these rates have been implemented in detailed chemical and radiative transfer models. Applications of these models to various astronomical sources show that inelastic collisions dominate the excitation of the rotational levels of OH{sup +}. In the models considered, the excitation resulting from the chemical formation of OH{sup +} increases the line fluxes by about 10% or less depending on the density of the gas.« less

Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

PubMed

Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

2017-08-10

Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

Resummation of divergent perturbation series: Application to the vibrational states of H2CO molecule

NASA Astrophysics Data System (ADS)

Duchko, A. N.; Bykov, A. D.

2015-10-01

Large-order Rayleigh-Schrödinger perturbation theory (RSPT) is applied to the calculation of anharmonic vibrational energy levels of H2CO molecule. We use the model of harmonic oscillators perturbed by anharmonic terms of potential energy. Since the perturbation series typically diverge due to strong couplings, we apply the algebraic approximation technique because of its effectiveness shown earlier by Goodson and Sergeev [J. Chem. Phys. 110, 8205 (1999); ibid. 124, 094111 (2006)] and in our previous articles [A. D. Bykov et al. Opt. Spectrosc. 114, 396 (2013); ibid. 116, 598 (2014)]. To facilitate the resummation of terms contributing to perturbed states, when resonance mixing between states is especially strong and perturbation series diverge very quick, we used repartition of the Hamiltonian by shifting the normal mode frequencies. Energy levels obtained by algebraic approximants were compared with the results of variational calculation. It was found that for low energy states (up to ˜5000 cm-1), algebraic approximants gave accurate values of energy levels, which were in excellent agreement with the variational method. For highly excited states, strong and multiple resonances complicate series resummation, but a suitable change of normal mode frequencies allows one to reduce the resonance mixing and to get accurate energy levels. The theoretical background of the problem of RSPT series divergence is discussed along with its numerical analysis. For these purposes, the vibrational energy is considered as a function of a complex perturbation parameter. Layout and classification of its singularities allow us to model the asymptotic behavior of the perturbation series and prove the robustness of the algorithm.

Resummation of divergent perturbation series: Application to the vibrational states of H2CO molecule.

PubMed

Duchko, A N; Bykov, A D

2015-10-21

Large-order Rayleigh-Schrödinger perturbation theory (RSPT) is applied to the calculation of anharmonic vibrational energy levels of H2CO molecule. We use the model of harmonic oscillators perturbed by anharmonic terms of potential energy. Since the perturbation series typically diverge due to strong couplings, we apply the algebraic approximation technique because of its effectiveness shown earlier by Goodson and Sergeev [J. Chem. Phys. 110, 8205 (1999); ibid. 124, 094111 (2006)] and in our previous articles [A. D. Bykov et al. Opt. Spectrosc. 114, 396 (2013); ibid. 116, 598 (2014)]. To facilitate the resummation of terms contributing to perturbed states, when resonance mixing between states is especially strong and perturbation series diverge very quick, we used repartition of the Hamiltonian by shifting the normal mode frequencies. Energy levels obtained by algebraic approximants were compared with the results of variational calculation. It was found that for low energy states (up to ∼5000 cm(-1)), algebraic approximants gave accurate values of energy levels, which were in excellent agreement with the variational method. For highly excited states, strong and multiple resonances complicate series resummation, but a suitable change of normal mode frequencies allows one to reduce the resonance mixing and to get accurate energy levels. The theoretical background of the problem of RSPT series divergence is discussed along with its numerical analysis. For these purposes, the vibrational energy is considered as a function of a complex perturbation parameter. Layout and classification of its singularities allow us to model the asymptotic behavior of the perturbation series and prove the robustness of the algorithm.

Observation of double-well potential of NaH C 1Σ+ state: Deriving the dissociation energy of its ground state

NASA Astrophysics Data System (ADS)

Chu, Chia-Ching; Huang, Hsien-Yu; Whang, Thou-Jen; Tsai, Chin-Chun

2018-03-01

Vibrational levels (v = 6-42) of the NaH C 1Σ+ state including the inner and outer wells and the near-dissociation region were observed by pulsed optical-optical double resonance fluorescence depletion spectroscopy. The absolute vibrational quantum number is identified by comparing the vibrational energy difference of this experiment with the ab initio calculations. The outer well with v up to 34 is analyzed using the Dunham expansion and a Rydberg-Klein-Rees (RKR) potential energy curve is constructed. A hybrid double-well potential combined with the RKR potential, the ab initio calculation, and a long-range potential is able to describe the whole NaH C 1Σ+ state including the higher vibrational levels (v = 35-42). The dissociation energy of the NaH C 1Σ+ state is determined to be De(C) = 6595.10 ± 5 cm-1 and then the dissociation energy of the NaH ground state De(X) = 15 807.87 ± 5 cm-1 can be derived.

A multivariate relationship for the impact sensitivities of energetic N-nitrocompounds based on bond dissociation energy.

PubMed

Li, Jinshan

2010-02-15

The ZPE-corrected N-NO(2) bond dissociation energies (BDEs(ZPE)) of a series of model N-nitrocompounds and typical energetic N-nitrocompounds have been calculated using density functional theory methods. Computed results show that using the 6-31G** basis set the UB3LYP calculated BDE(ZPE) is similar to the B3PW91 but is less than the UB3P86 and that for both UB3P86 and UB3PW91 methods the 6-31G(**) calculated BDE(ZPE) is close to the 6-31++G(**). For the series of model N-nitrocompounds it is drawn from the NBO analysis that at the UB3LYP/6-31G(**) level the order of BDE(ZPE) is not only in line with that of bond order but also with that of the energy gap between N-NO(2) bond and antibond orbitals. For the typical energetic N-nitrocompounds the impact sensitivity is strongly related to the BDE(ZPE) indeed, and based on the BDEs(ZPE) calculated at different density functional theory levels this work has established a good multivariate correlation of impact sensitivity with molecular parameters, which provides a method to address the sensitivity problem.

A harmonic adiabatic approximation to calculate highly excited vibrational levels of ``floppy molecules''

NASA Astrophysics Data System (ADS)

Lauvergnat, David; Nauts, André; Justum, Yves; Chapuisat, Xavier

2001-04-01

The harmonic adiabatic approximation (HADA), an efficient and accurate quantum method to calculate highly excited vibrational levels of molecular systems, is presented. It is well-suited to applications to "floppy molecules" with a rather large number of atoms (N>3). A clever choice of internal coordinates naturally suggests their separation into active, slow, or large amplitude coordinates q', and inactive, fast, or small amplitude coordinates q″, which leads to an adiabatic (or Born-Oppenheimer-type) approximation (ADA), i.e., the total wave function is expressed as a product of active and inactive total wave functions. However, within the framework of the ADA, potential energy data concerning the inactive coordinates q″ are required. To reduce this need, a minimum energy domain (MED) is defined by minimizing the potential energy surface (PES) for each value of the active variables q', and a quadratic or harmonic expansion of the PES, based on the MED, is used (MED harmonic potential). In other words, the overall picture is that of a harmonic valley about the MED. In the case of only one active variable, we have a minimum energy path (MEP) and a MEP harmonic potential. The combination of the MED harmonic potential and the adiabatic approximation (harmonic adiabatic approximation: HADA) greatly reduces the size of the numerical computations, so that rather large molecules can be studied. In the present article however, the HADA is applied to our benchmark molecule HCN/CNH, to test the validity of the method. Thus, the HADA vibrational energy levels are compared and are in excellent agreement with the ADA calculations (adiabatic approximation with the full PES) of Light and Bačić [J. Chem. Phys. 87, 4008 (1987)]. Furthermore, the exact harmonic results (exact calculations without the adiabatic approximation but with the MEP harmonic potential) are compared to the exact calculations (without any sort of approximation). In addition, we compare the densities of the bending motion during the HCN/CNH isomerization, computed with the HADA and the exact wave function.

Towards designing polymers for photovoltaic applications: A DFT and experimental study of polyazomethines with various chemical structures.

PubMed

Wojtkiewicz, Jacek; Iwan, Agnieszka; Pilch, Marek; Boharewicz, Bartosz; Wójcik, Kamil; Tazbir, Igor; Kaminska, Maria

2017-06-15

Theoretical studies of polyazomethines (PAZs) with various chemical structures designated for photovoltaic applications are presented. PAZ energy levels and optical properties were calculated within density-functional theory (DFT and TDDFT) framework for 28 oligomers (monomer, dimer and trimer) of PAZs. The correlations between chemical structure of PAZ and location of its highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels were examined. It turned out that the presence of triaminophenylene, dimethoxydiphenylene and fluorine group raises the orbital energies. As a consequence, it is a factor which improves the photovoltaic efficiency of solar cell built on the base of the corresponding PAZ and [6,6]-phenyl C 61 butyric acid methyl ester (PCBM). On the contrary, quinone, 1,3,5-triazine and perfluorophenylene groups lower orbital energies and have negative influence on the photovoltaic efficiency. Moreover, calculations for methyl, ethyl and butyl analogs of P3HT as well as polythiophenes were performed and compared with the results obtained for PAZs. In addition experimental data are presented, which cover optical, electrochemical and electrical transport properties of the studied PAZs, allowing to determine HOMO and LUMO energies of the polymers and their conductivity. Finally, comparison between calculated and experimental results were made and discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Computational modeling of properties

NASA Technical Reports Server (NTRS)

Franz, Judy R.

1994-01-01

A simple model was developed to calculate the electronic transport parameters in disordered semiconductors in strong scattered regime. The calculation is based on a Green function solution to Kubo equation for the energy-dependent conductivity. This solution together with a rigorous calculation of the temperature-dependent chemical potential allows the determination of the dc conductivity and the thermopower. For wise-gap semiconductors with single defect bands, these transport properties are investigated as a function of defect concentration, defect energy, Fermi level, and temperature. Under certain conditions the calculated conductivity is quite similar to the measured conductivity in liquid II-VI semiconductors in that two distinct temperature regimes are found. Under different conditions the conductivity is found to decrease with temperature; this result agrees with measurements in amorphous Si. Finally the calculated thermopower can be positive or negative and may change sign with temperature or defect concentration.

Computational modeling of properties

NASA Technical Reports Server (NTRS)

Franz, Judy R.

1994-01-01

A simple model was developed to calculate the electronic transport parameters in disordered semiconductors in strong scattered regime. The calculation is based on a Green function solution to Kubo equation for the energy-dependent conductivity. This solution together with a rigorous calculation of the temperature-dependent chemical potential allows the determination of the dc conductivity and the thermopower. For wide-gap semiconductors with single defect bands, these transport properties are investigated as a function of defect concentration, defect energy, Fermi level, and temperature. Under certain conditions the calculated conductivity is quite similar to the measured conductivity in liquid 2-6 semiconductors in that two distinct temperature regimes are found. Under different conditions the conductivity is found to decrease with temperature; this result agrees with measurements in amorphous Si. Finally the calculated thermopower can be positive or negative and may change sign with temperature or defect concentration.

Using monomer vibrational wavefunctions as contracted basis functions to compute rovibrational levels of an H2O-atom complex in full dimensionality.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2017-03-14

In this paper, we present new ideas for computing rovibrational energy levels of molecules composed of two components and apply them to H 2 O-Cl - . When both components are themselves molecules, Euler angles that specify their orientation with respect to an axis system attached to the inter-monomer vector are used as vibrational coordinates. For H 2 O-Cl - , there is only one set of Euler angles. Using Euler angles as intermolecular vibrational coordinates is advantageous because in many cases coupling between them and coordinates that describe the shape of the monomers is unimportant. The monomers are not assumed to be rigid. In the most efficient calculation, vibrational wavefunctions of the monomers are used as contracted basis functions. Energy levels are calculated using the Lanczos algorithm.

Using monomer vibrational wavefunctions as contracted basis functions to compute rovibrational levels of an H2O-atom complex in full dimensionality

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2017-03-01

In this paper, we present new ideas for computing rovibrational energy levels of molecules composed of two components and apply them to H2O-Cl-. When both components are themselves molecules, Euler angles that specify their orientation with respect to an axis system attached to the inter-monomer vector are used as vibrational coordinates. For H2O-Cl-, there is only one set of Euler angles. Using Euler angles as intermolecular vibrational coordinates is advantageous because in many cases coupling between them and coordinates that describe the shape of the monomers is unimportant. The monomers are not assumed to be rigid. In the most efficient calculation, vibrational wavefunctions of the monomers are used as contracted basis functions. Energy levels are calculated using the Lanczos algorithm.

Energy levels, lifetimes and radiative data of W LV

NASA Astrophysics Data System (ADS)

Ding, Xiao-bin; Sun, Rui; Koike, Fumihiro; Murakami, Izumi; Kato, Daiji; Sakaue, Hiroyuki A.; Nakamura, Nobuyuki; Dong, Chen-zhong

2018-01-01

Calculations of energy levels, radiative data and lifetimes are reported for tungsten Ca-like ion (W LV) by using multi-configuration Dirac-Fock (MCDF) method. The GRASP2K package is adopted to carry out a large-scale systematic computation with a restricted active space treatment; the Breit interaction and QED effects are included in subsequent relativistic configuration interaction calculations. The energies and lifetimes of the lowest 119 levels are listed; the main leading configuration of the levels is of the ground state configuration [Ne]3s23p63d2 and the first excited configuration [Ne]3s23p53d3. The wavelengths, radiative rates and oscillator strengths for relatively strong E1, E2, M1, and M2 transitions are listed. Comparisons with earlier experimental and theoretical values are made. The average relative deviations of energy levels from the NIST results and E1 transition wavelengths from the EBIT experimental results have turned to be only 0.20% and 0.13%, respectively. The other present results are in reasonable agreement with available data. These agreements confirm the reliability and accuracy of the current results. The present datasets may help us with the investigation of the electron-electron correlation effects in complex multi-electron highly charged heavy ions and of the diagnosis of tungsten impurity plasmas in fusion science.

DFT and ab initio study of the unimolecular decomposition of the lowest singlet and triplet states of nitromethane

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

Manaa, M.R.; Fried, L.E.

1998-11-26

The fully optimized potential energy curves for the unimolecular decomposition of the lowest singlet and triplet states of nitromethane through the C-NO{sub 2} bond dissociation pathway are calculated using various DFT and high-level ab initio electronic structure methods. The authors perform gradient corrected density functional theory (DFT) and multiconfiguration self-consistent field (MCSCF) to conclusively demonstrate that the triplet state of nitromethane is bound. The adiabatic curve of this state exhibits a 33 kcal/mol energy barrier as determined at the MCSCF level. DFT methods locate this barrier at a shorter C-N bond distance with 12--16 kcal/mol lower energy than does MCSCF.more » In addition to MCSCF and DFT, quadratic configuration interactions with single and double substitutions (QCISD) calculations are also performed for the singlet curve. The potential energy profiles of this state predicted by FT methods based on Becke`s 1988 exchange functional differ by as much as 17 kcal/mol from the predictions of MCSCF and QCISD in the vicinity of the equilibrium structure. The computational methods predict bond dissociation energies 5--9 kcal/mol lower than the experimental value. DFT techniques based on Becke`s 3-parameter exchange functional show the best overall agreement with the higher level methods.« less

Understanding the many-body expansion for large systems. III. Critical role of four-body terms, counterpoise corrections, and cutoffs.

PubMed

Liu, Kuan-Yu; Herbert, John M

2017-10-28

Papers I and II in this series [R. M. Richard et al., J. Chem. Phys. 141, 014108 (2014); K. U. Lao et al., ibid. 144, 164105 (2016)] have attempted to shed light on precision and accuracy issues affecting the many-body expansion (MBE), which only manifest in larger systems and thus have received scant attention in the literature. Many-body counterpoise (CP) corrections are shown to accelerate convergence of the MBE, which otherwise suffers from a mismatch between how basis-set superposition error affects subsystem versus supersystem calculations. In water clusters ranging in size up to (H 2 O) 37 , four-body terms prove necessary to achieve accurate results for both total interaction energies and relative isomer energies, but the sheer number of tetramers makes the use of cutoff schemes essential. To predict relative energies of (H 2 O) 20 isomers, two approximations based on a lower level of theory are introduced and an ONIOM-type procedure is found to be very well converged with respect to the appropriate MBE benchmark, namely, a CP-corrected supersystem calculation at the same level of theory. Results using an energy-based cutoff scheme suggest that if reasonable approximations to the subsystem energies are available (based on classical multipoles, say), then the number of requisite subsystem calculations can be reduced even more dramatically than when distance-based thresholds are employed. The end result is several accurate four-body methods that do not require charge embedding, and which are stable in large basis sets such as aug-cc-pVTZ that have sometimes proven problematic for fragment-based quantum chemistry methods. Even with aggressive thresholding, however, the four-body approach at the self-consistent field level still requires roughly ten times more processors to outmatch the performance of the corresponding supersystem calculation, in test cases involving 1500-1800 basis functions.

Understanding the many-body expansion for large systems. III. Critical role of four-body terms, counterpoise corrections, and cutoffs

NASA Astrophysics Data System (ADS)

Liu, Kuan-Yu; Herbert, John M.

2017-10-01

Papers I and II in this series [R. M. Richard et al., J. Chem. Phys. 141, 014108 (2014); K. U. Lao et al., ibid. 144, 164105 (2016)] have attempted to shed light on precision and accuracy issues affecting the many-body expansion (MBE), which only manifest in larger systems and thus have received scant attention in the literature. Many-body counterpoise (CP) corrections are shown to accelerate convergence of the MBE, which otherwise suffers from a mismatch between how basis-set superposition error affects subsystem versus supersystem calculations. In water clusters ranging in size up to (H2O)37, four-body terms prove necessary to achieve accurate results for both total interaction energies and relative isomer energies, but the sheer number of tetramers makes the use of cutoff schemes essential. To predict relative energies of (H2O)20 isomers, two approximations based on a lower level of theory are introduced and an ONIOM-type procedure is found to be very well converged with respect to the appropriate MBE benchmark, namely, a CP-corrected supersystem calculation at the same level of theory. Results using an energy-based cutoff scheme suggest that if reasonable approximations to the subsystem energies are available (based on classical multipoles, say), then the number of requisite subsystem calculations can be reduced even more dramatically than when distance-based thresholds are employed. The end result is several accurate four-body methods that do not require charge embedding, and which are stable in large basis sets such as aug-cc-pVTZ that have sometimes proven problematic for fragment-based quantum chemistry methods. Even with aggressive thresholding, however, the four-body approach at the self-consistent field level still requires roughly ten times more processors to outmatch the performance of the corresponding supersystem calculation, in test cases involving 1500-1800 basis functions.

Transition energy measurements in hydrogenlike and heliumlike ions strongly supporting bound-state QED calculations

NASA Astrophysics Data System (ADS)

Kubiček, K.; Mokler, P. H.; Mäckel, V.; Ullrich, J.; López-Urrutia, J. R. Crespo

2014-09-01

For the hydrogenlike Ar17+ ion, the 1s Lamb shift was absolutely determined with a 1.4% accuracy based on Lyman-α wavelength measurements that have negligible uncertainties from nuclear size effects. The result agrees with state-of-the-art quantum electrodynamics (QED) calculations, and demonstrates the suitability of Lyman-α transitions in highly charged ions as x-ray energy standards, accurate at the five parts-per-million level. For the heliumlike Ar16+ ion the transition energy for the 1s2p1P1→1s21S0 line was also absolutely determined on an even higher level of accuracy. Additionally, we present relative measurements of transitions in S15+,S14+, and Fe24+ ions. The data for the heliumlike S14+,Ar16+, and Fe24+ ions stringently confirm advanced bound-state QED predictions including screened QED terms that had recently been contested.

An adaptive interpolation scheme for molecular potential energy surfaces

NASA Astrophysics Data System (ADS)

Kowalewski, Markus; Larsson, Elisabeth; Heryudono, Alfa

2016-08-01

The calculation of potential energy surfaces for quantum dynamics can be a time consuming task—especially when a high level of theory for the electronic structure calculation is required. We propose an adaptive interpolation algorithm based on polyharmonic splines combined with a partition of unity approach. The adaptive node refinement allows to greatly reduce the number of sample points by employing a local error estimate. The algorithm and its scaling behavior are evaluated for a model function in 2, 3, and 4 dimensions. The developed algorithm allows for a more rapid and reliable interpolation of a potential energy surface within a given accuracy compared to the non-adaptive version.

Tight-binding modeling and low-energy behavior of the semi-Dirac point.

PubMed

Banerjee, S; Singh, R R P; Pardo, V; Pickett, W E

2009-07-03

We develop a tight-binding model description of semi-Dirac electronic spectra, with highly anisotropic dispersion around point Fermi surfaces, recently discovered in electronic structure calculations of VO2-TiO2 nanoheterostructures. We contrast their spectral properties with the well-known Dirac points on the honeycomb lattice relevant to graphene layers and the spectra of bands touching each other in zero-gap semiconductors. We also consider the lowest order dispersion around one of the semi-Dirac points and calculate the resulting electronic energy levels in an external magnetic field. In spite of apparently similar electronic structures, Dirac and semi-Dirac systems support diverse low-energy physics.

Long range intermolecular interactions between the alkali diatomics Na2, K2, and NaK

NASA Astrophysics Data System (ADS)

Zemke, Warren T.; Byrd, Jason N.; Michels, H. Harvey; Montgomery, John A.; Stwalley, William C.

2010-06-01

Long range interactions between the ground state alkali diatomics Na2-Na2, K2-K2, Na2-K2, and NaK-NaK are examined. Interaction energies are first determined from ab initio calculations at the coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] level of theory, including counterpoise corrections. Long range energies calculated from diatomic molecular properties (polarizabilities and dipole and quadrupole moments) are then compared with the ab initio energies. A simple asymptotic model potential ELR=Eelec+Edisp+Eind is shown to accurately represent the intermolecular interactions for these systems at long range.

Long range intermolecular interactions between the alkali diatomics Na(2), K(2), and NaK.

PubMed

Zemke, Warren T; Byrd, Jason N; Michels, H Harvey; Montgomery, John A; Stwalley, William C

2010-06-28

Long range interactions between the ground state alkali diatomics Na(2)-Na(2), K(2)-K(2), Na(2)-K(2), and NaK-NaK are examined. Interaction energies are first determined from ab initio calculations at the coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] level of theory, including counterpoise corrections. Long range energies calculated from diatomic molecular properties (polarizabilities and dipole and quadrupole moments) are then compared with the ab initio energies. A simple asymptotic model potential E(LR)=E(elec)+E(disp)+E(ind) is shown to accurately represent the intermolecular interactions for these systems at long range.

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

Smith, G.D.; Bharadwaj, R.K.

The molecular geometries and conformational energies of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 1,3-dimethyl-1,3-dinitro methyldiamine (DDMD) and have been determined from high-level quantum chemistry calculations and have been used in parametrizing a classical potential function for simulations of HMX. Geometry optimizations for HMX and DDMD and rotational energy barrier searches for DDMD were performed at the B3LYP/6-311G** level, with subsequent single-point energy calculations at the MP2/6-311G** level. Four unique low-energy conformers were found for HMX, two whose conformational geometries correspond closely to those found in HMX polymorphs from crystallographic studies and two additional, lower energy conformers that are not seen in the crystallinemore » phases. For DDMD, three unique low-energy conformers, and the rotational energy barriers between them, were located. In parametrizing the classical potential function for HMX, nonbonded repulsion/dispersion parameters, valence parameters, and parameters describing nitro group rotation and out-of-plane distortion at the amine nitrogen were taken from the previous studies of dimethylnitramine. Polar effects in HMX and DDMD were represented by sets of partial atomic charges that reproduce the electrostatic potential and dipole moments for the low-energy conformers of these molecules as determined from the quantum chemistry wave functions. Parameters describing conformational energetics for the C-N-C-N dihedrals were determined by fitting the classical potential function to reproduce relative conformational energies in HMX as found from quantum chemistry. The resulting potential was found to give a good representation of the conformer geometries and relative conformer energies in HMX and a reasonable description of the low-energy conformers and rotational energy barriers in DDMD.« less

One dimensional heavy ion beam transport: Energy independent model. M.S. Thesis

NASA Technical Reports Server (NTRS)

Farhat, Hamidullah

1990-01-01

Attempts are made to model the transport problem for heavy ion beams in various targets, employing the current level of understanding of the physics of high-charge and energy (HZE) particle interaction with matter are made. An energy independent transport model, with the most simplified assumptions and proper parameters is presented. The first and essential assumption in this case (energy independent transport) is the high energy characterization of the incident beam. The energy independent equation is solved and application is made to high energy neon (NE-20) and iron (FE-56) beams in water. The numerical solutions is given and compared to a numerical solution to determine the accuracy of the model. The lower limit energy for neon and iron to be high energy beams is calculated due to Barkas and Burger theory by LBLFRG computer program. The calculated values in the density range of interest (50 g/sq cm) of water are: 833.43 MeV/nuc for neon and 1597.68 MeV/nuc for iron. The analytical solutions of the energy independent transport equation gives the flux of different collision terms. The fluxes of individual collision terms are given and the total fluxes are shown in graphs relative to different thicknesses of water. The values for fluxes are calculated by the ANASTP computer code.

Formation Energies of Native Point Defects in Strained-Layer Superlattices (Postprint)

DTIC Science & Technology

2017-06-05

AFRL-RX-WP-JA-2017-0217 FORMATION ENERGIES OF NATIVE POINT DEFECTS IN STRAINED-LAYER SUPERLATTICES (POSTPRINT) Zhi-Gang Yu...2016 Interim 11 September 2013 – 5 November 2016 4. TITLE AND SUBTITLE FORMATION ENERGIES OF NATIVE POINT DEFECTS IN STRAINED-LAYER SUPERLATTICES...native point defect (NPD) formation energies and absence of mid-gap levels. In this Letter we use first-principles calculations to study the formation

Coupled-cluster and density functional theory studies of the electronic 0-0 transitions of the DNA bases.

PubMed

Ovchinnikov, Vasily A; Sundholm, Dage

2014-04-21

The 0-0 transitions of the electronic excitation spectra of the lowest tautomers of the four nucleotide (DNA) bases have been studied using linear-response approximate coupled-cluster singles and doubles (CC2) calculations. Excitation energies have also been calculated at the linear-response time-dependent density functional theory (TDDFT) level using the B3LYP functional. Large basis sets have been employed for ensuring that the obtained excitation energies are close to the basis-set limit. Zero-point vibrational energy corrections have been calculated at the B3LYP and CC2 levels for the ground and excited states rendering direct comparisons with high-precision spectroscopy measurements feasible. The obtained excitation energies for the 0-0 transitions of the first excited states of guanine tautomers are in good agreement with experimental values confirming the experimental assignment of the energetic order of the tautomers of the DNA bases. For the experimentally detected guanine tautomers, the first excited state corresponds to a π→π* transition, whereas for the tautomers of adenine, thymine, and the lowest tautomer of cytosine the transition to the first excited state has n →π* character. The calculations suggest that the 0-0 transitions of adenine, thymine, and cytosine are not observed in the absorption spectrum due to the weak oscillator strength of the formally symmetry-forbidden transitions, while 0-0 transitions of thymine have been detected in fluorescence excitation spectra.

Radiative lifetimes, branching fractions, and oscillator strengths of some levels in Be I

NASA Astrophysics Data System (ADS)

Wang, Xinghao; Quinet, Pascal; Li, Qiu; Yu, Qi; Li, Yongfan; Wang, Qian; Gong, Yimin; Dai, Zhenwen

2018-06-01

Radiative lifetimes of five levels in Be I lying in the energy range 64,506.45-71,160.52 cm-1 were measured by the time-resolved laser-induced fluorescence technique. These new data, together with previously measured radiative lifetimes and two reliable calculated lifetimes, were combined with branching fractions obtained from pseudo-relativistic Hartree-Fock calculations to deduce semi-empirical transition probabilities and oscillator strengths for 90 Be I spectral lines involving upper levels ranging from 42,565.35 to 72,251.27 cm-1.

Density of Electronic States in the Conduction Band of Ultrathin Films of Naphthalenedicarboxylic Anhydride and Naphthalenetetracarboxylic Dianhydride on the Surface of Oxidized Silicon

NASA Astrophysics Data System (ADS)

Komolov, A. S.; Lazneva, E. F.; Gerasimova, N. B.; Panina, Yu. A.; Baramygin, A. V.; Zashikhin, G. D.; Pshenichnyuk, S. A.

2018-04-01

The results of examination of the electronic structure of the conduction band of naphthalenedicarboxylic anhydride (NDCA) films in the process of their deposition on the surface of oxidized silicon are presented. These results were obtained using total current spectroscopy (TCS) in the energy range from 5 to 20 eV above the Fermi level. The energy position of the primary maxima of the density of unoccupied states (DOUS) of an NDCA film was determined based on the experimental TCS data and calculated data and compared with the position of the DOUS maxima of a naphthalenetetracarboxylic dianhydride (NTCDA) film. The theoretical analysis involved calculating the energies and the spatial distribution of orbitals of the molecules under study at the B3LYP/6-31G(d) DFT (density functional theory) level and correcting the obtained energies in accordance with the procedure that was proven effective in earlier studies of the conduction band of films of small conjugated organic molecules. It was found that the DOUS maxima of the NTCDA film in the studied energy interval from 5 to 20 eV above the Fermi level are shifted toward lower electron energies by 1-2 eV relative to the corresponding DOUS maxima of the NDCA film Subdivision of the Ufa Federal Research Centre of the.

VizieR Online Data Catalog: Energy levels of ionized vanadium (V II) (Saloman+, 2017)

NASA Astrophysics Data System (ADS)

Saloman, E. B.; Kramida, A.

2017-09-01

The energy levels, observed spectral lines, and transition probabilities of singly ionized vanadium, V II, have been compiled. The experimentally derived energy levels belong to the configurations 3d4, 3d3ns (n=4,5,6), 3d3np, and 3d3nd (n=4,5), 3d34f, 3d24s2, and 3d24s4p. Also included are values for some forbidden lines that may be of interest to the astrophysical community. Experimental Lande g-factors and leading percentages for the levels are included when available, as well as Ritz wavelengths calculated from the energy levels. Wavelengths and transition probabilities are reported for 3568 and 1896 transitions, respectively. From the list of observed wavelengths, 407 energy levels are determined. The observed intensities, normalized to a common scale, are provided. From the newly optimized energy levels, a revised value for the ionization energy is derived, 118,030(60)cm-1, corresponding to 14.634(7)eV. This is 130cm-1 higher than the previously recommended value from Iglesias+ (1988, Publ. Inst. Opt. Madrid 47 1). (3 data files).

VizieR Online Data Catalog: Stark broadening of XeVIII spectral lines (Dimitrijevic+, 2015)

NASA Astrophysics Data System (ADS)

Dimitrijevic, M. S.; Simic, Z.; Kovacevic, A.; Valjarevic, A.; Sahal-Brechot, S.

2018-01-01

By means of the code based on semiclassical perturbation theory we have calculated widths and shifts for 60 transitions of Xe VIII. The needed energy levels have been taken from Saloman (2004JPCRD..33..765S). Oscillator strengths have been calculated by using the method of Bates & Damgaard (1949RSPTA.242..101B) and the tables of Oertel & Shomo (1968ApJS...16..175O). For higher levels, oscillator strengths have been calculated according to Van Regemorter, Hoang Binh & Prud'homme (1979, J. Phys. B, 12, 1073). (1 data file).

The exact tree-level calculation of the dark photon production in high-energy electron scattering at the CERN SPS

NASA Astrophysics Data System (ADS)

Gninenko, S. N.; Kirpichnikov, D. V.; Kirsanov, M. M.; Krasnikov, N. V.

2018-07-01

Dark photon (A‧) that couples to the standard model fermions via the kinetic mixing with photons and serves as a mediator of dark matter production could be observed in the high-energy electron scattering e- + Z →e- + Z +A‧ off nuclei followed by the bremsstrahlung A‧ → invisible decay. We cross check the exact tree-level calculations of the A‧ production cross sections by other results and implement them in the program for the full simulation of such events in the experiment NA64 at the CERN SPS . Using simulations results, we study the missing energy signature for the A‧ → invisible decay that allows to probe the γ -A‧ mixing strength in a wide, from sub-MeV to sub-GeV, A‧ mass range. We refine and expand our earlier studies of this signature by including corrections to the previously used calculations based on the improved Weizsaker-Williams (IWW) approximation, which turn out to be significant. We find that the commonly used IWW approach can lead to substantial overestimation of the sensitivity to A‧ in fixed target experiments. The possibility of future searches with high-energy electron beams and their sensitivity to A‧ are briefly discussed.

Materials Design of the Codoping for the Fabrication of Low-Resistivity p-Type ZnSe and GaN by ab-initio Electronic Structure Calculation

NASA Astrophysics Data System (ADS)

Katayama-Yoshida, H.; Yamamoto, T.

1997-08-01

We propose an effective doping method, the codoping (doping with n- and p-type dopants at the same time) method, for the fabrication of low-resistivity p-type ZnSe and GaN with wide-band-gap based upon ab-initio electronic band structure calculations. p-type doping eminently leads to an increase in the electrostatic energy, called the Madelung energy, which shifts the Se 4p levels for p-type doped ZnSe and the N 2p levels for p-type doped GaN materials towards higher energy regions. This leads to a destabilization of ionic charge distributions in p-type ZnSe and p-type GaN crystals, resulting in the self-compensation of anion intrinsic defects. For ZnSe crystals, we propose the codoping of n-type In donors at Zn sites and p-type N acceptors at Se sites based on the calculation. In addition, we propose the codoping of n-type Si-donors at Ga sites (n-type O donors at N sites) and p-type Be- or Mg acceptors at Ga sites. The codoping decreases the Madelung energy and leads to an increase in the net acceptor carrier density.

Combined quantum mechanics/molecular mechanics (QM/MM) simulations for protein-ligand complexes: free energies of binding of water molecules in influenza neuraminidase.

PubMed

Woods, Christopher J; Shaw, Katherine E; Mulholland, Adrian J

2015-01-22

The applicability of combined quantum mechanics/molecular mechanics (QM/MM) methods for the calculation of absolute binding free energies of conserved water molecules in protein/ligand complexes is demonstrated. Here, we apply QM/MM Monte Carlo simulations to investigate binding of water molecules to influenza neuraminidase. We investigate five different complexes, including those with the drugs oseltamivir and peramivir. We investigate water molecules in two different environments, one more hydrophobic and one hydrophilic. We calculate the free-energy change for perturbation of a QM to MM representation of the bound water molecule. The calculations are performed at the BLYP/aVDZ (QM) and TIP4P (MM) levels of theory, which we have previously demonstrated to be consistent with one another for QM/MM modeling. The results show that the QM to MM perturbation is significant in both environments (greater than 1 kcal mol(-1)) and larger in the more hydrophilic site. Comparison with the same perturbation in bulk water shows that this makes a contribution to binding. The results quantify how electronic polarization differences in different environments affect binding affinity and also demonstrate that extensive, converged QM/MM free-energy simulations, with good levels of QM theory, are now practical for protein/ligand complexes.

Impact behaviour of Napier/polyester composites under different energy levels

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

Fahmi, I., E-mail: fahmi-unimap@yahoo.com; Majid, M. S. Abdul, E-mail: shukry@unimap.edu.my; Afendi, M., E-mail: afendirojan@unimap.edu.my

2016-07-19

The effects of different energy levels on the impact behaviour of Napier fibre/polyester reinforced composites were investigated. Napier fibre was extracted using traditional water retting process to be utilized as reinforcing materials in polyester composite laminates. 25% fibre loading composite laminates were prepared and impacted at three different energy levels; 2.5,5 and 7.5 J using an instrumented drop weight impact testing machine (IMATEK IM10). The outcomes show that peak force and contact time increase with increased impact load. The energy absorption was then calculated from the force displacement curve. The results indicated that the energy absorption decreases with increasing energymore » levels of the impact. Impacted specimens were observed visually for fragmentation fracture using an optical camera to identify the failure mechanisms. Fracture fragmentation pattern from permanent dent to perforation with radial and circumferential was observed.« less

The energy balance in coronal holes and average quiet-sun regions

NASA Technical Reports Server (NTRS)

Raymond, J. C.; Doyle, J. G.

1981-01-01

Emission measure curves are presented for average coronal hole and quiet-sun spectra taken during the Skylab mission by Vernazza and Reeves (1978), and the curves are used to discuss the energy balance in each region. Close-coupling calculations are used for the Be sequence, assuming a 10 level ion; for B sequence ions mainly distorted wave calculations in an 11 level ion are used, but close-coupling cross sections are used for some ions; for C and Mg sequence ions, distorted wave calculations are used with 15 and 10 level ions, respectively, and close-coupling results are used for Li-like ions with two levels. Results are presented and include the following: the coronal hole spectrum shows a smaller slope in the emission measure distribution, consistent with the expected outflow effects. It is concluded that the simple constant pressure models of static coronal loops of constant cross section are basically able to match the observed emission measure distribution of the average quiet sun between 1,000,000 and 10,000,000 K. However, the cell center and network distributions are respectively steeper and shallower than predicted by the detailed cooling curve.

Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals.

PubMed

Śmiga, Szymon; Fabiano, Eduardo; Laricchia, Savio; Constantin, Lucian A; Della Sala, Fabio

2015-04-21

We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded molecular systems. Meta-GGA functionals depend on the Kohn-Sham kinetic energy density (KED), which is not known as an explicit functional of the density. Therefore, they cannot be directly applied in subsystem DFT calculations. We propose a Laplacian-level approximation to the KED which overcomes this limitation and provides a simple and accurate way to apply meta-GGA exchange-correlation functionals in subsystem DFT calculations. The so obtained density and energy errors, with respect to the corresponding supermolecular calculations, are comparable with conventional approaches, depending almost exclusively on the approximations in the non-additive kinetic embedding term. An embedding energy error decomposition explains the accuracy of our method.

Potential energy surface interpolation with neural networks for instanton rate calculations

NASA Astrophysics Data System (ADS)

Cooper, April M.; Hallmen, Philipp P.; Kästner, Johannes

2018-03-01

Artificial neural networks are used to fit a potential energy surface (PES). We demonstrate the benefits of using not only energies but also their first and second derivatives as training data for the neural network. This ensures smooth and accurate Hessian surfaces, which are required for rate constant calculations using instanton theory. Our aim was a local, accurate fit rather than a global PES because instanton theory requires information on the potential only in the close vicinity of the main tunneling path. Elongations along vibrational normal modes at the transition state are used as coordinates for the neural network. The method is applied to the hydrogen abstraction reaction from methanol, calculated on a coupled-cluster level of theory. The reaction is essential in astrochemistry to explain the deuteration of methanol in the interstellar medium.

Quantum chemical calculations and analysis of FTIR, FT-Raman and UV-Vis spectra of temozolomide molecule

NASA Astrophysics Data System (ADS)

Bhat, Sheeraz Ahmad; Ahmad, Shabbir

2015-11-01

A combined experimental and theoretical study of the structure, vibrational and electronic spectra of temozolomide molecule, which is largely used in the treatment of brain tumours, is presented. FTIR (4000-400 cm-1) and FT-Raman spectra (4000‒50 cm-1) have been recorded and analysed using anharmonic frequency calculations using VPT2, VSCF and CC-VSCF levels of theory within B3LYP/6-311++G(d,p) framework. Anharmonic methods give accurate frequencies of fundamental modes, overtones as well as Fermi resonances and account for coupling of different modes. The anharmonic frequencies calculated using VPT2 and CC-VSCF methods show better agreement with the experimental data. Harmonic frequencies including solvent effects are also computed using IEF-PCM model. The magnitudes of coupling between pair of modes have been calculated using coupling integral based on 2MR-QFF approximation. Intermolecular interactions are discussed for three possible dimers of temozolomide. UV-Vis spectrum, examined in ethanol solvent, is compared with the calculated spectrum at TD-DFT/6-311++G(d,p) level of theory. The electronic properties, such as excitation energy, frontier molecular orbital energies and the assignments of the absorption bands are also discussed.

Comparative study of elastic electron collisions on the isoelectronic SiN{sub 2}, SiCO, and CSiO radicals

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

Fujimoto, M. M.; Michelin, S. E.; Mazon, K. T.

2007-07-15

We report a theoretical study of elastic electron collisions on three isoelectronic free radicals, namely, SiNN, SiCO, and CSiO. More specifically, differential, integral, and momentum-transfer cross sections are calculated and reported in the (1-100) eV energy range. Calculations are performed at the static-exchange-polarization-absorption level of approximation. A combination of the iterative Schwinger variational method and the distorted-wave approximation is used to solve the scattering equations. Our study reveals that the calculated cross sections for the e{sup -}-SiNN and e{sup -}-SiCO collisions are very similar even at incident energies as low as 3 eV. Strong isomeric effects are also observed inmore » the calculated cross sections for e{sup -}-CSiO and e{sup -}-SiCO collisions, particularly at incident energies below 20 eV. It is believed that the position of the silicon atom being at the center or extremity of the molecules may exert important influence on the calculated cross sections.« less

An accurate cost effective DFT approach to study the sensing behaviour of polypyrrole towards nitrate ions in gas and aqueous phases.

PubMed

Wasim, Fatima; Mahmood, Tariq; Ayub, Khurshid

2016-07-28

Density functional theory (DFT) calculations have been performed to study the response of polypyrrole towards nitrate ions in gas and aqueous phases. First, an accurate estimate of interaction energies is obtained by methods calibrated against the gold standard CCSD(T) method. Then, a number of low cost DFT methods are also evaluated for their ability to accurately estimate the binding energies of polymer-nitrate complexes. The low cost methods evaluated here include dispersion corrected potential (DCP), Grimme's D3 correction, counterpoise correction of the B3LYP method, and Minnesota functionals (M05-2X). The interaction energies calculated using the counterpoise (CP) correction and DCP methods at the B3LYP level are in better agreement with the interaction energies calculated using the calibrated methods. The interaction energies of an infinite polymer (polypyrrole) with nitrate ions are calculated by a variety of low cost methods in order to find the associated errors. The electronic and spectroscopic properties of polypyrrole oligomers nPy (where n = 1-9) and nPy-NO3(-) complexes are calculated, and then extrapolated for an infinite polymer through a second degree polynomial fit. Charge analysis, frontier molecular orbital (FMO) analysis and density of state studies also reveal the sensing ability of polypyrrole towards nitrate ions. Interaction energies, charge analysis and density of states analyses illustrate that the response of polypyrrole towards nitrate ions is considerably reduced in the aqueous medium (compared to the gas phase).

Comparative study for elastic electron collisions on C{sub 2}N{sub 2} isomers

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

Michelin, S. E.; Falck, A. S.; Mazon, K. T.

2006-08-15

In this work, we present a theoretical study on elastic electron collisions with the four C{sub 2}N{sub 2} isomers. More specifically, calculated differential, integral, and momentum transfer cross sections are reported in the 1-100 eV energy range. Calculations are performed at both the static-exchange-absorption and the static-exchange-polarization-absorption levels. The iterative Schwinger variational method combined with the distorted wave approximation is used to solve the scattering equations. Our study reveals an interesting trend of the calculated cross sections for the four isomers. In particular, strong isomer effect is seen at low incident energies. Also, we have identified a shape resonance whichmore » leads to a depression in the calculated partial integral cross section.« less

Relativistic many-body calculation of energies, multipole transition rates, and lifetimes in tungsten ions

NASA Astrophysics Data System (ADS)

Safronova, U. I.; Safronova, M. S.; Nakamura, N.

2017-04-01

Atomic properties of Cd-like W26 +, In-like W25 +, and Sn-like W24 + ions are evaluated by using a relativistic CI+all -order approach that combines configuration-interaction and the coupled-cluster methods. The energies, transition rates, and lifetimes of low-lying levels are calculated and compared with available theoretical and experimental values. The magnetic-dipole transition rates are calculated to determine the branching ratios and lifetimes for the 4 f3 states in W25 + and for the 4 f4 states in W24 + ions. Excellent agreement of the CI+all -order values provided a benchmark test of this method for the 4 fn configurations validating the recommended values of tungsten ion properties calculated in this work.

The effect of ambient pressure on well chamber response: Monte Carlo calculated results for the HDR 1000 plus.

PubMed

Bohm, Tim D; Griffin, Sheridan L; DeLuca, Paul M; DeWerd, Larry A

2005-04-01

The determination of the air kerma strength of a brachytherapy seed is necessary for effective treatment planning. Well ionization chambers are used on site at therapy clinics to determine the air kerma strength of seeds. In this work, the response of the Standard Imaging HDR 1000 Plus well chamber to ambient pressure is examined using Monte Carlo calculations. The experimental work examining the response of this chamber as well as other chambers is presented in a companion paper. The Monte Carlo results show that for low-energy photon sources, the application of the standard temperature pressure PTP correction factor produces an over-response at the reduced air densities/pressures corresponding to high elevations. With photon sources of 20 to 40 keV, the normalized PTP corrected chamber response is as much as 10% to 20% over unity for air densities/pressures corresponding to an elevation of 3048 m (10000 ft) above sea level. At air densities corresponding to an elevation of 1524 m (5000 ft), the normalized PTP-corrected chamber response is 5% to 10% over unity for these photon sources. With higher-energy photon sources (>100 keV), the normalized PTP corrected chamber response is near unity. For low-energy beta sources of 0.25 to 0.50 MeV, the normalized PTP-corrected chamber response is as much as 4% to 12% over unity for air densities/pressures corresponding to an elevation of 3048 m (10000 ft) above sea level. Higher-energy beta sources (>0.75 MeV) have a normalized PTP corrected chamber response near unity. Comparing calculated and measured chamber responses for common 103Pd- and 125I-based brachytherapy seeds show agreement to within 2.7% and 1.9%, respectively. Comparing MCNP calculated chamber responses with EGSnrc calculated chamber responses show agreement to within 3.1% at photon energies of 20 to 40 keV. We conclude that Monte Carlo transport calculations accurately model the response of this well chamber. Further, applying the standard PTP correction factor for this well chamber is insufficient in accounting for the change in chamber response with air pressure for low-energy (<100 keV) photon and low-energy (<0.75 MeV)beta sources.

Towards black-box calculations of tunneling splittings obtained from vibrational structure methods based on normal coordinates.

PubMed

Neff, Michael; Rauhut, Guntram

2014-02-05

Multidimensional potential energy surfaces obtained from explicitly correlated coupled-cluster calculations and further corrections for high-order correlation contributions, scalar relativistic effects and core-correlation energy contributions were generated in a fully automated fashion for the double-minimum benchmark systems OH3(+) and NH3. The black-box generation of the potentials is based on normal coordinates, which were used in the underlying multimode expansions of the potentials and the μ-tensor within the Watson operator. Normal coordinates are not the optimal choice for describing double-minimum potentials and the question remains if they can be used for accurate calculations at all. However, their unique definition is an appealing feature, which removes remaining errors in truncated potential expansions arising from different choices of curvilinear coordinate systems. Fully automated calculations are presented, which demonstrate, that the proposed scheme allows for the determination of energy levels and tunneling splittings as a routine application. Copyright © 2013 Elsevier B.V. All rights reserved.

Strong CH/O interactions between polycyclic aromatic hydrocarbons and water: Influence of aromatic system size.

PubMed

Veljković, Dušan Ž

2018-03-01

Energies of CH/O interactions between water molecule and polycyclic aromatic hydrocarbons with a different number of aromatic rings were calculated using ab initio calculations at MP2/cc-PVTZ level. Results show that an additional aromatic ring in structure of polycyclic aromatic hydrocarbons significantly strengthens CH/O interactions. Calculated interaction energies in optimized structures of the most stable tetracene/water complex is -2.27 kcal/mol, anthracene/water is -2.13 kcal/mol and naphthalene/water is -1.97 kcal/mol. These interactions are stronger than CH/O contacts in benzene/water complex (-1.44 kcal/mol) while CH/O contacts in tetracene/water complex are even stronger than CH/O contacts in pyridine/water complexes (-2.21 kcal/mol). Electrostatic potential maps for different polycyclic aromatic hydrocarbons were calculated and used to explain trends in the energies of interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

Atomic Data for the CHIANTI Database

NASA Technical Reports Server (NTRS)

Bhatia, Anand K.; Landi, E.

2012-01-01

The CHIANTI spectral code consists of an atomic database and a suite of computer programs to calculate the optically thin spectrum of astrophysical objects and to carry out spectroscopic plasma diagnostics. The database includes atomic energy levels, wavelengths, radiative transition rates, collisional excitation, ionization and recombination rate coefficients, as well as data to calculate free-free, free-bound and two-photon continuum emission. In recent years, we have been pursuing a program to calculate atomic data for ions whose lines have been observed in astrophysical spectra but have been neglected in the literature, and to provide CHIANTI with all the data necessary to predict line intensities. There are two types of such ions: those for which calculations are available for low-energy configurations but not for high-energy configurations (i.e., C-like, N-like, O-like systems), and ions that have never or only seldom been studied. This poster will summarize the current status of this project and indicate the future activities .

Theoretical prediction of the mechanistic pathways and kinetics of methylcyclohexane initiated by OH radicals

NASA Astrophysics Data System (ADS)

Begum, Saheen Shehnaz; Deka, Ramesh Chandra; Gour, Nand Kishor

2018-06-01

In this manuscript, we have systematically depicted the theoretical prediction of H-absorption from methylcyclohexane initiated by OH radical. For this we have performed dual-level of quantum chemical calculations on the gas-phase reactions between methylcyclohexane (MCH) and OH radical. Geometry optimisation and vibrational frequency calculations have been performed at BHandHLYP/6-311G(d,p) level of theory along with energetic calculations at coupled cluster CCSD(T) method using the same basis set. All the stationary points of titled reaction have been located on the potential energy surface. It has also been found that the H-abstraction takes place from -CH site of MCH, which is the minimum energy pathway than others. The rate constant was calculated using canonical transition state theory for MCH with OH radical and is found to be 3.27 × 10-12 cm3 molecule-1 s-1, which is in sound agreement with reported experimental data. The atmospheric lifetime of MCH and branching ratios of the reaction channels are also reported in the manuscript.

Aggregation of Electric Current Consumption Features to Extract Maintenance KPIs

NASA Astrophysics Data System (ADS)

Simon, Victor; Johansson, Carl-Anders; Galar, Diego

2017-09-01

All electric powered machines offer the possibility of extracting information and calculating Key Performance Indicators (KPIs) from the electric current signal. Depending on the time window, sampling frequency and type of analysis, different indicators from the micro to macro level can be calculated for such aspects as maintenance, production, energy consumption etc. On the micro-level, the indicators are generally used for condition monitoring and diagnostics and are normally based on a short time window and a high sampling frequency. The macro indicators are normally based on a longer time window with a slower sampling frequency and are used as indicators for overall performance, cost or consumption. The indicators can be calculated directly from the current signal but can also be based on a combination of information from the current signal and operational data like rpm, position etc. One or several of those indicators can be used for prediction and prognostics of a machine's future behavior. This paper uses this technique to calculate indicators for maintenance and energy optimization in electric powered machines and fleets of machines, especially machine tools.

Distributed information system on molecular spectroscopy

NASA Astrophysics Data System (ADS)

Bykov, A. D.; Fazliev, A. Z.; Kozodoev, A. V.; Privezentsev, A. I.; Sinitsa, L. N.; Tonkov, M. V.; Filippov, N. N.; Tretyakov, M. Yu.

2006-12-01

The urgency of creating the information-computational systems (ICS) on molecular spectroscopy follows from the circumstance that for some molecules the number of calculated energy levels counts hundreds of thousands, and the number of spectral lines sometimes reaches hundreds of millions. Publication of such data volumes in regular journals is inappropriate. Comparison of different calculated spectral characteristics or their comparison with experimental data beyond computer processing is hopeless. We find information systems to be an adequate form for holding such data volumes and a toolkit for handling them. Correct digital data processing requires appropriate sets of metadata arranged in the form of ontology of molecular spectroscopy. Our information system provides the data on spectral line parameters, water molecule energy levels, and absorption coefficients. Within this distributed IS one can solve two types of problems: manipulation with data and calculation of spectral functions. Among the latest experimental data in the IS there are data obtained at the Institute of Applied Physics RAS. To calculate the absorption coefficients for the molecules of carbonic acid gas, we take into consideration spectral line interference.

High-dimensional fitting of sparse datasets of CCSD(T) electronic energies and MP2 dipole moments, illustrated for the formic acid dimer and its complex IR spectrum

NASA Astrophysics Data System (ADS)

Qu, Chen; Bowman, Joel M.

2018-06-01

We present high-level, coupled-mode calculations of the infrared spectrum of the cyclic formic acid dimer. The calculations make use of full-dimensional, ab initio potential energy and dipole moment surfaces. The potential is a linear least-squares fit to 13 475 CCSD(T)-F12a/haTZ (haTZ means aug-cc-pVTZ basis set for O and C, and cc-pVTZ for H) energies, and the dipole moment surface is a fit to the dipole components, calculated at the MP2/haTZ level of theory. The variables of both fits are all (45) internuclear distances (actually Morse variables). The potential, which is fully permutationally invariant, is the one published recently and the dipole moment surface is newly reported here. Details of the fits, especially the dipole moment, and the database of configurations are given. The infrared spectrum of the dimer is calculated by solving the nuclear Schrödinger equation using a vibrational self-consistent field and virtual-state configuration interaction method, with subsets of the 24 normal modes, up to 15 modes. The calculations indicate strong mode-coupling in the C—H and O—H stretching region of the spectrum. Comparisons are made with experiments and the complexity of the experimental spectrum in the C—H and O—H stretching region is successfully reproduced.

Level density parameter behaviour at high excitation energy

NASA Astrophysics Data System (ADS)

D'Arrigo, A.; Giardina, G.; Taccone, A.

1991-06-01

We present a formalism to calculate the intrinsic (without collective effects) and effective (with collective effects) level density parameters over a wide range of excitation energy up to 180 MeV. The behaviour of aint and aeff as an energy function is shown for several typical nuclei (115Cd, 129Te, 148Pm, 173Yb, 192Ir and 248Cm). Moreover, local systematics of the parameter aeff as a function of the neutron number N, also for nuclei extremely far from the β-line, is shown for some typical nuclei (Rb, Pd, Sn, Ba and Hg) at excitation energies of 15, 80 and 150 MeV.

Regional thermal and electric energy output of salt-gradient solar ponds in the U.S.

NASA Technical Reports Server (NTRS)

Singer, M. J.; Lin, E. I. H.

1982-01-01

Salt-gradient solar pond thermal and electrical energy output was calculated for each of twelve regions within the United States as part of an effort to assess solar pond applicability and extent of requisite physical resources on a regional basis. The energy output level is one of the key factors affecting the economic feasibility of solar ponds. Calculated thermal energy output ranges from 6.9 Wt/sq m in Fairbanks, Alaska, to 73.1 Wt/sq m in Daggett, California, at an energy extraction temperature of 45 C. The output ranges from 0.0 Wt/sq m in Fairbanks to 63.2 Wt/sq m in Daggett at 60 C. Electrical energy output ranges from 0.0 We/sq m in Fairbanks to 3.11 We/sq m in Daggett. Although these estimates constitute a reasonable basis for regional comparison, site-specific analysis must be performed for an actual application design.

Theoretical study of transition-metal ions bound to benzene

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

1992-01-01

Theoretical binding energies are reported for all first-row and selected second-row transition metal ions (M+) bound to benzene. The calculations employ basis sets of at least double-zeta plus polarization quality and account for electron correlation using the modified coupled-pair functional method. While the bending is predominantly electrostatic, the binding energies are significantly increased by electron correlation, because the donation from the metal d orbitals to the benzene pi* orbitals is not well described at the self-consistent-field level. The uncertainties in the computed binding energies are estimated to be about 5 kcal/mol. Although the calculated and experimental binding energies generally agree to within their combined uncertainties, it is likely that the true binding energies lie in the lower portion of the experimental range. This is supported by the very good agreement between the theoretical and recent experimental binding energies for AgC6H6(+).

Energy Levels of Defects Created in Silicon Supersaturated with Transition Metals

NASA Astrophysics Data System (ADS)

García, H.; Castán, H.; Dueñas, S.; García-Hemme, E.; García-Hernansaz, R.; Montero, D.; González-Díaz, G.

2018-03-01

Intermediate-band semiconductors have attracted much attention for use in silicon-based solar cells and infrared detectors. In this work, n-Si substrates have been implanted with very high doses (1013 cm-2 and 1014 cm-2) of vanadium, which gives rise to a supersaturated layer inside the semiconductor. However, the Mott limit was not exceeded. The energy levels created in the supersaturated silicon were studied in detail by means of thermal admittance spectroscopy. We found a single deep center at energy near E C - 200 meV. This value agrees with one of the levels found for vanadium in silicon. The capture cross-section values of the deep levels were also calculated, and we found a relationship between the capture cross-section and the energy position of the deep levels which follows the Meyer-Neldel rule. This process usually appears in processes involving multiple excitations. The Meyer-Neldel energy values agree with those previously obtained for silicon supersaturated with titanium and for silicon contaminated with iron.

CALCULATIONS WITH SPECTROSCOPIC ACCURACY: ENERGIES AND TRANSITION RATES IN THE NITROGEN ISOELECTRONIC SEQUENCE FROM Ar XII TO Zn XXIV

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

Wang, K.; Dang, W.; Si, R.

2016-03-15

Combined relativistic configuration interaction and many-body perturbation calculations are performed for the 359 fine-structure levels of the 2s{sup 2} 2p{sup 3}, 2 s2p{sup 4}, 2p{sup 5}, 2s{sup 2} 2p{sup 2} 3l, 2 s2p{sup 3} 3l, 2p{sup 4} 3l, and 2s{sup 2} 2p{sup 2} 4l configurations in N-like ions from Ar xii to Zn xxiv. Complete and consistent data sets of energies, wavelengths, radiative rates, oscillator strengths, and line strengths for all possible electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transitions among the 359 levels are given for each ion. The present work significantly increases the amount of accuratemore » data for ions in the nitrogen-like sequence, and the accuracy of the energy levels is high enough to enable the identification and interpretation of observed spectra involving the n = 3, 4 levels, for which experimental values are largely scarce. Meanwhile, the results should be of great help for modeling and diagnosing astrophysical and fusion plasmas.« less

Ar(n)HF van der Waals clusters revisited: II. Energetics and HF vibrational frequency shifts from diffusion Monte Carlo calculations on additive and nonadditive potential-energy surfaces for n=1-12.

PubMed

Jiang, Hao; Xu, Minzhong; Hutson, Jeremy M; Bacić, Zlatko

2005-08-01

The ground-state energies and HF vibrational frequency shifts of Ar(n)HF clusters have been calculated on the nonadditive potential-energy surfaces (PESs) for n=2-7 and on the pairwise-additive PESs for the clusters with n=1-12, using the diffusion Monte Carlo (DMC) method. For n>3, the calculations have been performed for the lowest-energy isomer and several higher-lying isomers which are the closest in energy. They provide information about the isomer dependence of the HF redshift, and enable direct comparison with the experimental data recently obtained in helium nanodroplets. The agreement between theory and experiment is excellent, in particular, for the nonadditive DMC redshifts. The relative, incremental redshifts are reproduced accurately even at the lower level of theory, i.e., the DMC and quantum five-dimensional (rigid Ar(n)) calculations on the pairwise-additive PESs. The nonadditive interactions make a significant contribution to the frequency shift, on the order of 10%-12%, and have to be included in the PESs in order for the theory to yield accurate magnitude of the HF redshift. The energy gaps between the DMC ground states of the cluster isomers are very different from the energy separation of their respective minima on the PES, due to the considerable variations in the intermolecular zero-point energy of different Ar(n)HF isomers.

Calculations of kaonic nuclei based on chiral meson-baryon amplitudes

NASA Astrophysics Data System (ADS)

Gazda, Daniel; Mareš, Jiří

2013-09-01

In-medium KbarN scattering amplitudes developed within a chirally motivated coupled-channel model are used to construct K- nuclear potentials for calculations of K- nuclear quasi-bound states. Self-consistent evaluations yield K- potential depths -Re VK(ρ0) of order 100 MeV. Dynamical polarization effects and two-nucleon KbarNN→YN absorption modes are discussed. The widths ΓK of allK- nuclear quasi-bound states are comparable or even larger than the corresponding binding energies BK, exceeding considerably the energy level spacing.

Evidence from lattice data for a new particle on the worldsheet of the QCD flux tube.

PubMed

Dubovsky, Sergei; Flauger, Raphael; Gorbenko, Victor

2013-08-09

We propose a new approach for the calculation of the spectrum of excitations of QCD flux tubes. It relies on the fact that the worldsheet theory is integrable at low energies. With this approach, energy levels can be calculated for much shorter flux tubes than was previously possible, allowing for a quantitative comparison with existing lattice data. The improved theoretical control makes it manifest that existing lattice data provides strong evidence for a new pseudoscalar particle localized on the QCD flux tube--the worldsheet axion.

Hydrogenic impurity bound polaron in an anisotropic quantum dot

NASA Astrophysics Data System (ADS)

Chen, Shi-Hua

2018-01-01

The effect of the electron-phonon interaction on an electron bound to a hydrogenic impurity in a three-dimensional (3D) anisotropic quantum dot (QD) is studied theoretically. We use the Landau-Pekar variational approach to calculate the binding energy of ground state (GS) and first-excited state (ES) with considering electron-phonon interaction. The expressions of the GS and ES energies under investigation depict a rich variety of dependent relationship with the variational parameters in three different limiting cases. Numerical calculations were performed for ZnSe QDs with different confinement lengths in the xy-plane and the z-direction, respectively. It is illustrated that binding energies of impurity polarons corresponding to each level are larger in small QDs. Furthermore, the contribution to binding energy from phonon is about 15% of the total binding energy.

Prediction of core level binding energies in density functional theory: Rigorous definition of initial and final state contributions and implications on the physical meaning of Kohn-Sham energies.

PubMed

Pueyo Bellafont, Noèlia; Bagus, Paul S; Illas, Francesc

2015-06-07

A systematic study of the N(1s) core level binding energies (BE's) in a broad series of molecules is presented employing Hartree-Fock (HF) and the B3LYP, PBE0, and LC-BPBE density functional theory (DFT) based methods with a near HF basis set. The results show that all these methods give reasonably accurate BE's with B3LYP being slightly better than HF but with both PBE0 and LCBPBE being poorer than HF. A rigorous and general decomposition of core level binding energy values into initial and final state contributions to the BE's is proposed that can be used within either HF or DFT methods. The results show that Koopmans' theorem does not hold for the Kohn-Sham eigenvalues. Consequently, Kohn-Sham orbital energies of core orbitals do not provide estimates of the initial state contribution to core level BE's; hence, they cannot be used to decompose initial and final state contributions to BE's. However, when the initial state contribution to DFT BE's is properly defined, the decompositions of initial and final state contributions given by DFT, with several different functionals, are very similar to those obtained with HF. Furthermore, it is shown that the differences of Kohn-Sham orbital energies taken with respect to a common reference do follow the trend of the properly calculated initial state contributions. These conclusions are especially important for condensed phase systems where our results validate the use of band structure calculations to determine initial state contributions to BE shifts.

Tautomerism and spectroscopic properties of the immunosuppressant azathioprine.

PubMed

Makhyoun, Mohamed A; Massoud, Raghdaa A; Soliman, Saied M

2013-10-01

The molecular structure and the relative stabilities of the four possible tautomers of the immunosuppressant azathioprine (AZA) are calculated by DFT/B3LYP method using different basis sets. The results of the energy analysis and thermodynamic treatment of the obtained data are used to predict the relative stabilities of the AZA tautomers. The effect of solvents such as DMSO and water on the stability of the AZA tautomers was studied using the polarized continuum method (PCM) at the same level of theory. The calculation predicted that, the total energies of all tautomers are decreased indicating that all tautomers are more or less stabilized by the solvent effect. The vibrational spectra of AZA are calculated using the same level of theory and the results are compared with the experimentally measured FTIR spectra. Good correlation is obtained between the experimental and calculated vibrational frequencies (R(2)=0.997). The electronic spectra of AZA in gas phase and in methanol as solvent are calculated using the TD-DFT method. The calculations predicted bathochromic shift in all the spectral bands in presence of solvent compared to the gas phase. Also the NMR spectra of all tautomers are calculated and the results are correlated with the experimental NMR chemical shifts where the most stable tautomer gives the best correlation coefficient (R(2)=0.996). Copyright © 2013 Elsevier B.V. All rights reserved.

Collisional excitation of CH2 rotational/fine-structure levels by helium

NASA Astrophysics Data System (ADS)

Dagdigian, P. J.; Lique, F.

2018-02-01

Accurate determination of the abundance of CH2 in interstellar media relies on both radiative and collisional rate coefficients. We investigate here the rotational/fine-structure excitation of CH2 induced by collisions with He. We employ a recoupling technique to generate fine-structure-resolved cross-sections and rate coefficients from close coupling spin-free scattering calculations. The calculations are based on a recent, high-accuracy CH2-He potential energy surface computed at the coupled clusters level of theory. The collisional cross-section calculations are performed for all fine-structure transitions among the first 22 and 24 energy levels of ortho- and para-CH2, respectively, and for temperatures up to 300 K. As a first application, we simulate the excitation of CH2 in typical molecular clouds. The excitation temperatures of the CH2 lines are found to be small at typical densities of molecular clouds, showing that the non-local thermodynamic equilibrium approach has to be used to analyse interstellar spectra. We also found that the fine-structure lines connected with the 404 - 313 and 505 - 414 rotational transitions show possible maser emissions so that they can be easily seen in emission. These calculations show that CH2 may have to be detected mainly through absorption spectra.

Energies and transition rates in Ge-like ions between In XVIII and Ce XXVII

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin; Wang, Kai

2017-03-01

The energy levels, wavelengths, oscillator strengths, and radiative electric dipole (E1), magnetic quadrupole (M2) transition probabilities for Ge-like ions (49 ≤ Z ≤ 58) among the lowest 88 fine-structure levels belonging to the ([Ar] 3d10)4s24p2, ([Ar] 3d10)4s24p4d, ([Ar] 3d10)4s4p3, ([Ar] 3d10)4s4p24d, ([Ar] 3d10)4s24d2, and ([Ar] 3d10)4p4 configurations are calculated using the fully relativistic multiconfiguration Dirac-Fock (MCDF) approach including the correlations within the n = 7 complex, Breit interaction (BI) and quantum electrodynamics (QED) effects. For comparison, an independent calculation using the many-body perturbation theory (MBPT) method is also carried out to confirm the present energy levels accuracy, taking Xe XXIII as an example. The present results are compared with available experimental and theoretical results and good agreement is obtained. These accurate theoretical data are useful for controlled thermonuclear fusion research, plasma physics, and astrophysical applications.

The Calculation Study of Electronic Properties of Doped RE (Eu, Er and Tm)-GaN using Density Functional Theory

NASA Astrophysics Data System (ADS)

Zaharo, Aflah; Purqon, Acep

2017-07-01

The calculation of the structure and electronic properties of Rare Earth (RE) at the wurtzite Gallium Nitride (GaN) based on DFT has completed. GGA approximation used for exchange correlation and Ultra soft pseudo potential too. The stability structure of GaN is seen that difference lattice parameter 11% lower than another calculation and experiment result. It is shown the stability structure GaN have direct band gap energy on Gamma point hexagonal lattice Brillouin zone. The width Eg is 2.6 eV. When one atom Ga is substituted with one atom RE, the bond length is change 12 % longest. An in good agreement with theoretical doping RE concentration increases, the edge of energy level shifted towards to make the band gap narrow which is allow the optical transitions and help to improve the optical performance of GaN. The RE doped GaN is potentially applicable for various color of LED with lower energy consumption and potentially energy saving application

Benchmarking the Bethe–Salpeter Formalism on a Standard Organic Molecular Set

PubMed Central

2015-01-01

We perform benchmark calculations of the Bethe–Salpeter vertical excitation energies for the set of 28 molecules constituting the well-known Thiel’s set, complemented by a series of small molecules representative of the dye chemistry field. We show that Bethe–Salpeter calculations based on a molecular orbital energy spectrum obtained with non-self-consistent G0W0 calculations starting from semilocal DFT functionals dramatically underestimate the transition energies. Starting from the popular PBE0 hybrid functional significantly improves the results even though this leads to an average −0.59 eV redshift compared to reference calculations for Thiel’s set. It is shown, however, that a simple self-consistent scheme at the GW level, with an update of the quasiparticle energies, not only leads to a much better agreement with reference values, but also significantly reduces the impact of the starting DFT functional. On average, the Bethe–Salpeter scheme based on self-consistent GW calculations comes close to the best time-dependent DFT calculations with the PBE0 functional with a 0.98 correlation coefficient and a 0.18 (0.25) eV mean absolute deviation compared to TD-PBE0 (theoretical best estimates) with a tendency to be red-shifted. We also observe that TD-DFT and the standard adiabatic Bethe–Salpeter implementation may differ significantly for states implying a large multiple excitation character. PMID:26207104

The large amplitude motions of methylamine from the perspective of the highly correlated ab initio methods

NASA Astrophysics Data System (ADS)

Senent, M. L.

2018-01-01

CCSD(T)-F12 theory in connection with extended basis sets is employed to determine the electronic ground state spectroscopic parameters of methylamine at low temperatures. The geometry, the rotational constants, all the fundamental frequencies, the dipole moment and its components, and the centrifugal distortion constants, are provided. The ground vibrational state rotational constants were found to be A0 = 103067.15 MHz, B0 = 22588.29 MHz, and C0 = 21710.50 MHz and the dipole moment to be 1.4071D. Fermi displacements of the vibrational bands are predicted. The low vibrational energy levels corresponding to the large amplitude motions are determine variationally using a flexible three-dimensional model depending on three variables: the HNH bending, the NH2 wagging and the CH3 torsional coordinates. The computed levels are compared with previous experimental and calculated energies. Methylamine parameters are very sensitive to the level of ab initio calculations.

Study on Properties of Energy Spectra of the Molecular Crystals

NASA Astrophysics Data System (ADS)

Pang, Xiao-Feng; Chen, Xiang-Rong

The energy-spectra of nonlinear vibration of molecular crystals such as acetanilide have been calculated by using discrete nonlinear Schrödinger equation appropriate to the systems, containing various interactions. The energy levels including higher excited states are basically consistent with experimental values obtained by infrared absorption and Raman scattering in acetanilide. We further give the features of distribution of the energy-spectra for the acetanilide. Using the energy spectra we also explained well experimental results obtained by Careri et al..

Excited-state relaxation in PbSe quantum dots

NASA Astrophysics Data System (ADS)

An, Joonhee M.; Califano, Marco; Franceschetti, Alberto; Zunger, Alex

2008-04-01

In solids the phonon-assisted, nonradiative decay from high-energy electronic excited states to low-energy electronic excited states is picosecond fast. It was hoped that electron and hole relaxation could be slowed down in quantum dots, due to the unavailability of phonons energy matched to the large energy-level spacings ("phonon-bottleneck"). However, excited-state relaxation was observed to be rather fast (⩽1ps) in InP, CdSe, and ZnO dots, and explained by an efficient Auger mechanism, whereby the excess energy of electrons is nonradiatively transferred to holes, which can then rapidly decay by phonon emission, by virtue of the densely spaced valence-band levels. The recent emergence of PbSe as a novel quantum-dot material has rekindled the hope for a slow down of excited-state relaxation because hole relaxation was deemed to be ineffective on account of the widely spaced hole levels. The assumption of sparse hole energy levels in PbSe was based on an effective-mass argument based on the light effective mass of the hole. Surprisingly, fast intraband relaxation times of 1-7ps were observed in PbSe quantum dots and have been considered contradictory with the Auger cooling mechanism because of the assumed sparsity of the hole energy levels. Our pseudopotential calculations, however, do not support the scenario of sparse hole levels in PbSe: Because of the existence of three valence-band maxima in the bulk PbSe band structure, hole energy levels are densely spaced, in contradiction with simple effective-mass models. The remaining question is whether the Auger decay channel is sufficiently fast to account for the fast intraband relaxation. Using the atomistic pseudopotential wave functions of Pb2046Se2117 and Pb260Se249 quantum dots, we explicitly calculated the electron-hole Coulomb integrals and the P →S electron Auger relaxation rate. We find that the Auger mechanism can explain the experimentally observed P →S intraband decay time scale without the need to invoke any exotic relaxation mechanisms.

A new energy transfer channel from carotenoids to chlorophylls in purple bacteria.

PubMed

Feng, Jin; Tseng, Chi-Wei; Chen, Tingwei; Leng, Xia; Yin, Huabing; Cheng, Yuan-Chung; Rohlfing, Michael; Ma, Yuchen

2017-07-10

It is unclear whether there is an intermediate dark state between the S 2 and S 1 states of carotenoids. Previous two-dimensional electronic spectroscopy measurements support its existence and its involvement in the energy transfer from carotenoids to chlorophylls, but there is still considerable debate on the origin of this dark state and how it regulates the energy transfer process. Here we use ab initio calculations on excited-state dynamics and simulated two-dimensional electronic spectrum of carotenoids from purple bacteria to provide evidence supporting that the dark state may be assigned to a new A g + state. Our calculations also indicate that groups on the conjugation backbone of carotenoids may substantially affect the excited-state levels and the energy transfer process. These results contribute to a better understanding of carotenoid excited states.Carotenoids harvest energy from light and transfer it to chlorophylls during photosynthesis. Here, Feng et al. perform ab initio calculations on excited-state dynamics and simulated 2D electronic spectrum of carotenoids, supporting the existence of a new excited state in carotenoids.

Diurnal tides in the Arctic Ocean

NASA Technical Reports Server (NTRS)

Kowalik, Z.; Proshutinsky, A. Y.

1993-01-01

A 2D numerical model with a space grid of about 14 km is applied to calculate diurnal tidal constituents K(1) and O(1) in the Arctic Ocean. Calculated corange and cotidal charts show that along the continental slope, local regions of increased sea level amplitude, highly variable phase and enhanced currents occur. It is shown that in these local regions, shelf waves (topographic waves) of tidal origin are generated. In the Arctic Ocean and Northern Atlantic Ocean more than 30 regions of enhanced currents are identified. To prove the near-resonant interaction of the diurnal tides with the local bottom topography, the natural periods of oscillations for all regions have been calculated. The flux of energy averaged over the tidal period depicts the gyres of semitrapped energy, suggesting that the shelf waves are partially trapped over the irregularities of the bottom topography. It is shown that the occurrence of near-resonance phenomenon changes the energy flow in the tidal waves. First, the flux of energy from the astronomical sources is amplified in the shelf wave regions, and afterwards the tidal energy is strongly dissipated in the same regions.

Cs and Ag co-incorporation in cubic silicon carbide

NASA Astrophysics Data System (ADS)

Londono-Hurtado, Alejandro; Heim, Andrew J.; Kim, Sungtae; Szlufarska, Izabela; Morgan, Dane

2013-08-01

Understanding the diffusion of fission products Cs and Ag through the SiC layer of TRISO particles is of particular interest for the progress and improvement of the High Temperature Gas Reactor (HTGR) technologies. Although the SiC layer acts as a barrier for fission products, there is experimental evidence of Cs and Ag diffusion through this layer. Previous considerations of Ag and Cs in SiC have focused on the element interacting with SiC, but have not considered the possibility of co-incorporation with another species. This paper presents a ab initio study on the co-incorporation of Cs and Ag with an anion (Iodine (I) or Oxygen (O)) into SiC as an alternative incorporation mechanism. It is found that for crystalline SiC, Ag co-incorporation with Iodine (I) and Oxygen (O) into SiC is not energetically favorable, while Cs co-incorporation with O is a preferred mechanism under some oxygen partial pressures of interest. However, Cs-O co-incorporation into the crystalline portion of SiC is not sufficiently strong to enable a Cs solubility that accounts for the Cs release observed in some experiments. Formation energies are a function of the chemical potential of Si and C. Calculations in this paper are performed for Si-rich and C-rich conditions, which constitute the boundaries for which the formation energies are allowed to vary. Calculation of the electronic potential shift is required in order to ensure that the Fermi level in a defected cell is defined with respect to the same valence band level in the undefected cell [21,23]. The potential shift is calculated by aligning low energy levels in the total density of states (DOS) [24]. Spurious interactions between images of the charged defects make it necessary to correct for unphysical electrostatic interactions. Both the monopole-monopole and monopole-quadrupole Makov Payne corrections are used for this purpose. However, strain and incompletely corrected electrostatic interactions can still lead to significant finite size effects [25]. Based on finite size scaling studies of our largest charged cluster (CsC-OC-2VSi)4-, we estimate these effects lead to errors on the scale of 1.9 eV. Due to the fact that DFT formalism is unable to reproduce experimental band gaps in materials, underestimation of the band gap is expected. This can have an effect on the calculation of the charged defect formation energies. Therefore, the energetics and charge states of the defects must be treated as somewhat approximate. In this work, the value of the Fermi level is taken to be at the conduction band minimum, a choice that is consistent with an n-type material. This is justified by the fact that as-prepared SiC is generally n-type, with a low concentration of electron carriers [26-29]. It is also important to note that, even if SiC had an intrinsically lower Fermi level, under irradiation conditions long lived electronic excitations might provide effectively higher Fermi levels in the system. Irradiation induced defects such as vacancies and interstitials have been reported to lead to Fermi levels at the middle of the band gap [30,31]. For the case of negatively charged defects, having a Fermi level closer to the middle of the band gap will result in lower defect formation energies. This aspect is not critical for our study since our goal is not to calculate highly accurate formation energies or defect charge states but to compare these energies to identify qualitative trends of co-incorporate for the different defect clusters. Based on the above comments, results presented in this paper can be expected to have some quantitative inaccuracies but the conclusions drawn from these results are still of qualitative value. Furthermore, as will be shown in the result section, formation energy differences between competing energy clusters are above 1 eV for most cases. The main goals of this work are to identify whether Cs and Ag co-incorporation with O and I into SiC can lead to more stable defects than those calculated for simple Cs and Ag defect clusters in SiC and to identify the most stable Cs/Ag-O-V defect clusters in SiC. Although some error will be associated with the formation energies due the limitations discussed above, these do not undermine the qualitative objectives of this work.Oxygen and Iodine chemical potential: In order to calculate the formation energies for Cs/Ag-O defect clusters, it is necessary to define the reference states that will be used in Eq. (1). We make the approximation that the reference for Cs and Ag is their pure metal form. The reference cancels from all comparisons between direct and co-incorporation and therefore only plays a role when considering formation energies for estimating solubility. These reference states can be justified as a bounding case for solubility calculations since it can be argued that if Ag and Cs are not in metal form in the TRISO particle, it is because they are in a more stable state. Therefore, by choosing the metal form of Cs and Ag as the reference, formation energies can be viewed as an upper bound of their chemical potential. As a consequence, formation energies calculated using this reference provide the lower bound for the true formation energy (i.e., the true formation energy would be more positive, leading to lower solubility) [11]. For the anions O and I we use the gas phase O2 and I2 molecules as the reference states, which are calculated as follows:The chemical potential of O is calculated as proposed by Lee et al. [32]: μ={1}/{2}EOVASP+ΔhO0+[H(T,P0)-H(T0,P0)]-TS(T,P0)+kTln(P/P0) where EOVASP is the T = 0 K energy as obtained from the DFT calculations, ΔhO0 is the correction for errors of the oxygen energy in O2 molecules vs. a solid, H is the O2 gas enthalpy, S is the O2 gas entropy, P is the oxygen partial pressure (P0 = 1 atm), T is the temperature (T0 = 298.15 K), and k is the Boltzman constant. The term [H(T,P0)-H(T0,P0)]-TS(T,P0) constitutes the free energy per O of O2 gas relative to the gas enthalpy at P = P0 and T = T0. This term is evaluated based on experimental data from Ref. [33]. Eqs. (1) and (2) are employed to calculate the defect formation energies of oxygen co-incorporation with Cs and Ag into SiC as a function of partial pressure. This approach treats the enthalpy at P0 and T0 as equal to the VASP energy at T = 0 K and further, does not include vibrational terms in the adsorbed species that will be contributing to the gas phase. However, we believe that the contributions of these terms to the chemical potential are small enough for the systems used in our analysis that leaving it out of the model is consistent with the qualitative goals of this work.An analogous approach can be used to treat I2, which gives the relations: μI={1}/{2}EIVASP+ΔhI0+[H(T,P0)-H(T0,P0)]-TS(T,P0)+kTln(P/P0) where EIVASP is the T = 0 K energy as obtained from the DFT calculations, ΔhI0 is the correction for errors of the oxygen energy in I2 molecules vs. a solid, H is the I2 gas enthalpy, S and is the I2 gas entropy. However, we will use a simplified reference for the I chemical potential, which can be justified as follows. It is observed from Eq. (3) that the overall effect of enthalpy and entropy is to decrease the absolute value of the I2 chemical potential for any reasonable P and T that might be encountered under reactor conditions. Furthermore, we will assume that HI2 is small on the scale of the co-incorporation energies (see below), and does not have a significant impact on the overall energetics. With this approximation we see that by choosing the EIVASP as our reference, we are calculating the upper bound of the true formation energy. As will be presented in Section 3, formation energies calculated for the case Ag/Cs-I co-incorporation using the isolated I2 molecule in vacuum at 0 K as the reference state were found to be 5.6 eV or higher than the most stable incorporation defect. While this result does not correct for possible enthalpy errors (the ΔhI0 term), the term accounting for entalphy errors is very unlikely to be on the scale of a few eV. Therefore, we see that even with an upper bound of the chemical potential for I, we can rule out I co-incorporation. As a consequence, we simply take the chemical potential of I to be {1}/{2}EIVASP, and no further refining of the chemical potential was pursued using Eq. (3).

Resummation of divergent perturbation series: Application to the vibrational states of H{sub 2}CO molecule

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

Duchko, A. N.; V.E. Zuev Institute of Atmospheric Optics, Tomsk; Bykov, A. D., E-mail: adbykov@rambler.ru

2015-10-21

Large-order Rayleigh–Schrödinger perturbation theory (RSPT) is applied to the calculation of anharmonic vibrational energy levels of H{sub 2}CO molecule. We use the model of harmonic oscillators perturbed by anharmonic terms of potential energy. Since the perturbation series typically diverge due to strong couplings, we apply the algebraic approximation technique because of its effectiveness shown earlier by Goodson and Sergeev [J. Chem. Phys. 110, 8205 (1999); ibid. 124, 094111 (2006)] and in our previous articles [A. D. Bykov et al. Opt. Spectrosc. 114, 396 (2013); ibid. 116, 598 (2014)]. To facilitate the resummation of terms contributing to perturbed states, when resonancemore » mixing between states is especially strong and perturbation series diverge very quick, we used repartition of the Hamiltonian by shifting the normal mode frequencies. Energy levels obtained by algebraic approximants were compared with the results of variational calculation. It was found that for low energy states (up to ∼5000 cm{sup −1}), algebraic approximants gave accurate values of energy levels, which were in excellent agreement with the variational method. For highly excited states, strong and multiple resonances complicate series resummation, but a suitable change of normal mode frequencies allows one to reduce the resonance mixing and to get accurate energy levels. The theoretical background of the problem of RSPT series divergence is discussed along with its numerical analysis. For these purposes, the vibrational energy is considered as a function of a complex perturbation parameter. Layout and classification of its singularities allow us to model the asymptotic behavior of the perturbation series and prove the robustness of the algorithm.« less

Variational study on the vibrational level structure and IVR behavior of highly vibrationally excited S0 formaldehyde.

PubMed

Rashev, Svetoslav; Moule, David C

2012-02-15

We perform large scale converged variational vibrational calculations on S(0) formaldehyde up to very high excess vibrational energies (E(v)), E(v)∼17,000cm(-1), using our vibrational method, consisting of a specific search/selection/Lanczos iteration procedure. Using the same method we investigate the vibrational level structure and intramolecular vibrational redistribution (IVR) characteristics for various vibrational levels in this energy range in order to assess the onset of IVR. Copyright © 2011 Elsevier B.V. All rights reserved.

Optoelectronic studies on heterocyclic bases of deoxyribonucleic acid for DNA photonics.

PubMed

El-Diasty, Fouad; Abdel-Wahab, Fathy

2015-10-01

The optoelectronics study of large molecules, particularly π-stacking molecules, such as DNA is really an extremely difficult task. We perform first electronic structure calculations on the heterocyclic bases of 2'-deoxyribonucleic acid based on Lorentz-Fresnel dispersion theory. In the UV-VIS range of spectrum, many of the optoelectronic parameters for DNA four bases namely adenine, guanine, cytosine and thymine are calculated and discussed. The results demonstrate that adenine has the highest hyperpolarizability, whereas thymine has the lowest hyperpolarizability. Cytosine has the lower average oscillator energy and the higher lattice energy. Thymine infers the most stable nucleic base with the lower phonon energy. Thymine also has the highest average oscillator energy and the lower lattice energy. Moreover, the four nucleic acid bases have large band gap energies less than 5 eV with a semiconducting behavior. Guanine shows the smallest band gap and the highest Fermi level energy, whereas adenine elucidates the highest band gap energy. Copyright © 2015. Published by Elsevier B.V.

Treating Subvalence Correlation Effects in Domain Based Pair Natural Orbital Coupled Cluster Calculations: An Out-of-the-Box Approach.

PubMed

Bistoni, Giovanni; Riplinger, Christoph; Minenkov, Yury; Cavallo, Luigi; Auer, Alexander A; Neese, Frank

2017-07-11

The validity of the main approximations used in canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) in standard chemical applications is discussed. In particular, we investigate the dependence of the results on the number of electrons included in the correlation treatment in frozen-core (FC) calculations and on the main threshold governing the accuracy of DLPNO all-electron (AE) calculations. Initially, scalar relativistic orbital energies for the ground state of the atoms from Li to Rn in the periodic table are calculated. An energy criterion is used for determining the orbitals that can be excluded from the correlation treatment in FC coupled cluster calculations without significant loss of accuracy. The heterolytic dissociation energy (HDE) of a series of metal compounds (LiF, NaF, AlF 3 , CaF 2 , CuF, GaF 3 , YF 3 , AgF, InF 3 , HfF 4 , and AuF) is calculated at the canonical CCSD(T) level, and the dependence of the results on the number of correlated electrons is investigated. Although for many of the studied reactions subvalence correlation effects contribute significantly to the HDE, the use of an energy criterion permits a conservative definition of the size of the core, allowing FC calculations to be performed in a black-box fashion while retaining chemical accuracy. A comparison of the CCSD and the DLPNO-CCSD methods in describing the core-core, core-valence, and valence-valence components of the correlation energy is given. It is found that more conservative thresholds must be used for electron pairs containing at least one core electron in order to achieve high accuracy in AE DLPNO-CCSD calculations relative to FC calculations. With the new settings, the DLPNO-CCSD method reproduces canonical CCSD results in both AE and FC calculations with the same accuracy.

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.

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.

An experimental and theoretical core-level study of tautomerism in guanine.

PubMed

Plekan, Oksana; Feyer, Vitaliy; Richter, Robert; Coreno, Marcello; Vall-Llosera, Gemma; Prince, Kevin C; Trofimov, Alexander B; Zaytseva, Irina L; Moskovskaya, Tatyana E; Gromov, Evgeniy V; Schirmer, Jochen

2009-08-20

The core level photoemission and near edge X-ray photoabsorption spectra of guanine in the gas phase have been measured and the results interpreted with the aid of high level ab initio calculations. Tautomers are clearly identified spectroscopically, and their relative free energies and Boltzmann populations at the temperature of the experiment (600 K) have been calculated and compared with the experimental results and with previous calculations. We obtain good agreement between experiment and the Boltzmann weighted theoretical photoemission spectra, which allows a quantitative determination of the ratio of oxo to hydroxy tautomer populations. For the photoabsorption spectra, good agreement is found for the C 1s and O 1s spectra but only fair agreement for the N 1s edge.

Theoretical investigation of the laser cooling of a LiBe molecule

NASA Astrophysics Data System (ADS)

You, Yang; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang

2015-09-01

An optical scheme to create the simplest heteronuclear metal ultracold LiBe molecule is proposed based on ab initio quantum chemistry calculations. The potential energy curves, dipole moments, and transition dipole moments of 1 +2Σ , 2 +2Σ , 1 2Π , and 2 2Π states are calculated using the multireference configuration interaction and large basis sets. The analytical functions deduced from the obtained curves are used to determine the rovibrational energy levels, the Franck-Condon factors, and the Einstein coefficients of the states through solving the Schrödinger equation of nuclear movement. The spectroscopic parameters are deduced with the obtained rovibrational energy levels. The Franck-Condon factors (f00:0.998 , f11:0.986 , f22:0.920 ) for the 2 +2Σ(v =0 ) ↔1 +2Σ(v'=0 ) transition are highly diagonally distributed, and the calculated radiative lifetime (74.87 ns) of the 2 +2Σ state is found to be short enough for rapid laser cooling. The results demonstrate that LiBe could be a very promising candidate for laser cooling and a three-cycle laser cooling scheme for the molecule has been proposed.

Effect of feeding different dietary levels of energy and protein on growth performance and immune status of Vanaraja chicken in the tropic.

PubMed

Perween, Shahla; Kumar, Kaushalendra; Chandramoni; Kumar, Sanjay; Singh, Pankaj Kumar; Kumar, Manoj; Dey, Amitava

2016-08-01

The present study was conducted to observe the effect of feeding dietary level of energy and protein on growth performance and immune status of Vanaraja chicken in the tropic. The experiment was conducted for 56 days on 540 1-day-old chicks, which were individually weighed and distributed into nine groups having 60 birds in each. Each group was further subdivided into triplicates having 20 birds in each. Nine different experimental rations were formulated with three levels of protein, viz., 17%, 19%, and 21%; each with three levels of energy (2600, 2800, and 3000 kcal metabolizable energy [ME]/kg), respectively. Group T8 serves as control fed with 21% protein and 2800 kcal energy as per Project Directorate of Poultry, Hyderabad given requirement. Feed consumption, live weight gain, body weight change, and feed conversion ratio (FCR) were calculated based on the amount of feed consumed every week. All the birds were vaccinated following standard protocol. The hemagglutination inhibition (HI) test have been performed to assess the immunity potential of birds due to dietary effect, and serum samples were subjected to HI test at 7, 14, 21, and 28 days of age. Finally, economics of broiler production was calculated on the cost of feed per kg live weight gain. This study revealed that the effect of feeding different levels of energy and protein on growth parameters such as body weight gain and FCR was found to be significantly higher (p<0.05) containing 19% and 21% crude protein with 3000 kcal ME/kg in Vanaraja birds. There was a gradual increase in antibody titer against New castle disease virus as the level of protein and energy increase. It is speculated that the better body weight gain corroborate health and antibody titer. Moreover, the better immune response recorded in the study might be due to better nutrient utilization and its extension toward the better immune response. Higher energy with medium protein diet positively reflects to obtain desirable performance economically. It was positive inclination toward ration containing high protein and energy which influence the immune response of Vanaraja birds to obtained desirable performance economically also.

Octet baryons in large magnetic fields

NASA Astrophysics Data System (ADS)

Deshmukh, Amol; Tiburzi, Brian C.

2018-01-01

Magnetic properties of octet baryons are investigated within the framework of chiral perturbation theory. Utilizing a power counting for large magnetic fields, the Landau levels of charged mesons are treated exactly giving rise to baryon energies that depend nonanalytically on the strength of the magnetic field. In the small-field limit, baryon magnetic moments and polarizabilities emerge from the calculated energies. We argue that the magnetic polarizabilities of hyperons provide a testing ground for potentially large contributions from decuplet pole diagrams. In external magnetic fields, such contributions manifest themselves through decuplet-octet mixing, for which possible results are compared in a few scenarios. These scenarios can be tested with lattice QCD calculations of the octet baryon energies in magnetic fields.

An adaptive interpolation scheme for molecular potential energy surfaces

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

Kowalewski, Markus, E-mail: mkowalew@uci.edu; Larsson, Elisabeth; Heryudono, Alfa

The calculation of potential energy surfaces for quantum dynamics can be a time consuming task—especially when a high level of theory for the electronic structure calculation is required. We propose an adaptive interpolation algorithm based on polyharmonic splines combined with a partition of unity approach. The adaptive node refinement allows to greatly reduce the number of sample points by employing a local error estimate. The algorithm and its scaling behavior are evaluated for a model function in 2, 3, and 4 dimensions. The developed algorithm allows for a more rapid and reliable interpolation of a potential energy surface within amore » given accuracy compared to the non-adaptive version.« less

Energy status and oxidation reduction status in rat liver at high altitude /3.8 km/

NASA Technical Reports Server (NTRS)

Reed, R. D.; Pace, N.

1980-01-01

Adult male rats were exposed to 3.8-km altitude for intervals ranging from 1 h-60 d. Liver samples were taken under light ether anesthesia and were examined by enzymatic analyses. Within 1-6 h of hypoxic exposure, ATP levels decreased while ADP and AMP levels increased, producing a fall in calculated ATP/ADP and adenylate charge ratios. Concurrently, lactate/pyruvate and alpha-glycerophosphate/dihydroxyacetone phosphate ratios increased markedly. Direct measurements of cellular pyridine nucleotides indicated increased NADH/NAD and NADPH/NADP ratios. Levels of total adenosine phosphates and pyridine nucleotides decreased in a significant accompanying response. Many metabolite levels and calculated ratios returned to near-normal values within 1 week of exposure, indicating secondary intracellular adjustments to hypoxic stress; however, persistence of that stress is reflected in lactate concentrations and both substrate redox ratios. Results support and explore concepts that increased oxidation-reduction status and decreased energy status are primary events during hypoxia.

Experimental and Ab Initio Studies of the HDO Absorption Spectrum in the 13165-13500 1/cm Spectral Region

NASA Technical Reports Server (NTRS)

Schwenke, David; Naumenko, Olga; Bertseva, Elena; Campargue, Alain; Arnold, James O. (Technical Monitor)

2000-01-01

The HDO absorption spectrum has been recorded in the 13165 - 13500 cm(exp-1) spectral region by Intracavity Laser Absorption Spectroscopy. The spectrum (615 lines), dominated by the 2n2 + 3n3 and n1+3n3 bands was assigned and modeled leading to the derivation of 196 accurate energy levels of the (103) and (023) vibrational states. Finally, 150 of these levels have been reproduced by an effective Hamiltonian involving two vibrational dark states interacting with the (023) and ( 103) bright states. The rms deviation achieved by variation of 28 parameters is 0.05-1 cm, compared to an averaged experimental uncertainty of 0.007-1 cm, indicating the limit of validity of the effective Hamiltonian approach for HDO at high vibrational excitation. The predictions of previous ab initio calculations of the HDO spectrum were extensively used in the assignment process. The particular spectral region under consideration has been used to test and discuss the improvements of new ab initio calculations recently performed on the basis of the same potential energy surface but with an improved dipole moment surface. The improvements concern both the energy levels and the line intensities. In particular, the strong hybrid character of the n1+3n3 band is very well accounted for by the the new ab initio calculations.

PDB ligand conformational energies calculated quantum-mechanically.

PubMed

Sitzmann, Markus; Weidlich, Iwona E; Filippov, Igor V; Liao, Chenzhong; Peach, Megan L; Ihlenfeldt, Wolf-Dietrich; Karki, Rajeshri G; Borodina, Yulia V; Cachau, Raul E; Nicklaus, Marc C

2012-03-26

We present here a greatly updated version of an earlier study on the conformational energies of protein-ligand complexes in the Protein Data Bank (PDB) [Nicklaus et al. Bioorg. Med. Chem. 1995, 3, 411-428], with the goal of improving on all possible aspects such as number and selection of ligand instances, energy calculations performed, and additional analyses conducted. Starting from about 357,000 ligand instances deposited in the 2008 version of the Ligand Expo database of the experimental 3D coordinates of all small-molecule instances in the PDB, we created a "high-quality" subset of ligand instances by various filtering steps including application of crystallographic quality criteria and structural unambiguousness. Submission of 640 Gaussian 03 jobs yielded a set of about 415 successfully concluded runs. We used a stepwise optimization of internal degrees of freedom at the DFT level of theory with the B3LYP/6-31G(d) basis set and a single-point energy calculation at B3LYP/6-311++G(3df,2p) after each round of (partial) optimization to separate energy changes due to bond length stretches vs bond angle changes vs torsion changes. Even for the most "conservative" choice of all the possible conformational energies-the energy difference between the conformation in which all internal degrees of freedom except torsions have been optimized and the fully optimized conformer-significant energy values were found. The range of 0 to ~25 kcal/mol was populated quite evenly and independently of the crystallographic resolution. A smaller number of "outliers" of yet higher energies were seen only at resolutions above 1.3 Å. The energies showed some correlation with molecular size and flexibility but not with crystallographic quality metrics such as the Cruickshank diffraction-component precision index (DPI) and R(free)-R, or with the ligand instance-specific metrics such as occupancy-weighted B-factor (OWAB), real-space R factor (RSR), and real-space correlation coefficient (RSCC). We repeated these calculations with the solvent model IEFPCM, which yielded energy differences that were generally somewhat lower than the corresponding vacuum results but did not produce a qualitatively different picture. Torsional sampling around the crystal conformation at the molecular mechanics level using the MMFF94s force field typically led to an increase in energy. © 2012 American Chemical Society

Final excitation energy of fission fragments

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

Schmidt, Karl-Heinz; Jurado, Beatriz

We study how the excitation energy of the fully accelerated fission fragments is built up. It is stressed that only the intrinsic excitation energy available before scission can be exchanged between the fission fragments to achieve thermal equilibrium. This is in contradiction with most models used to calculate prompt neutron emission, where it is assumed that the total excitation energy of the final fragments is shared between the fragments by the condition of equal temperatures. We also study the intrinsic excitation-energy partition in statistical equilibrium for different level-density descriptions as a function of the total intrinsic excitation energy of themore » fissioning system. Excitation energies are found to be strongly enhanced in the heavy fragment, if the level density follows a constant-temperature behavior at low energies, e.g., in the composed Gilbert-Cameron description.« less

Electronic properties of Bilayer Fullerene onions

NASA Astrophysics Data System (ADS)

Pincak, R.; Shunaev, V. V.; Smotlacha, J.; Slepchenkov, M. M.; Glukhova, O. E.

2017-10-01

The HOMO-LUMO gaps of the bilayer fullerene onions were investigated. For this purpose, the HOMO and LUMO energies were calculated for the isolated fullerenes using the parametrization of the tight binding method with the Harrison-Goodwin modification. Next, the difference of the Fermi levels of the outer and inner shell was calculated by considering the hybridization of the orbitals on the base of the geometric parameters. The results were obtained by the combination of these calculations.

A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H{sub 2}

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

Denis-Alpizar, Otoniel, E-mail: otonieldenisalpizar@gmail.com; Departamento de Física, Universidad de Matanzas, Matanzas 40100; Kalugina, Yulia

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H{sub 2}. Ab initio calculations of the HCN–H{sub 2} van der Waals complex, considering both molecules as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN–H{sub 2} with the nitrogen pointing towards H{sub 2} at an intermolecular separation of 7.20 a{sub 0}. The corresponding well depth is −195.20 cm{sup −1}. A secondary minimum of −183.59 cm{sup −1}more » was found for a T-shape configuration with the H of HCN pointing to the center of mass of H{sub 2}. We also determine the rovibrational energy levels of the HCN–para-H{sub 2} and HCN–ortho-H{sub 2} complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm{sup −1} and 60.26 cm{sup −1}, respectively. The calculated ro-vibrational transitions in the HCN–H{sub 2} complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.« less

Structure of the Odd-Odd Nucleus {sup 188}Re

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

Balodis, M.; Berzins, J.; Simonova, L.

2009-01-28

Thermal neutron capture gamma-ray spectra for {sup 187}Re(n,{gamma}){sup 188}Re reaction were measured. Singles and coincidence spectra were detected in order to develop the level scheme. The evaluation is in progress, of which the first results are obtained from the analysis of coincidence spectra, allowing to check the level scheme below 500 keV excitation energy. Seven low-energy negative parity bands are developed in order to find better energies for rotational levels. With a good confidence, a few positive parity bands are developed as well. Rotor plus two quasiparticle model calculations, employing effective matrix element method are performed for the system ofmore » six negative parity rotational bands.« less

Quantum thermodynamics of the resonant-level model with driven system-bath coupling

NASA Astrophysics Data System (ADS)

Haughian, Patrick; Esposito, Massimiliano; Schmidt, Thomas L.

2018-02-01

We study nonequilibrium thermodynamics in a fermionic resonant-level model with arbitrary coupling strength to a fermionic bath, taking the wide-band limit. In contrast to previous theories, we consider a system where both the level energy and the coupling strength depend explicitly on time. We find that, even in this generalized model, consistent thermodynamic laws can be obtained, up to the second order in the drive speed, by splitting the coupling energy symmetrically between system and bath. We define observables for the system energy, work, heat, and entropy, and calculate them using nonequilibrium Green's functions. We find that the observables fulfill the laws of thermodynamics, and connect smoothly to the known equilibrium results.

Accelerating ab initio path integral molecular dynamics with multilevel sampling of potential surface

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

Geng, Hua Y., E-mail: huay.geng@gmail.com; Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, NY 14853

A multilevel approach to sample the potential energy surface in a path integral formalism is proposed. The purpose is to reduce the required number of ab initio evaluations of energy and forces in ab initio path integral molecular dynamics (AI-PIMD) simulation, without compromising the overall accuracy. To validate the method, the internal energy and free energy of an Einstein crystal are calculated and compared with the analytical solutions. As a preliminary application, we assess the performance of the method in a realistic model—the FCC phase of dense atomic hydrogen, in which the calculated result shows that the acceleration rate ismore » about 3 to 4-fold for a two-level implementation, and can be increased up to 10 times if extrapolation is used. With only 16 beads used for the ab initio potential sampling, this method gives a well converged internal energy. The residual error in pressure is just about 3 GPa, whereas it is about 20 GPa for a plain AI-PIMD calculation with the same number of beads. The vibrational free energy of the FCC phase of dense hydrogen at 300 K is also calculated with an AI-PIMD thermodynamic integration method, which gives a result of about 0.51 eV/proton at a density of r{sub s}=0.912.« less

Full Wave Function Optimization with Quantum Monte Carlo and Its Effect on the Dissociation Energy of FeS.

PubMed

Haghighi Mood, Kaveh; Lüchow, Arne

2017-08-17

Diffusion quantum Monte Carlo calculations with partial and full optimization of the guide function are carried out for the dissociation of the FeS molecule. For the first time, quantum Monte Carlo orbital optimization for transition metal compounds is performed. It is demonstrated that energy optimization of the orbitals of a complete active space wave function in the presence of a Jastrow correlation function is required to obtain agreement with the experimental dissociation energy. Furthermore, it is shown that orbital optimization leads to a 5 Δ ground state, in agreement with experiments but in disagreement with other high-level ab initio wave function calculations which all predict a 5 Σ + ground state. The role of the Jastrow factor in DMC calculations with pseudopotentials is investigated. The results suggest that a large Jastrow factor may improve the DMC accuracy substantially at small additional cost.

Theoretical studies of dissociative recombination

NASA Technical Reports Server (NTRS)

Guberman, S. L.

1985-01-01

The calculation of dissociative recombination rates and cross sections over a wide temperature range by theoretical quantum chemical techniques is described. Model calculations on electron capture by diatomic ions are reported which illustrate the dependence of the rates and cross sections on electron energy, electron temperature, and vibrational temperature for three model crossings of neutral and ionic potential curves. It is shown that cross sections for recombination to the lowest vibrational level of the ion can vary by several orders of magnitude depending upon the position of the neutral and ionic potential curve crossing within the turning points of the v = 1 vibrational level. A new approach for calculating electron capture widths is reported. Ab initio calculations are described for recombination of O2(+) leading to excited O atoms.

Does endogenous GLP-1 affect resting energy expenditure and fuel selection in overweight and obese adults?

PubMed

Poggiogalle, E; Donini, L M; Chiesa, C; Pacifico, L; Lenzi, A; Perna, S; Faliva, M; Naso, M; Rondanelli, M

2018-04-01

To investigate the association between fasting glucagon-like peptide 1 (GLP-1) levels and resting energy expenditure (REE), and respiratory quotient (RQ) in overweight and obese adults. Study participants were enrolled at the Dietetic and Metabolic Unit, University of Pavia, Italy. Inclusion criteria were age ≥ 25 and ≤ 45 years, and body mass index (BMI) ≥ 25 and ≤ 35 kg/m 2 . Diabetic subjects were excluded. Body composition was measured by dual-energy X-ray absorptiometry. REE was evaluated using indirect calorimetry, and RQ was calculated from respiratory gas exchanges. Fasting GLP-1, glucose, insulin and free fatty acid (FFA) levels, and 24-h norepinephrine urinary excretion were measured. Homeostasis model assessments of insulin resistance (HOMA-IR) and beta-cell function (HOMA-β) were calculated. Thirty-seven participants were included (age 43.4 ± 1.6 years; BMI 30.6 ± 0.5 kg/m 2 ). REE was not associated with fasting GLP-1 levels (p = 0.98) after adjustment for age, sex, fat-free mass (FFM), and fat mass (FM). Similarly, no association was observed between RQ and GLP-1 levels (p = 0.95), after adjustment for age, sex, and body fat. In adults subjects with increased adiposity fasting, GLP-1 levels do not seem to play a role in the regulation of energy metabolism and in fuel selection.

Potential energy surface and quantum dynamics study of rovibrational states for HO(3) (X (2)A'').

PubMed

Braams, Bastiaan J; Yu, Hua-Gen

2008-06-07

An analytic potential energy surface has been constructed by fitting to about 28 thousand energy points for the electronic ground-state (X (2)A'') of HO(3). The energy points are calculated using a hybrid density functional HCTH and a large basis set aug-cc-pVTZ, i.e., a HCTH/aug-cc-pVTZ density functional theory (DFT) method. The DFT calculations show that the trans-HO(3) isomer is the global minimum with a potential well depth of 9.94 kcal mol(-1) with respect to the OH + O(2) asymptote. The equilibrium geometry of the cis-HO(3) conformer is located 1.08 kcal mol(-1) above that of the trans-HO(3) one with an isomerization barrier of 2.41 kcal mol(-1) from trans- to cis-HO(3). By using this surface, a rigorous quantum dynamics (QD) study has been carried out for computing the rovibrational energy levels of HO(3). The calculated results determine a dissociation energy of 6.15 kcal mol(-1), which is in excellent agreement with the experimental value of Lester et al. [J. Phys. Chem. A, 2007, 111, 4727.].

The molecular structure and conformation of tetrabromoformaldazine: ab initio and DFT calculations

NASA Astrophysics Data System (ADS)

Jeong, Myongho; Kwon, Younghi

2000-06-01

Ab initio and density functional theory methods are applied to investigate the molecular structure and conformational nature of tetrabromoformaldazine. The calculations including the effects of the electron correlation at the B3LYP and MP2 levels with the basis set 6-311+G(d) can reproduce the experimental geometrical parameters at the skew conformation. The N-N bond torsional angle φ calculated at the MP2/6-311+G(d) level is found to be closest to the observed angle. The scanning of the potential energy surface suggests that the anti-conformation is at a saddle point corresponding to the transition state.

An economic prediction of the finer resolution level wavelet coefficients in electronic structure calculations.

PubMed

Nagy, Szilvia; Pipek, János

2015-12-21

In wavelet based electronic structure calculations, introducing a new, finer resolution level is usually an expensive task, this is why often a two-level approximation is used with very fine starting resolution level. This process results in large matrices to calculate with and a large number of coefficients to be stored. In our previous work we have developed an adaptively refined solution scheme that determines the indices, where the refined basis functions are to be included, and later a method for predicting the next, finer resolution coefficients in a very economic way. In the present contribution, we would like to determine whether the method can be applied for predicting not only the first, but also the other, higher resolution level coefficients. Also the energy expectation values of the predicted wave functions are studied, as well as the scaling behaviour of the coefficients in the fine resolution limit.

Northwest Energy Policy Project. Energy conservation policy evaluation: study module IA. Final report. Volume I. Summary report

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

Berney, R.E.; Butcher, W.R.; Carter, L.F.

1977-01-01

This summary report identifies potential energy conservation measures and evaluates measures and policy options not likely to be suitable for adoption in the Pacific Northwest. Potential and incentives for energy conservation are specifically identified in the residential, commercial, industrial, and transportation sectors and through urban design. Selection of preferable policies and estimation of response to policies are next discussed. Finally, a computer impact model for calculating energy savings and changes in the levels of residuals resulting from energy conservation activities is discussed. (MCW)

Cl-doping of Te-rich CdTe: Complex formation, self-compensation and self-purification from first principles

NASA Astrophysics Data System (ADS)

Lindström, A.; Klintenberg, M.; Sanyal, B.; Mirbt, S.

2015-08-01

The coexistence in Te-rich CdTe of substitutional Cl-dopants, ClTe, which act as donors, and Cd vacancies, VC d - 1 , which act as electron traps, was studied from first principles utilising the HSE06 hybrid functional. We find ClTe to preferably bind to VC d - 1 and to form an acceptor complex, (ClTe-VCd)-1. The complex has a (0,-1) charge transfer level close to the valence band and shows no trap state (deep level) in the band gap. During the complex formation, the defect state of VCd-1 is annihilated and leaves the Cl-doped CdTe bandgap without any trap states (self-purification). We calculate Cl-doped CdTe to be semi-insulating with a Fermi energy close to midgap. We calculate the formation energy of the complex to be sufficiently low to allow for spontanous defect formation upon Cl-doping (self-compensation). In addition, we quantitatively analyse the geometries, DOS, binding energies and formation energies of the (ClTe-VCd) complexes.

Physical nature of ethidium and proflavine interactions with nucleic acid bases in the intercalation plane.

PubMed

Langner, Karol M; Kedzierski, Pawel; Sokalski, W Andrzej; Leszczynski, Jerzy

2006-05-18

On the basis of the crystallographic structures of three nucleic acid intercalation complexes involving ethidium and proflavine, we have analyzed the interaction energies between intercalator chromophores and their four nearest bases, using a hybrid variation-perturbation method at the second-order Møller-Plesset theory level (MP2) with a 6-31G(d,p) basis set. A total MP2 interaction energy minimum precisely reproduces the crystallographic position of the ethidium chromophore in the intercalation plane between UA/AU bases. The electrostatic component constitutes the same fraction of the total energy for all three studied structures. The multipole electrostatic interaction energy, calculated from cumulative atomic multipole moments (CAMMs), was found to converge only after including components above the fifth order. CAMM interaction surfaces, calculated on grids in the intercalation planes of these structures, reasonably reproduce the alignment of intercalators in crystal structures; they exhibit additional minima in the direction of the DNA grooves, however, which also need to be examined at higher theory levels if no crystallographic data are given.

Charge transfer and optical properties of trifluoromethyl substituted benzodithiophene (TFMBDT): A theoretical study

NASA Astrophysics Data System (ADS)

Sahoo, Smruti Ranjan; Sahu, Sridhar; Sharma, Sagar

2018-05-01

We present density functional study of the charge transport and optical properties of trifluoromethyl substituted benzodithiophene (TFMBDT) molecule. We found the hole reorganization energy, reduced by 0.354 eV compared to the electron reorganization energy, thus favoring the hole transport across the molecular barrier. We found the maximum tH and tL at the tilting angle 85°, to be 0.473 eV and 0.472 eV, respectively. Although, both tH and tL are found to equivalent, however, low λh can contribute to the larger hole mobility. In the TD-DFT calculation, the low energy electronic transition (H→L) was found to be accordance with the electronic HOMO-LUMO energy gap of the conjugated organic molecule. The calculated gas phase maximum absorption (λmax) of TFMBDT molecule was observed at 337.31 nm (3.67 eV) for B3LYP/6-311+G(d, p) level and 328.04 nm (3.77 eV) for PBE1PBE/6-311+G(d, p) level, which is mostly associated with HOMO→LUMO transition.

Density Functional Theory Calculations of Activation Energies for Carrier Capture by Defects in Semiconductors

NASA Astrophysics Data System (ADS)

Modine, N. A.; Wright, A. F.; Lee, S. R.

The rate of defect-induced carrier recombination is determined by both defect levels and carrier capture cross-sections. Density functional theory (DFT) has been widely and successfully used to predict defect levels, but only recently has work begun to focus on using DFT to determine carrier capture cross-sections. Lang and Henry developed the theory of carrier-capture by multiphonon emission in the 1970s and showed that carrier-capture cross-sections differ between defects primarily due to differences in their carrier capture activation energies. We present an approach to using DFT to calculate carrier capture activation energies that does not depend on an assumed configuration coordinate and that fully accounts for anharmonic effects, which can substantially modify carrier activation energies. We demonstrate our approach for intrinisic defects in GaAs and GaN and discuss how our results depend on the choice of exchange-correlation functional and the treatment of spin polarization. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

Analysis of the physical activity patterns of a rural Afrikaner population in the south-western Cape.

PubMed

Noakes, T D; Benade, A J; Jooste, P L; van Zyl, F

1986-06-21

To determine whether low levels of energy expenditure at work or in leisure-time might contribute to the high prevalence of coronary heart disease among white rural Afrikaners, 7188 whites of both sexes in three rural communities were questioned about their physical activities. From these data, the percentage of the population at different ages participating in sedentary, moderate or vigorous activity at work or light, moderate or vigorous leisure-time activity was calculated. Total energy expenditure at work or in leisure-time was also calculated. At all ages, less than 1% of both men and women performed workday activities requiring high energy output. Beginning after the age of 24 years, there was a dramatic fall in the percentage of both men and women participating in either moderate or vigorous leisure-time physical activity. After the age of 44 years, less than 26% of men and 16% of women exceeded the coronary 'protective threshold' of 8400 kJ leisure-time energy expenditure per week. Thus the population studied is characterized by very low levels of energy expenditure particularly at work, but also during leisure-time.

A full-dimensional ab initio potential energy surface and rovibrational energies of the Ar–HF complex

NASA Astrophysics Data System (ADS)

Huang, Jing; Zhou, Yanzi; Xie, Daiqian

2018-04-01

We report a new full-dimensional ab initio potential energy surface for the Ar-HF van der Waals complex at the level of coupled-cluster singles and doubles with noniterative inclusion of connected triples levels [CCSD(T)] using augmented correlation-consistent quintuple-zeta basis set (aV5Z) plus bond functions. Full counterpoise correction was employed to correct the basis-set superposition error. The hypersurface was fitted using artificial neural network method with a root mean square error of 0.1085 cm-1 for more than 8000 ab initio points. The complex was found to prefer a linear Ar-H-F equilibrium structure. The three-dimensional discrete variable representation method and the Lanczos propagation algorithm were then employed to calculate the rovibrational states without separating inter- and intra- molecular nuclear motions. The calculated vibrational energies of Ar-HF differ from the experiment values within about 1 cm-1 on the first four HF vibrational states, and the predicted pure rotational energies on (0000) and (1000) vibrational states are deviated from the observed value by about 1%, which shows the accuracy of our new PES.

Design and development of Building energy simulation Software for prefabricated cabin type of industrial building (PCES)

NASA Astrophysics Data System (ADS)

Zhang, Jun; Li, Ri Yi

2018-06-01

Building energy simulation is an important supporting tool for green building design and building energy consumption assessment, At present, Building energy simulation software can't meet the needs of energy consumption analysis and cabinet level micro environment control design of prefabricated building. thermal physical model of prefabricated building is proposed in this paper, based on the physical model, the energy consumption calculation software of prefabricated cabin building(PCES) is developed. we can achieve building parameter setting, energy consumption simulation and building thermal process and energy consumption analysis by PCES.

Properties of Energy Spectra of Molecular Crystals Investigated by Nonlinear Theory

NASA Astrophysics Data System (ADS)

Pang, Xiao-Feng; Zhang, Huai-Wu

We calculate the quantum energy spectra of molecular crystals, such as acetanilide, by using discrete nonlinear Schrodinger equation, containing various interactions, appropriate to the systems. The energy spectra consist of many energy bands, in each energy band there are a lot of energy levels including some higher excited states. The result of energy spectrum is basically consistent with experimental values obtained by infrared absorption and Raman scattering in acetanilide and can also explain some experimental results obtained by Careri et al. Finally, we further discuss the influences of variously characteristic parameters on the energy spectra of the systems.

Comparative PV LCOE Calculator Documentation | Photovoltaic Research | NREL

Science.gov Websites

Comparative Photovoltaic (PV) Levelized Cost of Energy (LCOE) Calculator. Getting started This tool is and watch the LCOE values in the results section change immediately. Example: Cell cost reduction In the proposed section, drag the cell cost slider or type in the cell cost numeric input field to reduce

First Principles Electronic Structure of Mn doped GaAs, GaP, and GaN Semiconductors

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

Schulthess, Thomas C; Temmerman, Walter M; Szotek, Zdzislawa

We present first-principles electronic structure calculations of Mn doped III-V semiconductors based on the local spin-density approximation (LSDA) as well as the self-interaction corrected local spin density method (SIC-LSD). We find that it is crucial to use a self-interaction free approach to properly describe the electronic ground state. The SIC-LSD calculations predict the proper electronic ground state configuration for Mn in GaAs, GaP, and GaN. Excellent quantitative agreement with experiment is found for magnetic moment and p-d exchange in (GaMn)As. These results allow us to validate commonly used models for magnetic semiconductors. Furthermore, we discuss the delicate problem of extractingmore » binding energies of localized levels from density functional theory calculations. We propose three approaches to take into account final state effects to estimate the binding energies of the Mn-d levels in GaAs. We find good agreement between computed values and estimates from photoemisison experiments.« less

The structural, electronic and optical properties of Nd doped ZnO using first-principles calculations

NASA Astrophysics Data System (ADS)

Wen, Jun-Qing; Zhang, Jian-Min; Chen, Guo-Xiang; Wu, Hua; Yang, Xu

2018-04-01

The density functional theory calculations using general gradient approximation (GGA) applying Perdew-Burke-Ernzerhof (PBE) as correlation functional have been systematically performed to research the formation energy, the electronic structures, band structures, total and partial DOS, and optical properties of Nd doping ZnO with the content from 6.25% to 12.5%. The formation energies are negative for both models, which show that two structures are energetically stable. Nd doping ZnO crystal is found to be a direct band gap semiconductor and Fermi level shifts upward into conduction band, which show the properties of n-type semiconductor. Band structures are more compact after Nd doping ZnO, implying that Nd doping induces the strong interaction between different atoms. Nd doping ZnO crystal presents occupied states at near Fermi level, which mainly comes from the Nd 4f orbital. The calculated optical properties imply that Nd doping causes a red-shift of absorption peaks, and enhances the absorption of the visible light.

A theoretical study on 2-amino-5-nitroprydinium trifluoroaceta

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

Arioğlu, Çağla, E-mail: caglaarioglu@gmail.com; Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Başoğlu, Adil, E-mail: abasoglu@sakarya.edu.tr

The geometry optimization of 2-amino-5-nitroprydinium trifluoroacetate molecule was carried out by using Becke’s three-parameter exchange functional in conjunction with the Lee-Yang-Parr correlation functional (B3LYP) level of density functional theory (DFT) and 6-311++G(d,p) basis set at GAUSSIAN 09 program. The vibration spectrum of the title compound was simulated to predict the presence of functional groups and their vibrational modes. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were calculated at the same level, and the obtained small energy gap shows that charge transfer occurs in the title compound. The molecular dipole moment, polarizability and hyperpolarizability parametersmore » were determined to evaluate nonlinear optical efficiency of the title compound. Finally, the {sup 13}C and {sup 1}H Nuclear Magnetic Resonance (NMR) chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method. All of the calculations were carried out by using GAUSSIAN 09 program.« less

Vibrational spectra of halide-water dimers: Insights on ion hydration from full-dimensional quantum calculations on many-body potential energy surfaces

NASA Astrophysics Data System (ADS)

Bajaj, Pushp; Wang, Xiao-Gang; Carrington, Tucker; Paesani, Francesco

2018-03-01

Full-dimensional vibrational spectra are calculated for both X-(H2O) and X-(D2O) dimers (X = F, Cl, Br, I) at the quantum-mechanical level. The calculations are carried out on two sets of recently developed potential energy functions (PEFs), namely, Thole-type model energy (TTM-nrg) and many-body energy (MB-nrg), using the symmetry-adapted Lanczos algorithm with a product basis set including all six vibrational coordinates. Although both TTM-nrg and MB-nrg PEFs are derived from coupled-cluster single double triple-F12 data obtained in the complete basis set limit, they differ in how many-body effects are represented at short range. Specifically, while both models describe long-range interactions through the combination of two-body dispersion and many-body classical electrostatics, the relatively simple Born-Mayer functions employed in the TTM-nrg PEFs to represent short-range interactions are replaced in the MB-nrg PEFs by permutationally invariant polynomials to achieve chemical accuracy. For all dimers, the MB-nrg vibrational spectra are in close agreement with the available experimental data, correctly reproducing anharmonic and nuclear quantum effects. In contrast, the vibrational frequencies calculated with the TTM-nrg PEFs exhibit significant deviations from the experimental values. The comparison between the TTM-nrg and MB-nrg results thus reinforces the notion that an accurate representation of both short-range interactions associated with electron density overlap and long-range many-body electrostatic interactions is necessary for a correct description of hydration phenomena at the molecular level.

Effect of cation size at Gd and Al site on ce energy levels in Gd3(GaAl)5O12 sintered pellets

NASA Astrophysics Data System (ADS)

Tyagi, Mohit; Meng, Fang; Darby, Kaitlyn; Koschan, Merry; Melcher, C. L.

2013-02-01

Radioluminescence and reflectivity measurements performed on sintered powder pellets of garnet compositions R3GaxAl5-xO12 (where R: Lu, Gd, Sc, Y) have shown that replacing "R" in these compositions with ions of larger radius shifts the excited 5d states of Ce to lower energy, while increased ionic radius at Ga/Al sites shifts these levels to higher energy. Stokes shifts were also calculated and results were verified by comparing the performance of the pellets with that of single crystals.

Critically Evaluated Energy Levels, Spectral Lines, Transition Probabilities, and Intensities of Singly Ionized Vanadium (V ii)

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

Saloman, Edward B.; Kramida, Alexander

2017-08-01

The energy levels, observed spectral lines, and transition probabilities of singly ionized vanadium, V ii, have been compiled. The experimentally derived energy levels belong to the configurations 3 d {sup 4}, 3 d {sup 3} ns ( n  = 4, 5, 6), 3 d {sup 3} np , and 3 d {sup 3} nd ( n  = 4, 5), 3 d {sup 3}4 f , 3 d {sup 2}4 s {sup 2}, and 3 d {sup 2}4 s 4 p . Also included are values for some forbidden lines that may be of interest to the astrophysical community. Experimental Landé g -factorsmore » and leading percentages for the levels are included when available, as well as Ritz wavelengths calculated from the energy levels. Wavelengths and transition probabilities are reported for 3568 and 1896 transitions, respectively. From the list of observed wavelengths, 407 energy levels are determined. The observed intensities, normalized to a common scale, are provided. From the newly optimized energy levels, a revised value for the ionization energy is derived, 118,030(60) cm{sup −1}, corresponding to 14.634(7) eV. This is 130 cm{sup −1} higher than the previously recommended value from Iglesias et al.« less

Stability, Elastic Properties, and Deformation of LiBN2: A Potential High-Energy Material.

PubMed

Zhu, Chunye; Zhu, Wenjun; Yang, Yanqiang

2018-05-15

Searching for high-energy-density materials is of great interest in scientific research and for industrial applications. Using an unbiased structure prediction method and first-principles calculations, we investigated the phase stability of LiBN 2 from 0 to100 GPa. Two new structures with space groups P4̅2 1 m and Pnma were discovered. The theoretical calculations revealed that Pnma LiBN 2 is stable with respect to a mixture of 1 / 3 Li 3 N, BN, and 1 / 3 N 2 above 22 GPa. The electronic band structure revealed that Pnma LiBN 2 has an indirect band gap of 2.3 eV, which shows a nonmetallic feature. The Pnma phase has a high calculated bulk modulus and shear modulus, indicating its incompressible nature. The microscopic mechanism of the structural deformation was demonstrated by ideal tensile shear strength calculations. It is worth mentioning that Pnma LiBN 2 is dynamically stable under ambient conditions. The decomposition of this phase is exothermic, releasing an energy of approximately 1.23 kJ/g at the PBE level. The results provide new thoughts for designing and synthesizing novel high-energy compounds in ternary systems.

Weather data for simplified energy calculation methods. Volume IV. United States: WYEC data

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

Olsen, A.R.; Moreno, S.; Deringer, J.

The objective of this report is to provide a source of weather data for direct use with a number of simplified energy calculation methods available today. Complete weather data for a number of cities in the United States are provided for use in the following methods: degree hour, modified degree hour, bin, modified bin, and variable degree day. This report contains sets of weather data for 23 cities using Weather Year for Energy Calculations (WYEC) source weather data. Considerable overlap is present in cities (21) covered by both the TRY and WYEC data. The weather data at each city hasmore » been summarized in a number of ways to provide differing levels of detail necessary for alternative simplified energy calculation methods. Weather variables summarized include dry bulb and wet bulb temperature, percent relative humidity, humidity ratio, wind speed, percent possible sunshine, percent diffuse solar radiation, total solar radiation on horizontal and vertical surfaces, and solar heat gain through standard DSA glass. Monthly and annual summaries, in some cases by time of day, are available. These summaries are produced in a series of nine computer generated tables.« less

High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formations of iron carbide (FeC) and its cation (FeC+).

PubMed

Lau, Kai-Chung; Chang, Yih-Chung; Lam, Chow-Shing; Ng, C Y

2009-12-31

The ionization energy (IE) of FeC and the 0 K bond dissociation energies (D(0)) and the heats of formation at 0 K (DeltaH(o)(f0)) and 298 K (DeltaH(o)(f298)) for FeC and FeC(+) are predicted by the single-reference wave function based CCSDTQ(Full)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations. The zero-point vibrational energy (ZPVE) correction, the core-valence electronic corrections (up to CCSDT level), spin-orbit couplings, and relativistic effects (up to CCSDTQ level) are included in the calculations. The present calculations provide the correct symmetry predictions for the ground states of FeC and FeC(+) to be (3)Delta and (2)Delta, respectively. We have also examined the theoretical harmonic vibrational frequencies of FeC/FeC(+) at the ROHF-UCCSD(T) and UHF-UCCSD(T) levels. While the UHF-UCCSD(T) harmonic frequencies are in good agreement with the experimental measurements, the ROHF-UCCSD(T) yields significantly higher harmonic frequency predictions for FeC/FeC(+). The CCSDTQ(Full)/CBS IE(FeC) = 7.565 eV is found to compare favorably with the experimental IE value of 7.59318 +/- 0.00006 eV, suggesting that the single-reference-based coupled cluster theory is capable of providing reliable IE prediction for FeC, despite its multireference character. The CCSDTQ(Full)/CBS D(0)(Fe(+)-C) and D(0)(Fe-C) give the prediction of D(0)(Fe(+)-C) - D(0)(Fe-C) = 0.334 eV, which is consistent with the experimental determination of 0.3094 +/- 0.0001 eV. The D(0) calculations also support the experimental D(0)(Fe(+)-C) = 4.1 +/- 0.3 eV and D(0)(Fe-C) = 3.8 +/- 0.3 eV determined by the previous ion photodissociation study. The present calculations also provide the DeltaH(o)(f0)(DeltaH(o)(f298)) predictions for FeC/FeC(+). The analysis of the correction terms in these calculations shows that the core-valence and valence-valence electronic correlations beyond CCSD(T) wave function and the relativistic effects make significant contributions to the calculated thermochemical properties of FeC/FeC(+). For the experimental D(0) and DeltaH(o)(f0) values of FeC/FeC(+), which are not known to high precision, we recommend the CCSDTQ(Full)/CBS predictions [D(0)(Fe-C) = 3.778 eV, D(0)(Fe(+)-C) = 4.112 eV, DeltaH(o)(f0)(FeC) = 760.8 kJ/mol and DeltaH(o)(f0)(FeC(+)) = 1490.6 kJ/mol] based on the ZPVE corrections using the experimental vibrational frequencies of FeC and FeC(+).

Microscopic study of spin cut-off factors of nuclear level densities

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

Gholami, M.; Kildir, M.; Behkami, A. N.

Level densities and spin cut-off factors have been investigated within the microscopic approach based on the BCS Hamiltonian. In particular, the spin cut-off parameters have been calculated at neutron binding energies over a large range of nuclear mass using the BCS theory. The spin cut-off parameters {sigma}{sup 2}(E) have also been obtained from the Gilbert and Cameron expression and from rigid body calculations. The results were compared with their corresponding macroscopic values. It was found that the values of {sigma}{sup 2}(E) did not increase smoothly with A as expected based on macroscopic theory. Instead, the values of {sigma}{sup 2}(E) showmore » structure reflecting the angular momentum of the shell model orbitals near the Fermi energy.« less

Study of nuclear structure of 76-86Sr isotopes in the pn interacting boson model

NASA Astrophysics Data System (ADS)

Saxena, M.; Gupta, J. B.; Mandal, S.

2015-08-01

The proton neutron interacting boson model (IBM-2) has been used to make a systematic study of Strontium isotopes in this mass region of A ˜ 80 with 38 ≤slant N ≤slant 48 and Z = 38. The three-term Talmi-Otsuka general Hamiltonian in the framework of the neutron proton version of the Interaction boson model was used to perform the calculations. The yrast levels energy are reproduced. The beta and gamma band energy levels also matched well. The reduced transition probabilities were also calculated and were found to be in agreement with the experimental values. In addition, g-factor for the {2}1+ state was evaluated. Possible candidates for mixed symmetry states were also predicted for several nuclei in this isotopic chain.

Numerical renormalization group calculation of impurity internal energy and specific heat of quantum impurity models

NASA Astrophysics Data System (ADS)

Merker, L.; Costi, T. A.

2012-08-01

We introduce a method to obtain the specific heat of quantum impurity models via a direct calculation of the impurity internal energy requiring only the evaluation of local quantities within a single numerical renormalization group (NRG) calculation for the total system. For the Anderson impurity model we show that the impurity internal energy can be expressed as a sum of purely local static correlation functions and a term that involves also the impurity Green function. The temperature dependence of the latter can be neglected in many cases, thereby allowing the impurity specific heat Cimp to be calculated accurately from local static correlation functions; specifically via Cimp=(∂Eionic)/(∂T)+(1)/(2)(∂Ehyb)/(∂T), where Eionic and Ehyb are the energies of the (embedded) impurity and the hybridization energy, respectively. The term involving the Green function can also be evaluated in cases where its temperature dependence is non-negligible, adding an extra term to Cimp. For the nondegenerate Anderson impurity model, we show by comparison with exact Bethe ansatz calculations that the results recover accurately both the Kondo induced peak in the specific heat at low temperatures as well as the high-temperature peak due to the resonant level. The approach applies to multiorbital and multichannel Anderson impurity models with arbitrary local Coulomb interactions. An application to the Ohmic two-state system and the anisotropic Kondo model is also given, with comparisons to Bethe ansatz calculations. The approach could also be of interest within other impurity solvers, for example, within quantum Monte Carlo techniques.

Van der Waals potential and vibrational energy levels of the ground state radon dimer

NASA Astrophysics Data System (ADS)

Sheng, Xiaowei; Qian, Shifeng; Hu, Fengfei

2017-08-01

In the present paper, the ground state van der Waals potential of the Radon dimer is described by the Tang-Toennies potential model, which requires five essential parameters. Among them, the two dispersion coefficients C6 and C8 are estimated from the well determined dispersion coefficients C6 and C8 of Xe2. C10 is estimated by using the approximation equation that C6C10/C82 has an average value of 1.221 for all the rare gas dimers. With these estimated dispersion coefficients and the well determined well depth De and Re the Born-Mayer parameters A and b are derived. Then the vibrational energy levels of the ground state radon dimer are calculated. 40 vibrational energy levels are observed in the ground state of Rn2 dimer. The last vibrational energy level is bound by only 0.0012 cm-1.

Statistical γ -decay properties of 64Ni and deduced (n ,γ ) cross section of the s -process branch-point nucleus 63Ni

NASA Astrophysics Data System (ADS)

Crespo Campo, L.; Bello Garrote, F. L.; Eriksen, T. K.; Görgen, A.; Guttormsen, M.; Hadynska-Klek, K.; Klintefjord, M.; Larsen, A. C.; Renstrøm, T.; Sahin, E.; Siem, S.; Springer, A.; Tornyi, T. G.; Tveten, G. M.

2016-10-01

Particle-γ coincidence data have been analyzed to obtain the nuclear level density and the γ -strength function of 64Ni by means of the Oslo method. The level density found in this work is in very good agreement with known energy levels at low excitation energies as well as with data deduced from particle-evaporation measurements at excitation energies above Ex≈5.5 MeV. The experimental γ -strength function presents an enhancement at γ energies below Eγ≈3 MeV and possibly a resonancelike structure centered at Eγ≈9.2 MeV. The obtained nuclear level density and γ -strength function have been used to estimate the (n ,γ ) cross section for the s -process branch-point nucleus 63Ni, of particular interest for astrophysical calculations of elemental abundances.

Exciplex formation in blended spin-cast films of fluorene-linked dyes and bisphthalimide quenchers.

PubMed

Stewart, David J; Dalton, Matthew J; Swiger, Rachel N; Cooper, Thomas M; Haley, Joy E; Tan, Loon-Seng

2013-05-16

Spin-cast films of dyes (donor-π-donor, donor-π-acceptor, and acceptor-π-acceptor type, where the donor is Ph2N-, the acceptor is 2-benzothiazoyl, and the π-linker is 9,9-diethylfluorene) blended with nonconjugated bisphthalimides were prepared. Upon visible-light excitation of the dyes, quenching of the excited state occurs by exciplex formation between dye and bisphthalimide molecules or, in some cases, by excimer formation or aggregation-induced emission between two dye molecules. The extent of exciplex formation is dependent on the driving force, which can be calculated using the energy difference between the lowest unoccupied molecular orbitals (LUMOs) of the dyes and bisphthalimides. The results show that complete exciplex formation occurs when this driving force is greater than 0.57 eV whereas partial exciplex formation occurs when the driving force is between 0.28 and 0.57 eV. The exciplex emission energies can also be predicted by calculating the difference between the LUMO level of the bisphthalimide and the highest occupied molecular orbital (HOMO) of the dye. These calculated values, which were obtained from the electrochemically determined energy levels, showed good agreement with the observed emission energies. The exciplex lifetimes were found to be significantly longer than the lifetimes of the lone dyes. These exciplexes formed from nonlinked donors and acceptors in the solid state might have potential uses in nonlinear photonics.

Theoretical study on the antitumor properties of Ru(II) complexes containing 2-pyridyl, 2-pyridine-4-carboxylic acid ligands

NASA Astrophysics Data System (ADS)

Erkan kariper, Sultan; Sayin, Koray; Karakaş, Duran

2017-12-01

[Ru(bipy)2(CppH)]2+(1), [Ru(bipy)2(Cpp-NH-Hex-COOH)]2+(2), [Ru(dppz)2(CppH)]2+(3) and [Ru(dppz)2(Cpp-NH-Hex-COOH)]2+(4) were calculated by Hartree-Fock (HF), Density Functional Theory (DFT) hybrid B3LYP and Moller-Plesset Perturbation (MPn n = 2,3) theory method and CEP-4G, CEP-31G, CEP-121G, LANL2DZ, LANL2MB, SDD basic sets and a mixed basic set with the keyword GEN in gas phase and water. Structure parameters obtained from optimized structures were compared with experimental parameters. M062X/(6-31G(d))(CEP-4G) level was taken into account for the most appropriate calculation level. IR, UV-VIS and NMR spectrums were examined for structural characterization. The optimal structure was identified via structure parameters, IR, UV-VIS and NMR spectrums. For the most compatible structure, the highest molecular orbital energy (EHOMO) which one of the most effective chemical determiners on the antitumor activity of the complexes, the lowest molecular orbital energy (ELUMO), LUMO-HOMO energy gap, hardness (η), softness (σ), electronegativity (χ), chemical potential (μ), electrophilicity index (ω), molar volume (V), dipole moment (DM), total negative charge (TNC), enthalpy (H), entropy (S) and total energy (E) were calculated. The causes of anticancer activity of the complexes have been studied.

A simplified approach to the band gap correction of defect formation energies: Al, Ga, and In-doped ZnO

NASA Astrophysics Data System (ADS)

Saniz, R.; Xu, Y.; Matsubara, M.; Amini, M. N.; Dixit, H.; Lamoen, D.; Partoens, B.

2013-01-01

The calculation of defect levels in semiconductors within a density functional theory approach suffers greatly from the band gap problem. We propose a band gap correction scheme that is based on the separation of energy differences in electron addition and relaxation energies. We show that it can predict defect levels with a reasonable accuracy, particularly in the case of defects with conduction band character, and yet is simple and computationally economical. We apply this method to ZnO doped with group III elements (Al, Ga, In). As expected from experiment, the results indicate that Zn substitutional doping is preferred over interstitial doping in Al, Ga, and In-doped ZnO, under both zinc-rich and oxygen-rich conditions. Further, all three dopants act as shallow donors, with the +1 charge state having the most advantageous formation energy. Also, doping effects on the electronic structure of ZnO are sufficiently mild so as to affect little the fundamental band gap and lowest conduction bands dispersion, which secures their n-type transparent conducting behavior. A comparison with the extrapolation method based on LDA+U calculations and with the Heyd-Scuseria-Ernzerhof hybrid functional (HSE) shows the reliability of the proposed scheme in predicting the thermodynamic transition levels in shallow donor systems.

Theoretical calculations of rotationally inelastic collisions of He with NaK(A {sup 1}Σ{sup +}): Transfer of population, orientation, and alignment

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

Malenda, R. F.; Price, T. J.; Stevens, J.

2015-06-14

We have performed extensive calculations to investigate thermal energy, rotationally inelastic collisions of NaK (A{sup 1}Σ{sup +}) with He. We determined a potential energy surface using a multi-reference configuration interaction wave function as implemented by the GAMESS electronic structure code, and we have performed coupled channel scattering calculations using the Arthurs and Dalgarno formalism. We also calculate the Grawert coefficients B{sub λ}(j, j′) for each j → j′ transition. These coefficients are used to determine the probability that orientation and alignment are preserved in collisions taking place in a cell environment. The calculations include all rotational levels with j ormore » j′ between 0 and 50, and total (translational and rotational) energies in the range 0.0002–0.0025 a.u. (∼44–550 cm{sup −1}). The calculated cross sections for transitions with even values of Δj tend to be larger than those for transitions with odd Δj, in agreement with the recent experiments of Wolfe et al. (J. Chem. Phys. 134, 174301 (2011)). The calculations of the energy dependence of the cross sections and the calculations of the fraction of orientation and alignment preserved in collisions also exhibit distinctly different behaviors for odd and even values of Δj. The calculations also indicate that the average fraction of orientation or alignment preserved in a transition becomes larger as j increases. We interpret this behavior using the semiclassical model of Derouard, which also leads to a simple way of visualizing the distribution of the angles between the initial and final angular momentum vectors j and j′. Finally, we compare the exact quantum results for j → j′ transitions with results based on the simpler, energy sudden approximation. That approximation is shown to be quite accurate.« less

Bibliography of Soviet Laser Developments

DTIC Science & Technology

1975-09-22

Nagibarov, V. R. , I. A. Nagibarova, and A. M. Shegeda (0). Nonresonant supermigration [of energy ] in concentrated specimens of ruby. ZhETF P...Korniyenko (1). Relationship of luminescence energies of various transitions with the metastable level of the Nd ion in glass. KE, no. 2, 1975...12Ye8) 98. 99. 100. Anan’kin, A. I. (0). Calculating the energy characteriitJcs of a thermally excited CG-, laser. KE, no. 1, 1975

Energy Levels, Lifetimes, and Transition Rates for P-like Ions from Cr X to Zn XVI from Large-scale Relativistic Multiconfiguration Calculations

NASA Astrophysics Data System (ADS)

Wang, K.; Jönsson, P.; Gaigalas, G.; Radžiūtė, L.; Rynkun, P.; Del Zanna, G.; Chen, C. Y.

2018-04-01

The fully relativistic multiconfiguration Dirac–Hartree–Fock method is used to compute excitation energies and lifetimes for the 143 lowest states of the 3{s}23{p}3, 3s3p 4, 3{s}23{p}23d, 3s3p 33d, 3p 5, 3{s}23p3{d}2 configurations in P-like ions from Cr X to Zn XVI. Multipole (E1, M1, E2, M2) transition rates, line strengths, oscillator strengths, and branching fractions among these states are also given. Valence–valence and core–valence electron correlation effects are systematically accounted for using large basis function expansions. Computed excitation energies are compared with the NIST ASD and CHIANTI compiled values and previous calculations. The mean average absolute difference, removing obvious outliers, between computed and observed energies for the 41 lowest identified levels in Fe XII, is only 0.057%, implying that the computed energies are accurate enough to aid identification of new emission lines from the Sun and other astrophysical sources. The amount of energy and transition data of high accuracy are significantly increased for several P-like ions of astrophysics interest, where experimental data are still very scarce.

Quantum chemical studies on hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes

NASA Astrophysics Data System (ADS)

Gövdeli, Nezafet; Karakaş, Duran

2018-07-01

Quantum chemical calculations at B3LYP/LANL2DZ/6-31G(d) level were made on anti-eclipsed, anti-staggered, syn-eclipsed, syn-staggered conformers of hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes in the gas phase. The most stable conformer of the complexes was found to be anti-staggered according to the total energy values calculated at given level. Structural parameters, vibration spectra, charge distributions, molecular orbital energy diagrams, contour diagrams of frontier orbitals, molecular electrostatic potential maps and some electronic structure descriptors were obtained for the most stable conformers. NMR spectra of the most stable conformers were calculated at GIAO/B3LYP/LANL2DZ level. The most stable conformer geometry was found to be distorted octahedral. IR and NMR spectra of the complexes are consistent with their geometry. HOMOs of the complexes were found to be center-atomic character and LUMOs were carbene-carbon character. From the calculated charge analysis and molecular electrostatic potential maps, it is found that carbene-carbon acts as electrofil and metal center nucleophile. It is suggested that the catalytic properties of the carbene complexes may be due to the fact that the carbene-carbon behave as electrophile and metal center nucleophile. Some electronic structure descriptors of the complexes were calculated and the molecular properties were estimated.

Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

NASA Astrophysics Data System (ADS)

Li, Guo; Rangel, Tonatiuh; Liu, Zhen-Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

2016-03-01

Using density functional theory (DFT) with a van der Waals density functional, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously studied monomeric phases. Moreover, using a model, which includes nonlocal polarization effects from the substrate and the neighboring molecules and incorporates many-body perturbation theory calculations within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. We find that, independent of coverage, the HOMO energy of the linear chain phase is lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy.

Learning molecular energies using localized graph kernels.

PubMed

Ferré, Grégoire; Haut, Terry; Barros, Kipton

2017-03-21

Recent machine learning methods make it possible to model potential energy of atomic configurations with chemical-level accuracy (as calculated from ab initio calculations) and at speeds suitable for molecular dynamics simulation. Best performance is achieved when the known physical constraints are encoded in the machine learning models. For example, the atomic energy is invariant under global translations and rotations; it is also invariant to permutations of same-species atoms. Although simple to state, these symmetries are complicated to encode into machine learning algorithms. In this paper, we present a machine learning approach based on graph theory that naturally incorporates translation, rotation, and permutation symmetries. Specifically, we use a random walk graph kernel to measure the similarity of two adjacency matrices, each of which represents a local atomic environment. This Graph Approximated Energy (GRAPE) approach is flexible and admits many possible extensions. We benchmark a simple version of GRAPE by predicting atomization energies on a standard dataset of organic molecules.

Learning molecular energies using localized graph kernels

NASA Astrophysics Data System (ADS)

Ferré, Grégoire; Haut, Terry; Barros, Kipton

2017-03-01

Recent machine learning methods make it possible to model potential energy of atomic configurations with chemical-level accuracy (as calculated from ab initio calculations) and at speeds suitable for molecular dynamics simulation. Best performance is achieved when the known physical constraints are encoded in the machine learning models. For example, the atomic energy is invariant under global translations and rotations; it is also invariant to permutations of same-species atoms. Although simple to state, these symmetries are complicated to encode into machine learning algorithms. In this paper, we present a machine learning approach based on graph theory that naturally incorporates translation, rotation, and permutation symmetries. Specifically, we use a random walk graph kernel to measure the similarity of two adjacency matrices, each of which represents a local atomic environment. This Graph Approximated Energy (GRAPE) approach is flexible and admits many possible extensions. We benchmark a simple version of GRAPE by predicting atomization energies on a standard dataset of organic molecules.

Energetic, structural and electronic properties of metal vacancies in strained AlN/GaN interfaces.

PubMed

Kioseoglou, J; Pontikis, V; Komninou, Ph; Pavloudis, Th; Chen, J; Karakostas, Th

2015-04-01

AlN/GaN heterostructures have been studied using density-functional pseudopotential calculations yielding the formation energies of metal vacancies under the influence of local interfacial strains, the associated charge distribution and the energies of vacancy-induced electronic states. Interfaces are built normal to the polar <0 0 0 1> direction of the wurtzite structure by joining two single crystals of AlN and GaN that are a few atomic layers thick; thus, periodic boundary conditions generate two distinct heterophase interfaces. We show that the formation energy of vacancies is a function of their distance from the interfaces: the vacancy-interface interaction is found repulsive or attractive, depending on the type of the interface. When the interaction is attractive, the vacancy formation energy decreases with increasing the associated electric charge, and hence the equilibrium vacancy concentration at the interface is greater. This finding can reveal the well-known morphological differences existing between the two types of investigated interfaces. Moreover, we found that the electric charge is strongly localized around the Ga vacancy, while in the case of Al vacancies is almost uniformly distributed throughout the AlN/GaN heterostructure. Crucially, for the applications of heterostructures, metal vacancies introduce deep states in the calculated bandgap at energy levels from 0.5 to 1 eV above the valence band maximum (VBM). It is, therefore, predicted that vacancies could initiate 'green luminescence' i.e. light emission in the energy range of 2.5 eV stemming from electronic transitions between these extra levels, and the conduction band, or energy levels, due to shallow donors.

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range.

PubMed

Tyuterev, Vladimir G; Kochanov, Roman V; Tashkun, Sergey A; Holka, Filip; Szalay, Péter G

2013-10-07

An accurate description of the complicated shape of the potential energy surface (PES) and that of the highly excited vibration states is of crucial importance for various unsolved issues in the spectroscopy and dynamics of ozone and remains a challenge for the theory. In this work a new analytical representation is proposed for the PES of the ground electronic state of the ozone molecule in the range covering the main potential well and the transition state towards the dissociation. This model accounts for particular features specific to the ozone PES for large variations of nuclear displacements along the minimum energy path. The impact of the shape of the PES near the transition state (existence of the "reef structure") on vibration energy levels was studied for the first time. The major purpose of this work was to provide accurate theoretical predictions for ozone vibrational band centres at the energy range near the dissociation threshold, which would be helpful for understanding the very complicated high-resolution spectra and its analyses currently in progress. Extended ab initio electronic structure calculations were carried out enabling the determination of the parameters of a minimum energy path PES model resulting in a new set of theoretical vibrational levels of ozone. A comparison with recent high-resolution spectroscopic data on the vibrational levels gives the root-mean-square deviations below 1 cm(-1) for ozone band centres up to 90% of the dissociation energy. New ab initio vibrational predictions represent a significant improvement with respect to all previously available calculations.

Impact of Many-Body Effects on Landau Levels in Graphene

NASA Astrophysics Data System (ADS)

Sonntag, J.; Reichardt, S.; Wirtz, L.; Beschoten, B.; Katsnelson, M. I.; Libisch, F.; Stampfer, C.

2018-05-01

We present magneto-Raman spectroscopy measurements on suspended graphene to investigate the charge carrier density-dependent electron-electron interaction in the presence of Landau levels. Utilizing gate-tunable magnetophonon resonances, we extract the charge carrier density dependence of the Landau level transition energies and the associated effective Fermi velocity vF. In contrast to the logarithmic divergence of vF at zero magnetic field, we find a piecewise linear scaling of vF as a function of the charge carrier density, due to a magnetic-field-induced suppression of the long-range Coulomb interaction. We quantitatively confirm our experimental findings by performing tight-binding calculations on the level of the Hartree-Fock approximation, which also allow us to estimate an excitonic binding energy of ≈6 meV contained in the experimentally extracted Landau level transitions energies.

System-size convergence of point defect properties: The case of the silicon vacancy

NASA Astrophysics Data System (ADS)

Corsetti, Fabiano; Mostofi, Arash A.

2011-07-01

We present a comprehensive study of the vacancy in bulk silicon in all its charge states from 2+ to 2-, using a supercell approach within plane-wave density-functional theory, and systematically quantify the various contributions to the well-known finite size errors associated with calculating formation energies and stable charge state transition levels of isolated defects with periodic boundary conditions. Furthermore, we find that transition levels converge faster with respect to supercell size when only the Γ-point is sampled in the Brillouin zone, as opposed to a dense k-point sampling. This arises from the fact that defect level at the Γ-point quickly converges to a fixed value which correctly describes the bonding at the defect center. Our calculated transition levels with 1000-atom supercells and Γ-point only sampling are in good agreement with available experimental results. We also demonstrate two simple and accurate approaches for calculating the valence band offsets that are required for computing formation energies of charged defects, one based on a potential averaging scheme and the other using maximally-localized Wannier functions (MLWFs). Finally, we show that MLWFs provide a clear description of the nature of the electronic bonding at the defect center that verifies the canonical Watkins model.

Optical model with multiple band couplings using soft rotator structure

NASA Astrophysics Data System (ADS)

Martyanov, Dmitry; Soukhovitskii, Efrem; Capote, Roberto; Quesada, Jose Manuel; Chiba, Satoshi

2017-09-01

A new dispersive coupled-channel optical model (DCCOM) is derived that describes nucleon scattering on 238U and 232Th targets using a soft-rotator-model (SRM) description of the collective levels of the target nucleus. SRM Hamiltonian parameters are adjusted to the observed collective levels of the target nucleus. SRM nuclear wave functions (mixed in K quantum number) have been used to calculate coupling matrix elements of the generalized optical model. Five rotational bands are coupled: the ground-state band, β-, γ-, non-axial- bands, and a negative parity band. Such coupling scheme includes almost all levels below 1.2 MeV of excitation energy of targets. The "effective" deformations that define inter-band couplings are derived from SRM Hamiltonian parameters. Conservation of nuclear volume is enforced by introducing a monopolar deformed potential leading to additional couplings between rotational bands. The present DCCOM describes the total cross section differences between 238U and 232Th targets within experimental uncertainty from 50 keV up to 200 MeV of neutron incident energy. SRM couplings and volume conservation allow a precise calculation of the compound-nucleus (CN) formation cross sections, which is significantly different from the one calculated with rigid-rotor potentials with any number of coupled levels.

Positron scattering from pyridine

NASA Astrophysics Data System (ADS)

Stevens, D.; Babij, T. J.; Machacek, J. R.; Buckman, S. J.; Brunger, M. J.; White, R. D.; García, G.; Blanco, F.; Ellis-Gibbings, L.; Sullivan, J. P.

2018-04-01

We present a range of cross section measurements for the low-energy scattering of positrons from pyridine, for incident positron energies of less than 20 eV, as well as the independent atom model with the screening corrected additivity rule including interference effects calculation, of positron scattering from pyridine, with dipole rotational excitations accounted for using the Born approximation. Comparisons are made between the experimental measurements and theoretical calculations. For the positronium formation cross section, we also compare with results from a recent empirical model. In general, quite good agreement is seen between the calculations and measurements although some discrepancies remain which may require further investigation. It is hoped that the present study will stimulate development of ab initio level theoretical methods to be applied to this important scattering system.

Ortho-, meta-, and para-benzyne. A comparative CCSD (T) investigation

NASA Astrophysics Data System (ADS)

Kraka, Elfi; Cremer, Dieter

1993-12-01

Geometries and energies of ortho-benzyne ( 1), mata-benzyne ( 2), and para-benzyne ( 3) have been calculated at the CCSD (T), GVB, GVB-LSDC, and MBPT (2) levels of theory employing the 6-31G(d, p) basis. Calculations suggest relative energies of O, 13.7, and 25.3 kcal/mol, respectively, and Δ H0f(298) values of 110.8, 123.9, and 135.7 kcal/mol for 1, 2, and 3. With the Δ H0f(298) value of 3, the reaction enthalpy Δ RH(298) and the activation enthalpy Δ H#(298) for the Bergman cyclization of (Z)-hexa-1,5-diy -ene to 3 are calculated to be 9.1 and 28.5 kcal/mol.

An automated exploration of the isomerization and dissociation pathways of (E)-1,2-dichloroethene cations and anions

NASA Astrophysics Data System (ADS)

Kishimoto, Naoki; Nishi, Yuito

2017-04-01

Isomerization and dissociation pathways after the photoionization or electron attachment of (E)-1,2-dichloroethene were calculated with an automated exploration method utilizing a scaled hypersphere search of the anharmonic downward distortion following algorithm at the UB3LYP/6-311G(2d,d,p) level of theory. The potential energies of transition states and dissociation channels were calculated by a composite method ((RO)CBS-QB3) and compared with the breakdown diagrams and electron attachment spectra observed in previous spectroscopic studies. The results of single point calculations with several DFT and post-SCF methods are compared using the root mean square deviations from the (RO)CBS-QB3 energies for six states of anionic dichloroethene.

Relativistic all-order many-body calculation of energies, wavelengths, and M 1 and E 2 transition rates for the 3 dn configurations in tungsten ions

NASA Astrophysics Data System (ADS)

Safronova, M. S.; Safronova, U. I.; Porsev, S. G.; Kozlov, M. G.; Ralchenko, Yu.

2018-01-01

Energy levels, wavelengths, magnetic-dipole and electric-quadrupole transition rates between the low-lying states are evaluated for W51 + to W54 + ions with 3 dn (n =2 to 5) electronic configurations by using an approach combining configuration interaction with the linearized coupled-cluster single-double method. The QED corrections are directly incorporated into the calculations and their effect is studied in detail. Uncertainties of the calculations are discussed. This study of such highly charged ions with the present method opens the way for future applications allowing an accurate prediction of properties for a very wide range of highly charged ions aimed at providing precision benchmarks for various applications.

A refined quartic potential energy surface and large scale vibrational calculations for S0 thiophosgene.

PubMed

Rashev, Svetoslav; Moule, David C

2015-04-05

In this work we present a full 6D quartic potential energy surface (PES) for S0 thiophosgene in curvilinear symmetrized bond-angle coordinates. The PES was refined starting from an ab initio field derived from acc-pVTZ basis set with CCSD(T) corrections for electron correlation. In the present calculations we used our variational method that was recently tested on formaldehyde and some of its isotopomers, along with additional improvements. The lower experimentally known vibrational levels for 35Cl2CS were reproduced quite well in the calculations, which can be regarded as a test for the feasibility of the obtained quartic PES. Copyright © 2015 Elsevier B.V. All rights reserved.

Double negatively charged carbon vacancy at the h- and k-sites in 4H-SiC: Combined Laplace-DLTS and DFT study

NASA Astrophysics Data System (ADS)

Capan, Ivana; Brodar, Tomislav; Pastuović, Željko; Siegele, Rainer; Ohshima, Takeshi; Sato, Shin-ichiro; Makino, Takahiro; Snoj, Luka; Radulović, Vladimir; Coutinho, José; Torres, Vitor J. B.; Demmouche, Kamel

2018-04-01

We present results from combined Laplace-Deep Level Transient Spectroscopy (Laplace-DLTS) and density functional theory studies of the carbon vacancy (VC) in n-type 4H-SiC. Using Laplace-DLTS, we were able to distinguish two previously unresolved sub-lattice-inequivalent emissions, causing the broad Z1/2 peak at 290 K that is commonly observed by conventional DLTS in n-type 4H-SiC. This peak has two components with activation energies for electron emission of 0.58 eV and 0.65 eV. We compared these results with the acceptor levels of VC obtained by means of hybrid density functional supercell calculations. The calculations support the assignment of the Z1/2 signal to a superposition of emission peaks from double negatively charged VC defects. Taking into account the measured and calculated energy levels, the calculated relative stability of VC in hexagonal (h) and cubic (k) lattice sites, as well as the observed relative amplitude of the Laplace-DLTS peaks, we assign Z1 and Z2 to VC(h) and VC(k), respectively. We also present the preliminary results of DLTS and Laplace-DLTS measurements on deep level defects (ET1 and ET2) introduced by fast neutron irradiation and He ion implantation in 4H-SiC. The origin of ET1 and ET2 is still unclear.

Photoluminescence characteristics of Eu2O3 doped calcium fluoroborate glasses

NASA Astrophysics Data System (ADS)

Krishnapuram, Pavani; Jakka, Suresh Kumar; Thummala, Chengaiah; Lalapeta, Rama Moorthy

2012-11-01

The present work reports the preparation and characterization of calcium fluoroborate (CFB) glasses doped with different concentrations of Eu2O3. The spectroscopic free-ion parameters are evaluated from the experimentally observed energy levels of Eu3+ ions in CFB glasses by using the free-ion Hamiltonian model (HFI). The phenomenological Judd-Ofelt (J-O) parameters, Ω2, Ω4 and Ω6, are evaluated from the intensities of Eu3+ ion absorption bands by various constraints. From these J-O parameters (Ωλ), the radiative parameters such as transition probabilities (AR), branching ratios (βR), stimulated emission cross sections (σe) and radiative lifetimes (τR) are evaluated for 5D→7(4fASO+αL(L+1)+βG(G2)+γG(R7)+∑j=0,2,4 Mjmj+∑k=2,4,6 PKpK where Eavg includes the kinetic energy of the electrons and their interaction with the nucleus. It shifts only the barycentre of the whole 4fN configuration. Fk (k = 2, 4, 6) are free electron repulsion parameters, ξ4f is the spin-orbit coupling constant, α, β and γ are the three interaction parameters, Mj (j = 0, 2, 4) and Pk (k = 2, 4, 6) are magnetic interaction parameters. Among all the interactions, Fk and ξ4f are the main ones which give rise to the 2LJ levels. The rest only make corrections in the energies of these levels without removing their degeneracy. The parametric fits have been carried out as has been done in our earlier work [16]. The quality of the parametric fit is generally described in terms of the root mean square (rms) deviation, σrms between the experimental and calculated energies by the relation σrms=√{{∑}/{i=1N(Eiexp-Eical)2N}} where Eiexp and Eical are the experimental and calculated energies, respectively, for level 'i' and N denotes the total number of levels included in the energy level fit.

Spectroscopy of the simplest Criegee intermediate CH2OO: simulation of the first bands in its electronic and photoelectron spectra.

PubMed

Lee, Edmond P F; Mok, Daniel K W; Shallcross, Dudley E; Percival, Carl J; Osborn, David L; Taatjes, Craig A; Dyke, John M

2012-09-24

CH(2)OO, the simplest Criegee intermediate, and ozone are isoelectronic. They both play very important roles in atmospheric chemistry. Whilst extensive experimental studies have been made on ozone, there were no direct gas-phase studies on CH(2)OO until very recently when its photoionization spectrum was recorded and kinetics studies were made of some reactions of CH(2)OO with a number of molecules of atmospheric importance, using photoionization mass spectrometry to monitor CH(2)OO. In order to encourage more direct studies on CH(2)OO and other Criegee intermediates, the electronic and photoelectron spectra of CH(2)OO have been simulated using high level electronic structure calculations and Franck-Condon factor calculations, and the results are presented here. Adiabatic and vertical excitation energies of CH(2)OO were calculated with TDDFT, EOM-CCSD, and CASSCF methods. Also, DFT, QCISD and CASSCF calculations were performed on neutral and low-lying ionic states, with single energy calculations being carried out at higher levels to obtain more reliable ionization energies. The results show that the most intense band in the electronic spectrum of CH(2) OO corresponds to the B(1)A' ← X(1)A' absorption. It is a broad band in the region 250-450 nm showing extensive structure in vibrational modes involving O-O stretching and C-O-O bending. Evidence is presented to show that the electronic absorption spectrum of CH(2)OO has probably been recorded in earlier work, albeit at low resolution. We suggest that CH(2)OO was prepared in this earlier work from the reaction of CH(2)I with O(2) and that the assignment of the observed spectrum solely to CH(2)IOO is incorrect. The low ionization energy region of the photoelectron spectrum of CH(2)OO consists of two overlapping vibrationally structured bands corresponding to one-electron ionizations from the highest two occupied molecular orbitals of the neutral molecule. In each case, the adiabatic component is the most intense and the adiabatic ionization energies of these bands are expected to be very close, at 9.971 and 9.974 eV at the highest level of theory used. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calculations for energies, transition rates, and lifetimes in Al-like Kr XXIV

NASA Astrophysics Data System (ADS)

Zhang, C. Y.; Si, R.; Liu, Y. W.; Yao, K.; Wang, K.; Guo, X. L.; Li, S.; Chen, C. Y.

2018-05-01

Using the second-order many-body perturbation theory (MBPT) method, a complete and accurate data set of excitation energies, lifetimes, wavelengths, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), and magnetic quadrupole (M2) line strengths, transition rates, and oscillator strengths for the lowest 880 levels arising from the 3l3 (0 ≤ l ≤ 2), 3l2 4l‧ (0 ≤ l ≤ 2, 0 ≤l‧ ≤ 3), 3s2 5 l (0 ≤ l ≤ 4), 3p2 5 l (0 ≤ l ≤ 1), and 3s3p5 l (0 ≤ l ≤ 4) configurations in Al-like Kr XXIV is provided. Comparisons are made with available experimental and theoretical results. Our calculated energies are expected to be accurate enough to facilitate identifications of observed lines involving the n = 4 , 5 levels. The complete data set is also useful for modeling and diagnosing fusion plasma.

X-ray and gamma-ray line production by nonthermal ions

NASA Technical Reports Server (NTRS)

Bussard, R. W.; Omidvar, K.; Ramaty, R.

1977-01-01

X-ray production was calculated at approximately 6.8 keV by the 2p to 1s transition in fast hydrogen- and helium-like iron ions, following both electron capture to excited levels and collisional excitation. A refinement of the OBK approximation was used to obtain an improved charge exchange cross section. This, and the corresponding ionization cross section were used to determine equilibrium charge fractions for iron ions as functions of their energy. The effective X-ray line production cross section was found to be sharply peaked in energy at about 8 to 12 MeV/amu. Because fast ions of similar energies can also excite nuclear levels, the ratio of selected strong gamma ray line emissivities to the X-ray line emissivity was also calculated. Limits set by this method on the intensity of gamma ray line emission from the galactic center and the radio galaxy Centaurus A are generally lower than those reported in the literature.

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

Schultz, Peter A.

For the purposes of making reliable first-principles predictions of defect energies in semiconductors, it is crucial to distinguish between effective-mass-like defects, which cannot be treated accurately with existing supercell methods, and deep defects, for which density functional theory calculations can yield reliable predictions of defect energy levels. The gallium antisite defect GaAs is often associated with the 78/203 meV shallow double acceptor in Ga-rich gallium arsenide. Within a conceptual framework of level patterns, analyses of structure and spin stabilization can be used within a supercell approach to distinguish localized deep defect states from shallow acceptors such as B As. Thismore » systematic approach determines that the gallium antisite supercell results has signatures inconsistent with an effective mass state and cannot be the 78/203 shallow double acceptor. Lastly, the properties of the Ga antisite in GaAs are described, total energy calculations that explicitly map onto asymptotic discrete localized bulk states predict that the Ga antisite is a deep double acceptor and has at least one deep donor state.« less

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

Rebolini, Elisa, E-mail: rebolini@lct.jussieu.fr; Toulouse, Julien, E-mail: julien.toulouse@upmc.fr; Savin, Andreas, E-mail: savin@lct.jussieu.fr

We present a study of the variation of total energies and excitation energies along a range-separated adiabatic connection. This connection links the non-interacting Kohn–Sham electronic system to the physical interacting system by progressively switching on the electron–electron interactions whilst simultaneously adjusting a one-electron effective potential so as to keep the ground-state density constant. The interactions are introduced in a range-dependent manner, first introducing predominantly long-range, and then all-range, interactions as the physical system is approached, as opposed to the conventional adiabatic connection where the interactions are introduced by globally scaling the standard Coulomb interaction. Reference data are reported for themore » He and Be atoms and the H{sub 2} molecule, obtained by calculating the short-range effective potential at the full configuration-interaction level using Lieb's Legendre-transform approach. As the strength of the electron–electron interactions increases, the excitation energies, calculated for the partially interacting systems along the adiabatic connection, offer increasingly accurate approximations to the exact excitation energies. Importantly, the excitation energies calculated at an intermediate point of the adiabatic connection are much better approximations to the exact excitation energies than are the corresponding Kohn–Sham excitation energies. This is particularly evident in situations involving strong static correlation effects and states with multiple excitation character, such as the dissociating H{sub 2} molecule. These results highlight the utility of long-range interacting reference systems as a starting point for the calculation of excitation energies and are of interest for developing and analyzing practical approximate range-separated density-functional methodologies.« less

Prediction and Analysis of CO2 Emission in Chongqing for the Protection of Environment and Public Health

PubMed Central

Yang, Shuai; Wang, Yu; Ao, Wengang; Bai, Yun; Li, Chuan

2018-01-01

Based on the consumption of fossil energy, the CO2 emissions of Chongqing are calculated and analyzed from 1997 to 2015 in this paper. Based on the calculation results, the consumption of fossil fuels and the corresponding CO2 emissions of Chongqing in 2020 are predicted, and the supporting data and corresponding policies are provided for the government of Chongqing to reach its goal as the economic unit of low-carbon emission in the ‘13th Five-Year Plan’. The results of the analysis show that there is a rapid decreasing trend of CO2 emissions in Chongqing during the ‘12th Five-Year Plan’, which are caused by the adjustment policy of the energy structure in Chongqing. Therefore, the analysis and prediction are primarily based on the adjustment of Chongqing’s coal energy consumption in this paper. At the initial stage, support vector regression (SVR) method is applied to predict the other fossil energy consumption and the corresponding CO2 emissions of Chongqing in 2020. Then, with the energy intensity of 2015 and the official target of CO2 intensity in 2020, the total fossil energy consumption and CO2 emissions of Chongqing in 2020 are predicted respectively. By the above results of calculation, the coal consumption and its corresponding CO2 emissions of Chongqing in 2020 are determined. To achieve the goal of CO2 emissions of Chongqing in 2020, the coal consumption level and energy intensity of Chongqing are calculated, and the adjustment strategies for energy consumption structure in Chongqing are proposed. PMID:29547505

Relativistic scattered wave calculations on UF6

NASA Technical Reports Server (NTRS)

Case, D. A.; Yang, C. Y.

1980-01-01

Self-consistent Dirac-Slater multiple scattering calculations are presented for UF6. The results are compared critically to other relativistic calculations, showing that the results of all molecular orbital calculations are in qualitative agreement, as measured by energy levels, population analyses, and spin-orbit splittings. A detailed comparison is made to the relativistic X alpha(RX alpha) method of Wood and Boring, which also uses multiple scattering theory, but incorporates relativistic effects in a more approximate fashion. For the most part, the RX alpha results are in agreement with the present results.

Tunneling of coupled methyl quantum rotors in 4-methylpyridine: Single rotor potential versus coupling interaction

NASA Astrophysics Data System (ADS)

Khazaei, Somayeh; Sebastiani, Daniel

2017-11-01

We study the influence of rotational coupling between a pair of methyl rotators on the tunneling spectrum in condensed phase. Two interacting adjacent methyl groups are simulated within a coupled-pair model composed of static rotational potential created by the chemical environment and the interaction potential between two methyl groups. We solve the two-dimensional time-independent Schrödinger equation analytically by expanding the wave functions on the basis set of two independent free-rotor functions. We investigate three scenarios which differ with respect to the relative strength of single-rotor and coupling potential. For each scenario, we illustrate the dependence of the energy level scheme on the coupling strength. It is found that the main determinant of splitting energy levels tends to be a function of the ratio of strengths of coupling and single-rotor potential. The tunnel splitting caused by coupling is maximized for the coupled rotors in which their total hindering potential is relatively shallow. Such a weakly hindered methyl rotational potential is predicted for 4-methylpyridine at low temperature. The experimental observation of multiple tunneling peaks arising from a single type of methyl group in 4-methylpyridine in the inelastic neutron scattering spectrum is widely attributed to the rotor-rotor coupling. In this regard, using a set of first-principles calculations combined with the nudged elastic band method, we investigate the rotational potential energy surface (PES) of the coaxial pairs of rotors in 4-methylpyridine. A Numerov-type method is used to numerically solve the two-dimensional time-independent Schrödinger equation for the calculated 2D-density functional theory profile. Our computed energy levels reproduce the observed tunneling transitions well. Moreover, the calculated density distribution of the three methyl protons resembles the experimental nuclear densities obtained from the Fourier difference method. By mapping the calculated first-principles PES on the model, it is confirmed that the hindering potential in 4-methylpyridine consists of proportionally shallow single-rotor potential to coupling interaction.

Tunneling of coupled methyl quantum rotors in 4-methylpyridine: Single rotor potential versus coupling interaction.

PubMed

Khazaei, Somayeh; Sebastiani, Daniel

2017-11-21

We study the influence of rotational coupling between a pair of methyl rotators on the tunneling spectrum in condensed phase. Two interacting adjacent methyl groups are simulated within a coupled-pair model composed of static rotational potential created by the chemical environment and the interaction potential between two methyl groups. We solve the two-dimensional time-independent Schrödinger equation analytically by expanding the wave functions on the basis set of two independent free-rotor functions. We investigate three scenarios which differ with respect to the relative strength of single-rotor and coupling potential. For each scenario, we illustrate the dependence of the energy level scheme on the coupling strength. It is found that the main determinant of splitting energy levels tends to be a function of the ratio of strengths of coupling and single-rotor potential. The tunnel splitting caused by coupling is maximized for the coupled rotors in which their total hindering potential is relatively shallow. Such a weakly hindered methyl rotational potential is predicted for 4-methylpyridine at low temperature. The experimental observation of multiple tunneling peaks arising from a single type of methyl group in 4-methylpyridine in the inelastic neutron scattering spectrum is widely attributed to the rotor-rotor coupling. In this regard, using a set of first-principles calculations combined with the nudged elastic band method, we investigate the rotational potential energy surface (PES) of the coaxial pairs of rotors in 4-methylpyridine. A Numerov-type method is used to numerically solve the two-dimensional time-independent Schrödinger equation for the calculated 2D-density functional theory profile. Our computed energy levels reproduce the observed tunneling transitions well. Moreover, the calculated density distribution of the three methyl protons resembles the experimental nuclear densities obtained from the Fourier difference method. By mapping the calculated first-principles PES on the model, it is confirmed that the hindering potential in 4-methylpyridine consists of proportionally shallow single-rotor potential to coupling interaction.

Laser induced fluorescence of BaS: Sm phosphor and energy level splitting of Sm 3+ ion

NASA Astrophysics Data System (ADS)

Thomas, Reethamma; Nampoori, V. P. N.

1990-03-01

Fluorescence of BaS: Sm phosphor has been studied using a pulsed Nitrogen laser (337.1 nm) as the excitation source. The spectrum consists of a broad band in the region 540-660nm superposed by the characteristic Sm 3+ lines. Energy level splitting pattern of Sm 3+ due to crystal field effects has been calculated and relevent field parameters are evaluated. Analysis shows that Sm 3+ takes up Ba 2+ substitutional sites.

Exact solution to the Schrödinger’s equation with pseudo-Gaussian potential

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

Iacob, Felix, E-mail: felix@physics.uvt.ro; Lute, Marina, E-mail: marina.lute@upt.ro

2015-12-15

We consider the radial Schrödinger equation with the pseudo-Gaussian potential. By making an ansatz to the solution of the eigenvalue equation for the associate Hamiltonian, we arrive at the general exact eigenfunction. The values of energy levels for the bound states are calculated along with their corresponding normalized wave-functions. The case of positive energy levels, known as meta-stable states, is also discussed and the magnitude of transmission coefficient through the potential barrier is evaluated.

Energy Level Alignment at Aqueous GaN and ZnO Interfaces

NASA Astrophysics Data System (ADS)

Hybertsen, Mark S.; Kharche, Neerav; Muckerman, James T.

2014-03-01

Electronic energy level alignment at semiconductor-electrolyte interfaces is fundamental to electrochemical activity. Motivated in particular by the search for new materials that can be more efficient for photocatalysis, we develop a first principles method to calculate this alignment at aqueous interfaces and demonstrate it for the specific case of non-polar GaN and ZnO interfaces with water. In the first step, density functional theory (DFT) based molecular dynamics is used to sample the physical interface structure and to evaluate the electrostatic potential step at the interface. In the second step, the GW approach is used to evaluate the reference electronic energy level separately in the bulk semiconductor (valence band edge energy) and in bulk water (the 1b1 energy level), relative to the internal electrostatic energy reference. Use of the GW approach naturally corrects for errors inherent in the use of Kohn-Sham energy eigenvalues to approximate the electronic excitation energies in each material. With this predicted interface alignment, specific redox levels in water, with potentials known relative to the 1b1 level, can then be compared to the semiconductor band edge positions. Our results will be discussed in the context of experiments in which photoexcited GaN and ZnO drive the hydrogen evolution reaction. Research carried out at Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy.

Atomic structure calculations and identification of EUV and SXR spectral lines in Sr XXX

NASA Astrophysics Data System (ADS)

Goyal, Arun; Khatri, Indu; Aggarwal, Sunny; Singh, A. K.; Mohan, Man

2015-08-01

We report an extensive theoretical study of atomic data for Sr XXX in a wide range with L-shell electron excitations to the M-shell. We have calculated energy levels, wave-function compositions and lifetimes for lowest 113 fine structure levels and wavelengths of an extreme Ultraviolet (EUV) and soft X-ray (SXR) transitions. We have employed multi-configuration Dirac Fock method (MCDF) approach within the framework of Dirac-Coulomb Hamiltonian including quantum electrodynamics (QED) and Breit corrections. We have also presented the radiative data for electric and magnetic dipole (E1, M1) and quadrupole (E2, M2) transitions from the ground state. We have made comparisons with available energy levels compiled by NIST and achieve good agreement. But due to inadequate data in the literature, analogous relativistic distorted wave calculations have also been performed using flexible atomic code (FAC) to assess the reliability and accuracy of our results. Additionally, we have provided new atomic data for Sr XXX which is not published elsewhere in the literature and we believe that our results may be beneficial in fusion plasma research and astrophysical investigations and applications.

Thermal decomposition pathways of ethane

NASA Astrophysics Data System (ADS)

Gordon, Mark S.; Truong, Thanh N.; Pople, John A.

1986-10-01

The alternate thermal decomposition pathways for ethane in its ground state have been investigated, using ab initio electronic structure calculations. Single-point energies were obtained at the full MP4/6-311 G ∗∗ level, using 6-31 G ∗ geometries for reactant, products, and transition states. The thermodynamically favored products are ethylene and molecular hydrogen, but a very large barrier (130 kcal/mol) is found for the direct 1,2-elimination of hydrogen. When calculated barriers are taken into account, the lowest-energy process is the homolytic cleavage of the C-C bond to form two methyl radicals.

Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions.

PubMed

Ramos, Pablo; Papadakis, Markos; Pavanello, Michele

2015-06-18

We have carried out a thorough benchmark of the frozen density-embedding (FDE) method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 nonadditive kinetic energy functionals, and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE and PW91 functionals coupled with the PW91k nonadditive kinetic energy functional and a TZP basis set constitute the most stable and accurate levels of theory for hole transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.

Utilization of the Boltzmann tail of TED for the calculation of the ``absolute'' work function and local field strength in FEM

NASA Astrophysics Data System (ADS)

Wysocki, J. K.

1984-02-01

The idea of Young and Clark of independent evaluation of the work function φ and electric field strength F in FEM [R.D. Young and H.E. Clark, Phys. Rev. Letters 17 (1966) 351] has been extended to the energy region above the Fermi level. The estimation of slowly varying elliptic functions, necessary to compute φ and F, using only experimental data is presented. Calculations for the W(111) plane using the field electron energy distribution and the integral field-emission current dependence on retarding voltage have been performed.

Low dose out-of-field radiotherapy, part 2: Calculating the mean photon energy values for the out-of-field photon energy spectrum from scattered radiation using Monte Carlo methods.

PubMed

Skrobala, A; Adamczyk, S; Kruszyna-Mochalska, M; Skórska, M; Konefał, A; Suchorska, W; Zaleska, K; Kowalik, A; Jackowiak, W; Malicki, J

2017-08-01

During radiotherapy, leakage from the machine head and collimator expose patients to out-of-field irradiation doses, which may cause secondary cancers. To quantify the risks of secondary cancers due to out-of-field doses, it is first necessary to measure these doses. Since most dosimeters are energy-dependent, it is essential to first determine the type of photon energy spectrum in the out-of-field area. The aim of this study was to determine the mean photon energy values for the out-of-field photon energy spectrum for a 6 MV photon beam using the GEANT 4-Monte Carlo method. A specially-designed large water phantom was simulated with a static field at gantry 0°. The source-to-surface distance was 92cm for an open field size of 10×10cm2. The photon energy spectra were calculated at five unique positions (at depths of 0.5, 1.6, 4, 6, 8, and 10cm) along the central beam axis and at six different off-axis distances. Monte Carlo simulations showed that mean radiation energy levels drop rapidly beyond the edge of the 6 MV photon beam field: at a distance of 10cm, the mean energy level is close to 0.3MeV versus 1.5MeV at the central beam axis. In some cases, the energy level actually increased even as the distance from the field edge increased: at a depth of 1.6cm and 15cm off-axis, the mean energy level was 0.205MeV versus 0.252MeV at 20cm off-axis. The out-of-field energy spectra and dose distribution data obtained in this study with Monte Carlo methods can be used to calibrate dosimeters to measure out-of-field radiation from 6MV photons. Copyright © 2017 Société française de radiothérapie oncologique (SFRO). Published by Elsevier SAS. All rights reserved.

A high-performance Fortran code to calculate spin- and parity-dependent nuclear level densities

NASA Astrophysics Data System (ADS)

Sen'kov, R. A.; Horoi, M.; Zelevinsky, V. G.

2013-01-01

A high-performance Fortran code is developed to calculate the spin- and parity-dependent shell model nuclear level densities. The algorithm is based on the extension of methods of statistical spectroscopy and implies exact calculation of the first and second Hamiltonian moments for different configurations at fixed spin and parity. The proton-neutron formalism is used. We have applied the method for calculating the level densities for a set of nuclei in the sd-, pf-, and pf+g- model spaces. Examples of the calculations for 28Si (in the sd-model space) and 64Ge (in the pf+g-model space) are presented. To illustrate the power of the method we estimate the ground state energy of 64Ge in the larger model space pf+g, which is not accessible to direct shell model diagonalization due to the prohibitively large dimension, by comparing with the nuclear level densities at low excitation energy calculated in the smaller model space pf. Program summaryProgram title: MM Catalogue identifier: AENM_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AENM_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 193181 No. of bytes in distributed program, including test data, etc.: 1298585 Distribution format: tar.gz Programming language: Fortran 90, MPI. Computer: Any architecture with a Fortran 90 compiler and MPI. Operating system: Linux. RAM: Proportional to the system size, in our examples, up to 75Mb Classification: 17.15. External routines: MPICH2 (http://www.mcs.anl.gov/research/projects/mpich2/) Nature of problem: Calculating of the spin- and parity-dependent nuclear level density. Solution method: The algorithm implies exact calculation of the first and second Hamiltonian moments for different configurations at fixed spin and parity. The code is parallelized using the Message Passing Interface and a master-slaves dynamical load-balancing approach. Restrictions: The program uses two-body interaction in a restricted single-level basis. For example, GXPF1A in the pf-valence space. Running time: Depends on the system size and the number of processors used (from 1 min to several hours).

Levelized Cost of Energy Analysis of Marine and Hydrokinetic Reference Models: Preprint

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

Jenne, D. S.; Yu, Y. H.; Neary, V.

2015-04-24

In 2010 the U.S. Department of Energy initiated the development of six marine energy converter reference models. The reference models are point designs of well-known marine energy converters. Each device was designed to operate in a specific marine resource, instead of a generic device that can be deployed at any location. This method allows each device to be used as a benchmark for future reference model to benchmark future devices. The six designs consist of three current energy converters and three wave energy converters. The reference model project has generated both technical and economic data sets that are available inmore » the public domain. The methodology to calculate the levelized cost of energy for the reference model project and an overall comparison of the cost of energy from these six reference-model designs are presented in this paper.« less

Spectroscopic (FT-IR, FT-Raman, and UV-visible) and quantum chemical studies on molecular geometry, Frontier molecular orbitals, NBO, NLO and thermodynamic properties of 1-acetylindole.

PubMed

Shukla, Vikas K; Al-Abdullah, Ebtehal S; El-Emam, Ali A; Sachan, Alok K; Pathak, Shilendra K; Kumar, Amarendra; Prasad, Onkar; Bishnoi, Abha; Sinha, Leena

2014-12-10

Quantum chemical calculations of ground state energy, geometrical structure and vibrational wavenumbers of 1-acetylindole were carried out using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. The FT-IR and FT-Raman spectra were recorded in the condensed state. The fundamental vibrational wavenumbers were calculated and a good correlation between experimental and scaled calculated wavenumbers has been accomplished. Electric dipole moment, polarizability and first static hyperpolarizability values of 1-acetylindole have been calculated at the same level of theory and basis set. The results show that the 1-acetylindole molecule possesses nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-Visible spectrum of the molecule was recorded in the region 200-500nm and the electronic properties like HOMO and LUMO energies and composition were obtained using TD-DFT method. The calculated energies and oscillator strengths are in good correspondence with the experimental data. The thermodynamic properties of the compound under investigation were calculated at different temperatures. Copyright © 2014 Elsevier B.V. All rights reserved.

DFT calculation and vibrational spectroscopic studies of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine

NASA Astrophysics Data System (ADS)

Premkumar, S.; Jawahar, A.; Mathavan, T.; Kumara Dhas, M.; Sathe, V. G.; Milton Franklin Benial, A.

2014-08-01

The molecular structure of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine (BABP) was optimized by the DFT/B3LYP method with 6-311G (d,p), 6-311++G (d,p) and cc-pVTZ basis sets using the Gaussian 09 program. The most stable optimized structure of the molecule was predicted by the DFT/B3LYP method with cc-pVTZ basis set. The vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals and thermodynamical parameters were calculated. These calculations were done at the ground state energy level of BABP without applying any constraint on the potential energy surface. The vibrational spectra were experimentally recorded using Fourier Transform-Infrared (FT-IR) and micro-Raman spectrometer. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies. The complete theoretically calculated and experimentally observed vibrational frequencies were assigned on the basis of Potential Energy Distribution (PED) calculation using the VEDA 4.0 program. The vibrational modes assignments were performed by using the animation option of GaussView 05 graphical interface for Gaussian program. The Mulliken atomic charge distribution was calculated for BABP molecule. The molecular reactivity and stability of BABP were also studied by frontier molecular orbitals (FMOs) analysis.

Capacity market design and renewable energy: Performance incentives, qualifying capacity, and demand curves

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

Byers, Conleigh; Levin, Todd; Botterud, Audun

A review of capacity markets in the United States in the context of increasing levels of variable renewable energy finds substantial differences with respect to incentives for operational performance, methods to calculate qualifying capacity for variable renewable energy and energy storage, and demand curves for capacity. The review also reveals large differences in historical capacity market clearing prices. The authors conclude that electricity market design must continue to evolve to achieve cost-effective policies for resource adequacy.