Imaging the square of the correlated two-electron wave function of a hydrogen molecule

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

Waitz, M.; Bello, R. Y.; Metz, D.

The toolbox for imaging molecules is well-equipped today. Some techniques visualize the geometrical structure, others the electron density or electron orbitals. Molecules are many-body systems for which the correlation between the constituents is decisive and the spatial and the momentum distribution of one electron depends on those of the other electrons and the nuclei. Such correlations have escaped direct observation by imaging techniques so far. Here, we implement an imaging scheme which visualizes correlations between electrons by coincident detection of the reaction fragments after high energy photofragmentation. With this technique, we examine the H 2 two-electron wave function in whichmore » electron-electron correlation beyond the mean-field level is prominent. We visualize the dependence of the wave function on the internuclear distance. High energy photoelectrons are shown to be a powerful tool for molecular imaging. Finally, our study paves the way for future time resolved correlation imaging at FELs and laser based X-ray sources.« less

Rapid estimation of the electron correlation energy for van der Waals complexes RgX (Rg = Kr, Xe, X = Br, I)

NASA Astrophysics Data System (ADS)

Xinying, Li; Yongfang, Zhao; Xiaogong, Jing; Fengli, Liu; Fengyou, Hao

2006-01-01

We present the rules of electron correlation energies for RgX (Rg = Kr, Xe, X = Br, I) van der Waals (vdW) complex systems at CCSD(T) theoretical level with SDB-cc-pVQZ basis set by the Gaussian 98 program. A new method to derive the dispersion coefficient C6 by fitting the intermonomer electron correlation energies to C6R-6 function is introduced. The present C6 values are compared with the corresponding theoretical ones.

Four-electron model for singlet and triplet excitation energy transfers with inclusion of coherence memory, inelastic tunneling and nuclear quantum effects

NASA Astrophysics Data System (ADS)

Suzuki, Yosuke; Ebina, Kuniyoshi; Tanaka, Shigenori

2016-08-01

A computational scheme to describe the coherent dynamics of excitation energy transfer (EET) in molecular systems is proposed on the basis of generalized master equations with memory kernels. This formalism takes into account those physical effects in electron-bath coupling system such as the spin symmetry of excitons, the inelastic electron tunneling and the quantum features of nuclear motions, thus providing a theoretical framework to perform an ab initio description of EET through molecular simulations for evaluating the spectral density and the temporal correlation function of electronic coupling. Some test calculations have then been carried out to investigate the dependence of exciton population dynamics on coherence memory, inelastic tunneling correlation time, magnitude of electronic coupling, quantum correction to temporal correlation function, reorganization energy and energy gap.

Relation between the Z-1 type expansion of the total energy of isoelectronic atoms and the many-electron theory on the electron correlation by Sinanoǧlu

NASA Astrophysics Data System (ADS)

Anno, Tosinobu; Teruya, Hirohide

1987-07-01

By applying the economical formula for the total energies of isoelectronic atoms presented by the present authors [J. Chem. Phys. 84, 6895 (1986)] to both the nonrelativistic exact energy and the Hartree-Fock energy, an expression of the Z-1 expansion type for the correlation energy is obtained for isoelectronic series involving the first-row atoms. Based upon the expression obtained, the following conclusions are derived on the relation between the Z-1 type expansion theory and Sinanoǧlu's many-electron theory (MET): (i) the Z2 term has nothing to do with the electron correlation; (ii) the term proportional to Z represents the internal correlation energy Eint in MET, at least when Z is large in comparison with the number of electrons N; (iii) the constant term in the Z-1 type expansion is the limiting value of the sum of the semi-internal and the all-external correlation energy (EF+Eu) when Z→∞ and its values for the ground-state atoms show a systematic trend when plotted against N; (iv) the sum of the Z-1 and the higher order terms in Z-1 represents the Z dependence of EF+Eu, although its small amount is attributable to a part of Eint when Z-N≲1.

Balancing single- and multi-reference correlation in the chemiluminescent reaction of dioxetanone using the anti-Hermitian contracted Schrödinger equation.

PubMed

Greenman, Loren; Mazziotti, David A

2011-05-07

Direct computation of energies and two-electron reduced density matrices (2-RDMs) from the anti-Hermitian contracted Schrödinger equation (ACSE) [D. A. Mazziotti, Phys. Rev. Lett. 97, 143002 (2006)], it is shown, recovers both single- and multi-reference electron correlation in the chemiluminescent reaction of dioxetanone especially in the vicinity of the conical intersection where strong correlation is important. Dioxetanone, the light-producing moiety of firefly luciferin, efficiently converts chemical energy into light by accessing its excited-state surface via a conical intersection. Our previous active-space 2-RDM study of dioxetanone [L. Greenman and D. A. Mazziotti, J. Chem. Phys. 133, 164110 (2010)] concluded that correlating 16 electrons in 13 (active) orbitals is required for realistic surfaces without correlating the remaining (inactive) orbitals. In this paper we pursue two complementary goals: (i) to correlate the inactive orbitals in 2-RDMs along dioxetanone's reaction coordinate and compare these results with those from multireference second-order perturbation theory (MRPT2) and (ii) to assess the size of the active space-the number of correlated electrons and orbitals-required by both MRPT2 and ACSE for accurate energies and surfaces. While MRPT2 recovers very different amounts of correlation with (4,4) and (16,13) active spaces, the ACSE obtains a similar amount of correlation energy with either active space. Nevertheless, subtle differences in excitation energies near the conical intersection suggest that the (16,13) active space is necessary to determine both energetic details and properties. Strong electron correlation is further assessed through several RDM-based metrics including (i) total and relative energies, (ii) the von Neumann entropy based on the 1-electron RDM, as well as the (iii) infinity and (iv) squared Frobenius norms based on the cumulant 2-RDM.

Electron-electron correlation in two-photon double ionization of He-like ions [Counterintuitive electron correlation in two-photon double ionization of He-like ions

DOE PAGES

Hu, S. X.

2018-01-18

Electron correlation plays a crucial role in quantum many-body physics ranging from molecular bonding, strong-field–induced multi-electron ionization, to superconducting in materials. Understanding the dynamic electron correlation in the photoionization of relatively simple quantum three-body systems, such as He and He-like ions, is an important step toward manipulating complex systems through photo-induced processes. Here we have performed ab initio investigations of two-photon double ionization (TPDI) of He and He-like ions [Li +, Be 2+, and C 4+] exposed to intense attosecond x-ray pulses. Results from such fully correlated quantum calculations show weaker and weaker electron correlation effects in TPDI spectra asmore » the ionic charge increases, which is counterintuitive to the belief that the strongly correlated ground state and the strong Coulomb field of He-like ions should lead to more equal-energy sharing in photoionization. Lastly, these findings indicate that the final-state electron–electron correlation ultimately determines their energy sharing in TPDI.« less

Electron-electron correlation in two-photon double ionization of He-like ions [Counterintuitive electron correlation in two-photon double ionization of He-like ions

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

Hu, S. X.

Electron correlation plays a crucial role in quantum many-body physics ranging from molecular bonding, strong-field–induced multi-electron ionization, to superconducting in materials. Understanding the dynamic electron correlation in the photoionization of relatively simple quantum three-body systems, such as He and He-like ions, is an important step toward manipulating complex systems through photo-induced processes. Here we have performed ab initio investigations of two-photon double ionization (TPDI) of He and He-like ions [Li +, Be 2+, and C 4+] exposed to intense attosecond x-ray pulses. Results from such fully correlated quantum calculations show weaker and weaker electron correlation effects in TPDI spectra asmore » the ionic charge increases, which is counterintuitive to the belief that the strongly correlated ground state and the strong Coulomb field of He-like ions should lead to more equal-energy sharing in photoionization. Lastly, these findings indicate that the final-state electron–electron correlation ultimately determines their energy sharing in TPDI.« less

One-electron reduced density matrices of strongly correlated harmonium atoms.

PubMed

Cioslowski, Jerzy

2015-03-21

Explicit asymptotic expressions are derived for the reduced one-electron density matrices (the 1-matrices) of strongly correlated two- and three-electron harmonium atoms in the ground and first excited states. These expressions, which are valid at the limit of small confinement strength ω, yield electron densities and kinetic energies in agreement with the published values. In addition, they reveal the ω(5/6) asymptotic scaling of the exchange components of the electron-electron repulsion energies that differs from the ω(2/3) scaling of their Coulomb and correlation counterparts. The natural orbitals of the totally symmetric ground state of the two-electron harmonium atom are found to possess collective occupancies that follow a mixed power/Gaussian dependence on the angular momentum in variance with the simple power-law prediction of Hill's asymptotics. Providing rigorous constraints on energies as functionals of 1-matrices, these results are expected to facilitate development of approximate implementations of the density matrix functional theory and ensure their proper description of strongly correlated systems.

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.

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

PubMed Central

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

2015-01-01

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

Correlation between core ion energization, suprathermal electron bursts, and broadband ELF plasma waves

NASA Astrophysics Data System (ADS)

Knudsen, David J.; Clemmons, James H.; Wahlund, Jan-Erik

1998-03-01

Observations of the lowest energy or core ions provide a particularly sensitive measure of the early stages of auroral ion energization. Freja satellite observations of 0-20 eV core ions in the topside auroral ionosphere and cusp/cleft show signs of heating within both regions of VLF hiss and broadband ELF plasma waves. However, heating to several eV or more is associated predominantly with the ELF waves. A correlation analysis of wave and core ion data formed from orbital segments shows that, on average, correlations are highest for wave frequencies below several hundred Hz, and less at VLF hiss frequencies. A similar analysis shows a higher correlation between electron precipitation and ion heating for electron energies below several hundred eV (i.e., the energies associated with suprathermal electron bursts) and a lower correlation above the 1 keV energies associated with auroral inverted-V's. Signs of core ion heating begin to appear when wave power at the O+ gyrofrequency exceeds about 10-3(mVm-1)2/Hz, and when the integrated field-aligned electron flux exceeds a few times 107cm-2s-1sr-1. This electron energy flux threshold is at least an order of magnitude lower than previously inferred from earlier studies comparing suprathermal electron fluxes and energetic ions. Almost all observed heating events occur during enhanced or active geomagnetic conditions; i.e., Kp>=4. While the most intense core ion heating is correlated with broadband ELF waves, we also present one example of weak ion heating of a few eV in a region of VLF auroral hiss.

Anomalous High-Energy Waterfall-Like Electronic Structure in 5 d Transition Metal Oxide Sr2IrO4 with a Strong Spin-Orbit Coupling

PubMed Central

Liu, Yan; Yu, Li; Jia, Xiaowen; Zhao, Jianzhou; Weng, Hongming; Peng, Yingying; Chen, Chaoyu; Xie, Zhuojin; Mou, Daixiang; He, Junfeng; Liu, Xu; Feng, Ya; Yi, Hemian; Zhao, Lin; Liu, Guodong; He, Shaolong; Dong, Xiaoli; Zhang, Jun; Xu, Zuyan; Chen, Chuangtian; Cao, Gang; Dai, Xi; Fang, Zhong; Zhou, X. J.

2015-01-01

The low energy electronic structure of Sr2IrO4 has been well studied and understood in terms of an effective Jeff = 1/2 Mott insulator model. However, little work has been done in studying its high energy electronic behaviors. Here we report a new observation of the anomalous high energy electronic structure in Sr2IrO4. By taking high-resolution angle-resolved photoemission measurements on Sr2IrO4 over a wide energy range, we have revealed for the first time that the high energy electronic structures show unusual nearly-vertical bands that extend over a large energy range. Such anomalous high energy behaviors resemble the high energy waterfall features observed in the cuprate superconductors. While strong electron correlation plays an important role in producing high energy waterfall features in the cuprate superconductors, the revelation of the high energy anomalies in Sr2IrO4, which exhibits strong spin-orbit coupling and a moderate electron correlation, points to an unknown and novel route in generating exotic electronic excitations. PMID:26267653

Beyond the random-phase approximation for the electron correlation energy: the importance of single excitations.

PubMed

Ren, Xinguo; Tkatchenko, Alexandre; Rinke, Patrick; Scheffler, Matthias

2011-04-15

The random-phase approximation (RPA) for the electron correlation energy, combined with the exact-exchange (EX) energy, represents the state-of-the-art exchange-correlation functional within density-functional theory. However, the standard RPA practice--evaluating both the EX and the RPA correlation energies using Kohn-Sham (KS) orbitals from local or semilocal exchange-correlation functionals--leads to a systematic underbinding of molecules and solids. Here we demonstrate that this behavior can be corrected by adding a "single excitation" contribution, so far not included in the standard RPA scheme. A similar improvement can also be achieved by replacing the non-self-consistent EX total energy by the corresponding self-consistent Hartree-Fock total energy, while retaining the RPA correlation energy evaluated using KS orbitals. Both schemes achieve chemical accuracy for a standard benchmark set of noncovalent intermolecular interactions.

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

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

NASA Astrophysics Data System (ADS)

Tiwari, Vivek; Peters, William K.; Jonas, David M.

2017-10-01

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer.

PubMed

Tiwari, Vivek; Peters, William K; Jonas, David M

2017-10-21

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE PAGES

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

2017-11-20

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

NASA Astrophysics Data System (ADS)

Tao, Jianmin; Ye, Lin-Hui; Duan, Yuhua

2017-12-01

The primary goal of Kohn-Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao-Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE), Tao-Perdew-Staroverov-Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree-Fock density yields the exchange and correlation energies in good agreement with the Optimized Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Finally, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

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

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Importance of dispersion and electron correlation in ab initio protein folding.

PubMed

He, Xiao; Fusti-Molnar, Laszlo; Cui, Guanglei; Merz, Kenneth M

2009-04-16

Dispersion is well-known to be important in biological systems, but the effect of electron correlation in such systems remains unclear. In order to assess the relationship between the structure of a protein and its electron correlation energy, we employed both full system Hartree-Fock (HF) and second-order Møller-Plesset perturbation (MP2) calculations in conjunction with the Polarizable Continuum Model (PCM) on the native structures of two proteins and their corresponding computer-generated decoy sets. Because of the expense of the MP2 calculation, we have utilized the fragment molecular orbital method (FMO) in this study. We show that the sum of the Hartree-Fock (HF) energy and force field (LJ6)-derived dispersion energy (HF + LJ6) is well correlated with the energies obtained using second-order Møller-Plesset perturbation (MP2) theory. In one of the two examples studied, the correlation energy as well as the empirical dispersive energy term was able to discriminate between native and decoy structures. On the other hand, for the second protein we studied, neither the correlation energy nor dispersion energy showed discrimination capabilities; however, the ab initio MP2 energy and the HF+LJ6 both ranked the native structure correctly. Furthermore, when we randomly scrambled the Lennard-Jones parameters, the correlation between the MP2 energy and the sum of the HF energy and dispersive energy (HF+LJ6) significantly drops, which indicates that the choice of Lennard-Jones parameters is important.

Exchange and correlation energies in silicene illuminated by circularly polarized light

NASA Astrophysics Data System (ADS)

Iurov, Andrii; Gumbs, Godfrey; Huang, Danhong

2017-05-01

Both the exchange and correlation energies due to Coulomb and spin-orbit interactions in a monolayer silicene with a buckled honeycomb lattice are calculated. We use Lindhard formalism for the polarizability. Many-body effects in such Dirac-like materials are studied with an emphasis on the influence of on-site potential difference ? between two sublattices. Our calculations have shown that the presence of an energy bandgap ? leads to a reduced exchange energy, which has some potential applications, such as, tunability of entanglement of electrons for quantum information devices. Since silicene acquires two energy gaps associated with up- and down-pseudospin, we can adjust its electronic properties in a wider range by varying these two bandgaps as compared to graphene. Another way to tune silicene electronic properties is through impurity doping. Our numerical results demonstrate the dependence of exchange and correlation energies on the energy bandgaps, doping and temperature under circularly polarized light.

Narrowing the error in electron correlation calculations by basis set re-hierarchization and use of the unified singlet and triplet electron-pair extrapolation scheme: Application to a test set of 106 systems

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

Varandas, A. J. C., E-mail: varandas@uc.pt; Departamento de Física, Universidade Federal do Espírito Santo, 29075-910 Vitória; Pansini, F. N. N.

2014-12-14

A method previously suggested to calculate the correlation energy at the complete one-electron basis set limit by reassignment of the basis hierarchical numbers and use of the unified singlet- and triplet-pair extrapolation scheme is applied to a test set of 106 systems, some with up to 48 electrons. The approach is utilized to obtain extrapolated correlation energies from raw values calculated with second-order Møller-Plesset perturbation theory and the coupled-cluster singles and doubles excitations method, some of the latter also with the perturbative triples corrections. The calculated correlation energies have also been used to predict atomization energies within an additive scheme.more » Good agreement is obtained with the best available estimates even when the (d, t) pair of hierarchical numbers is utilized to perform the extrapolations. This conceivably justifies that there is no strong reason to exclude double-zeta energies in extrapolations, especially if the basis is calibrated to comply with the theoretical model.« less

Conical intersections of free energy surfaces in solution: Effect of electron correlation on a protonated Schiff base in methanol solution

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

Mori, Toshifumi; Nakano, Katsuhiro; Kato, Shigeki

2010-08-14

The minimum energy conical intersection (MECI) optimization method with taking account of the dynamic electron correlation effect [T. Mori and S. Kato, Chem. Phys. Lett. 476, 97 (2009)] is extended to locate the MECI of nonequilibrium free energy surfaces in solution. A multistate electronic perturbation theory is introduced into the nonequilibrium free energy formula, which is defined as a function of solute and solvation coordinates. The analytical free energy gradient and interstate coupling vectors are derived, and are applied to locate MECIs in solution. The present method is applied to study the cis-trans photoisomerization reaction of a protonated Schiff basemore » molecule (PSB3) in methanol (MeOH) solution. It is found that the effect of dynamic electron correlation largely lowers the energy of S{sub 1} state. We also show that the solvation effect strongly stabilizes the MECI obtained by twisting the terminal C=N bond to become accessible in MeOH solution, whereas the conical intersection is found to be unstable in gas phase. The present study indicates that both electron correlation and solvation effects are important in the photoisomerization reaction of PSB3. The effect of counterion is also examined, and seems to be rather small in solution. The structures of free energy surfaces around MECIs are also discussed.« less

A diagnostic for determining the quality of single-reference electron correlation methods

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Taylor, Peter R.

1989-01-01

It was recently proposed that the Euclidian norm of the t(sub 1) vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appopriate. This diagnostic, T(sub 1) is defined for use with self-consistent-field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T(sub 1) is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of non-dynamical electron correlation and is far superior to C(sub 0) from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T(sub 1) (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.

A diagnostic for determining the quality of single-reference electron correlation methods

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Taylor, Peter R.

1989-01-01

It was recently proposed that the Euclidian norm of the t sub 1 vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appropriate. This diagnostic, T sub 1, is defined for use with self consistent field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T sub 1 is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of nondynamical electron correlation and is far superior to C sub 0 from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T sub 1 (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.

Correlation energy, correlated electron density, and exchange-correlation potential in some spherically confined atoms.

PubMed

Vyboishchikov, Sergei F

2016-12-05

We report correlation energies, electron densities, and exchange-correlation potentials obtained from configuration interaction and density functional calculations on spherically confined He, Be, Be 2+ , and Ne atoms. The variation of the correlation energy with the confinement radius R c is relatively small for the He, Be 2+ , and Ne systems. Curiously, the Lee-Yang-Parr (LYP) functional works well for weak confinements but fails completely for small R c . However, in the neutral beryllium atom the CI correlation energy increases markedly with decreasing R c . This effect is less pronounced at the density-functional theory level. The LYP functional performs very well for the unconfined Be atom, but fails badly for small R c . The standard exchange-correlation potentials exhibit significant deviation from the "exact" potential obtained by inversion of Kohn-Sham equation. The LYP correlation potential behaves erratically at strong confinements. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Importance of conduction electron correlation in a Kondo lattice, Ce₂CoSi₃.

PubMed

Patil, Swapnil; Pandey, Sudhir K; Medicherla, V R R; Singh, R S; Bindu, R; Sampathkumaran, E V; Maiti, Kalobaran

2010-06-30

Kondo systems are usually described by the interaction of the correlation induced local moments with the highly itinerant conduction electrons. Here, we study the role of electron correlations among conduction electrons in the electronic structure of a Kondo lattice compound, Ce₂CoSi₃, using high resolution photoemission spectroscopy and ab initio band structure calculations, where Co 3d electrons contribute in the conduction band. High energy resolution employed in the measurements helped to reveal the signatures of Ce 4f states derived Kondo resonance features at the Fermi level and the dominance of Co 3d contributions at higher binding energies in the conduction band. The lineshape of the experimental Co 3d band is found to be significantly different from that obtained from the band structure calculations within the local density approximations, LDA. Consideration of electron-electron Coulomb repulsion, U, among Co 3d electrons within the LDA + U method leads to a better representation of experimental results. The signature of an electron correlation induced satellite feature is also observed in the Co 2p core level spectrum. These results clearly demonstrate the importance of the electron correlation among conduction electrons in deriving the microscopic description of such Kondo systems.

Effective homogeneity of the exchange-correlation and non-interacting kinetic energy functionals under density scaling.

PubMed

Borgoo, Alex; Teale, Andrew M; Tozer, David J

2012-01-21

Correlated electron densities, experimental ionisation potentials, and experimental electron affinities are used to investigate the homogeneity of the exchange-correlation and non-interacting kinetic energy functionals of Kohn-Sham density functional theory under density scaling. Results are presented for atoms and small molecules, paying attention to the influence of the integer discontinuity and the choice of the electron affinity. For the exchange-correlation functional, effective homogeneities are highly system-dependent on either side of the integer discontinuity. By contrast, the average homogeneity-associated with the potential that averages over the discontinuity-is generally close to 4/3 when the discontinuity is computed using positive affinities for systems that do bind an excess electron and negative affinities for those that do not. The proximity to 4/3 becomes increasingly pronounced with increasing atomic number. Evaluating the discontinuity using a zero affinity in systems that do not bind an excess electron instead leads to effective homogeneities on the electron abundant side that are close to 4/3. For the non-interacting kinetic energy functional, the effective homogeneities are less system-dependent and the effect of the integer discontinuity is less pronounced. Average values are uniformly below 5/3. The study provides information that may aid the development of improved exchange-correlation and non-interacting kinetic energy functionals. © 2012 American Institute of Physics

A minimalistic approach to static and dynamic electron correlations: Amending generalized valence bond method with extended random phase approximation correlation correction

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

Chatterjee, Koushik; Jawulski, Konrad; Pastorczak, Ewa

A perfect-pairing generalized valence bond (GVB) approximation is known to be one of the simplest approximations, which allows one to capture the essence of static correlation in molecular systems. In spite of its attractive feature of being relatively computationally efficient, this approximation misses a large portion of dynamic correlation and does not offer sufficient accuracy to be generally useful for studying electronic structure of molecules. We propose to correct the GVB model and alleviate some of its deficiencies by amending it with the correlation energy correction derived from the recently formulated extended random phase approximation (ERPA). On the examples ofmore » systems of diverse electronic structures, we show that the resulting ERPA-GVB method greatly improves upon the GVB model. ERPA-GVB recovers most of the electron correlation and it yields energy barrier heights of excellent accuracy. Thanks to a balanced treatment of static and dynamic correlation, ERPA-GVB stays reliable when one moves from systems dominated by dynamic electron correlation to those for which the static correlation comes into play.« less

Kinetic energy as functional of the correlation hole

NASA Astrophysics Data System (ADS)

Nalewajski, Roman F.

2003-01-01

Using the marginal decomposition of the many-body probability distribution the electronic kinetic energy is expressed as the functional of the electron density and correlation hole. The analysis covers both the molecule as a whole and its constituent subsystems. The importance of the Fisher information for locality is emphasized.

Magnetic properties and core electron binding energies of liquid water

NASA Astrophysics Data System (ADS)

Galamba, N.; Cabral, Benedito J. C.

2018-01-01

The magnetic properties and the core and inner valence electron binding energies of liquid water are investigated. The adopted methodology relies on the combination of molecular dynamics and electronic structure calculations. Born-Oppenheimer molecular dynamics with the Becke and Lee-Yang-Parr functionals for exchange and correlation, respectively, and includes an empirical correction (BLYP-D3) functional and classical molecular dynamics with the TIP4P/2005-F model were carried out. The Keal-Tozer functional was applied for predicting magnetic shielding and spin-spin coupling constants. Core and inner valence electron binding energies in liquid water were calculated with symmetry adapted cluster-configuration interaction. The relationship between the magnetic shielding constant σ(17O), the role played by the oxygen atom as a proton acceptor and donor, and the tetrahedral organisation of liquid water are investigated. The results indicate that the deshielding of the oxygen atom in water is very dependent on the order parameter (q) describing the tetrahedral organisation of the hydrogen bond network. The strong sensitivity of magnetic properties on changes of the electronic density in the nuclei environment is illustrated by a correlation between σ(17O) and the energy gap between the 1a1[O1s] (core) and the 2a1 (inner valence) orbitals of water. Although several studies discussed the eventual connection between magnetic properties and core electron binding energies, such a correlation could not be clearly established. Here, we demonstrate that for liquid water this correlation exists although involving the gap between electron binding energies of core and inner valence orbitals.

Variation of Radiation Belt Content Indices and total electron energy During Magnetic Storms Based On Van Allen Probe Observations

NASA Astrophysics Data System (ADS)

Xiong, Y.; Xie, L.; Chen, L.; Pu, Z.

2017-12-01

We investigate the variability of the RBC indices and total electron energy for varying energies within outer belt during 42 isolate magnetic storms based on the electron flux data from MagEIS and REPT onboard Van Allen Probe-A spacecraft. Van Allan Probes travel throughout the entire radiation belt twice during each orbit, providing an excellent opportunity to measure the electron's pitch angle distributions near the magnetic equatorial plane which is essential to calculate the RBC index accurately. Instead of assuming an isotropic electron pitch angle distribution which is widely used in previous studies, we develop a new and reliable technique to infer the equatorial pitch angle distributions based on the off-equator measurements. The statistic results show that the total electron energy in outer belt increase in 80% storms and has a positive correlation with median value of AE during recovery phase and minimum -Dst. The possibility of observing RBC depletion increase at high energies. The upper limit energy of RBC enhancement has a positive correlation with median value of AE and Vsw during recovery phase and a negative correlation with median value of Nsw during storm, which is consist of the balance of acceleration by chorus waves and loss by EMIC waves.

Discontinuity of the exchange-correlation potential and the functional derivative of the noninteracting kinetic energy as the number of electrons crosses integer boundaries in Li, Be, and B.

PubMed

Morrison, Robert C

2015-01-07

Accurate densities were determined from configuration interaction wave functions for atoms and ions of Li, Be, and B with up to four electrons. Exchange-correlation potentials, Vxc(r), and functional derivatives of the noninteracting kinetic energy, δK[ρ]/δρ(r), obtained from these densities were used to examine their discontinuities as the number of electrons N increases across integer boundaries for N = 1, N = 2, and N = 3. These numerical results are consistent with conclusions that the discontinuities are characterized by a jump in the chemical potential while the shape of Vxc(r) varies continuously as an integer boundary is crossed. The discontinuity of the Vxc(r) is positive, depends on the ionization potential, electron affinity, and orbital energy differences, and the discontinuity in δK[ρ]/δρ(r) depends on the difference between the energies of the highest occupied and lowest unoccupied orbitals. The noninteracting kinetic energy and the exchange correlation energy have been computed for integer and noninteger values of N between 1 and 4.

Electron Pairing, Repulsion, and Correlation: A Simplistic Approach

ERIC Educational Resources Information Center

Olsson, Lars-Fride; Kloo, Lars

2004-01-01

The interplay between a nucleus and an electron pair is explained through a basic application of an electrostatic and balanced model to determine the correlated and repulsive movements of the electron pair. The stable correlation depends on the positive charge produced by the combined force, which in turn establishes a negative potential energy.

Wigner molecules: the strong-correlation limit of the three-electron harmonium.

PubMed

Cioslowski, Jerzy; Pernal, Katarzyna

2006-08-14

At the strong-correlation limit, electronic states of the three-electron harmonium atom are described by asymptotically exact wave functions given by products of distinct Slater determinants and a common Gaussian factor that involves interelectron distances and the center-of-mass position. The Slater determinants specify the angular dependence and the permutational symmetry of the wave functions. As the confinement strength becomes infinitesimally small, the states of different spin multiplicities become degenerate, their limiting energy reflecting harmonic vibrations of the electrons about their equilibrium positions. The corresponding electron densities are given by products of angular factors and a Gaussian function centered at the radius proportional to the interelectron distance at equilibrium. Thanks to the availability of both the energy and the electron density, the strong-correlation limit of the three-electron harmonium is well suited for testing of density functionals.

Nonequilibrium electron and lattice dynamics of strongly correlated Bi2Sr2CaCu2O8+δ single crystals

PubMed Central

Li, Renkai; Gu, Genda; Avigo, Isabella; Dürr, Hermann A.; Johnson, Peter D.; Wang, Xijie

2018-01-01

The interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped Bi2Sr2CaCu2O8+δ. Quantitative analysis of the lattice and electron subsystems’ dynamics provides a unified picture of nonequilibrium electron-phonon interactions in the cuprates beyond the N-temperature model. The work provides new insights on the specific phonon branches involved in the nonequilibrium heat dissipation from the high-energy Cu–O bond stretching “hot” phonons to the lowest-energy acoustic phonons with correlated atomic motion along the <110> crystal directions and their characteristic time scales. It reveals a highly nonthermal phonon population during the first several picoseconds after the photoexcitation. The approach, taking advantage of the distinct nature of electrons and photons as probes, is applicable for studying energy relaxation in other strongly correlated electron systems. PMID:29719862

Exchange and correlation in positronium-molecule scattering

NASA Astrophysics Data System (ADS)

Fabrikant, I. I.; Wilde, R. S.

2018-05-01

Exchange and correlations play a particularly important role in positronium (Ps) collisions with atoms and molecules, since the static potential for Ps interaction with a neutral system is zero. Theoretical description of both effects is a very challenging task. In the present work we use the free-electron-gas model to describe exchange and correlations in Ps collisions with molecules similar to the approach widely used in the theory of electron-molecule collisions. The results for exchange and correlation energies are presented as functions of the Fermi momentum of the electron gas and the Ps incident energy. Using the Thomas-Fermi model, these functions can be converted into exchange and correlation potentials for Ps interaction with molecules as functions of the distance between the projectile and the target.

Stopping dynamics of ions passing through correlated honeycomb clusters

NASA Astrophysics Data System (ADS)

Balzer, Karsten; Schlünzen, Niclas; Bonitz, Michael

2016-12-01

A combined nonequilibrium Green functions-Ehrenfest dynamics approach is developed that allows for a time-dependent study of the energy loss of a charged particle penetrating a strongly correlated system at zero and finite temperatures. Numerical results are presented for finite inhomogeneous two-dimensional Fermi-Hubbard models, where the many-electron dynamics in the target are treated fully quantum mechanically and the motion of the projectile is treated classically. The simulations are based on the solution of the two-time Dyson (Keldysh-Kadanoff-Baym) equations using the second-order Born, third-order, and T -matrix approximations of the self-energy. As application, we consider protons and helium nuclei with a kinetic energy between 1 and 500 keV/u passing through planar fragments of the two-dimensional honeycomb lattice and, in particular, examine the influence of electron-electron correlations on the energy exchange between projectile and electron system. We investigate the time dependence of the projectile's kinetic energy (stopping power), the electron density, the double occupancy, and the photoemission spectrum. Finally, we show that, for a suitable choice of the Hubbard model parameters, the results for the stopping power are in fair agreement with ab initio simulations for particle irradiation of single-layer graphene.

Microscopic Electron Variations Measured Simultaneously By The Cluster Spacecraft

NASA Astrophysics Data System (ADS)

Buckley, A. M.; Carozzi, T. D.; Gough, M. P.; Beloff, N.

Data is used from the Particle Correlator experiments running on each of the four Cluster spacecraft so as to determine common microscopic behaviour in the elec- tron population observed over the macroscopic Cluster separations. The Cluster par- ticle correlator experiments operate by forming on board Auto Correlation Functions (ACFs) generated from short time series of electron counts obtained, as a function of electron energy, from the PEACE HEEA sensor. The information on the microscopic variation of the electron flux covers the frequency range DC up to 41 kHz (encom- passing typical electron plasma frequencies and electron gyro frequencies and their harmonics), the electron energy range is that covered by the PEACE HEEA sensor (within the range 1 eV to 26 keV). Results are presented of coherent electron struc- tures observed simultaneously by the four spacecraft in the differing plasma interac- tion regions and boundaries encountered by Cluster. As an aid to understanding the plasma interactions, use is made of numerical simulations which model both the un- derlying statistical properties of the electrons and also the manner in which particle correlator experiments operate.

Theoretical development and first-principles analysis of strongly correlated systems

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

Liu, Chen

A variety of quantum many-body methods have been developed for studying the strongly correlated electron systems. We have also proposed a computationally efficient and accurate approach, named the correlation matrix renormalization (CMR) method, to address the challenges. The initial implementation of the CMR method is designed for molecules which have theoretical advantages, including small size of system, manifest mechanism and strongly correlation effect such as bond breaking process. The theoretic development and benchmark tests of the CMR method are included in this thesis. Meanwhile, ground state total energy is the most important property of electronic calculations. We also investigated anmore » alternative approach to calculate the total energy, and extended this method for magnetic anisotropy energy (MAE) of ferromagnetic materials. In addition, another theoretical tool, dynamical mean- field theory (DMFT) on top of the DFT , has also been used in electronic structure calculations for an Iridium oxide to study the phase transition, which results from an interplay of the d electrons' internal degrees of freedom.« less

Electronic Zero-Point Oscillations in the Strong-Interaction Limit of Density Functional Theory.

PubMed

Gori-Giorgi, Paola; Vignale, Giovanni; Seidl, Michael

2009-04-14

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron Hamiltonian, this same operator is multiplied by a real parameter λ varying between 0 (Kohn-Sham system) and 1 (physical system). In this process, usually called adiabatic connection, the one-electron density is kept fixed by a suitable local one-body potential. The strong-interaction limit of density functional theory, defined as the limit λ→∞, turns out to be like the opposite noninteracting Kohn-Sham limit (λ→0) mathematically simpler than the physical (λ = 1) case and can be used to build an approximate interpolation formula between λ→0 and λ→∞ for the exchange-correlation energy. Here we extend the systematic treatment of the λ→∞ limit [Phys. Rev. A 2007, 75, 042511] to the next leading term, describing zero-point oscillations of strictly correlated electrons, with numerical examples for small spherical atoms. We also propose an improved approximate functional for the zero-point term and a revised interpolation formula for the exchange-correlation energy satisfying more exact constraints.

Cavity Born-Oppenheimer Approximation for Correlated Electron-Nuclear-Photon Systems.

PubMed

Flick, Johannes; Appel, Heiko; Ruggenthaler, Michael; Rubio, Angel

2017-04-11

In this work, we illustrate the recently introduced concept of the cavity Born-Oppenheimer approximation [ Flick et al. PNAS 2017 , 10.1073/pnas.1615509114 ] for correlated electron-nuclear-photon problems in detail. We demonstrate how an expansion in terms of conditional electronic and photon-nuclear wave functions accurately describes eigenstates of strongly correlated light-matter systems. For a GaAs quantum ring model in resonance with a photon mode we highlight how the ground-state electronic potential-energy surface changes the usual harmonic potential of the free photon mode to a dressed mode with a double-well structure. This change is accompanied by a splitting of the electronic ground-state density. For a model where the photon mode is in resonance with a vibrational transition, we observe in the excited-state electronic potential-energy surface a splitting from a single minimum to a double minimum. Furthermore, for a time-dependent setup, we show how the dynamics in correlated light-matter systems can be understood in terms of population transfer between potential energy surfaces. This work at the interface of quantum chemistry and quantum optics paves the way for the full ab initio description of matter-photon systems.

The use of displacement damage dose to correlate degradation in solar cells exposed to different radiations

NASA Technical Reports Server (NTRS)

Summers, Geoffrey P.; Burke, Edward A.; Shapiro, Philip; Statler, Richard; Messenger, Scott R.; Walters, Robert J.

1994-01-01

It has been found useful in the past to use the concept of 'equivalent fluence' to compare the radiation response of different solar cell technologies. Results are usually given in terms of an equivalent 1 MeV electron or an equivalent 10 MeV proton fluence. To specify cell response in a complex space-radiation environment in terms of an equivalent fluence, it is necessary to measure damage coefficients for a number of representative electron and proton energies. However, at the last Photovoltaic Specialist Conference we showed that nonionizing energy loss (NIEL) could be used to correlate damage coefficients for protons, using measurements for GaAs as an example. This correlation means that damage coefficients for all proton energies except near threshold can be predicted from a measurement made at one particular energy. NIEL is the exact equivalent for displacement damage of linear energy transfer (LET) for ionization energy loss. The use of NIEL in this way leads naturally to the concept of 10 MeV equivalent proton fluence. The situation for electron damage is more complex, however. It is shown that the concept of 'displacement damage dose' gives a more general way of unifying damage coefficients. It follows that 1 MeV electron equivalent fluence is a special case of a more general quantity for unifying electron damage coefficients which we call the 'effective 1 MeV electron equivalent dose'.

Comparing Solar-Flare Acceleration of >-20 MeV Protons and Electrons Above Various Energies

NASA Technical Reports Server (NTRS)

Shih, Albert Y.

2010-01-01

A large fraction (up to tens of percent) of the energy released in solar flares goes into accelerated ions and electrons, and studies indicate that these two populations have comparable energy content. RHESSI observations have shown a striking close linear correlation between the 2.223 MeV neutron-capture gamma-ray line and electron bremsstrahlung emission >300 keV, indicating that the flare acceleration of >^20 MeV protons and >300 keV electrons is roughly proportional over >3 orders of magnitude in fluence. We show that the correlations of neutron-capture line fluence with GOES class or with bremsstrahlung emission at lower energies show deviations from proportionality, primarily for flares with lower fluences. From analyzing thirteen flares, we demonstrate that there appear to be two classes of flares with high-energy acceleration: flares that exhibit only proportional acceleration of ions and electrons down to 50 keV and flares that have an additional soft, low-energy bremsstrahlung component, suggesting two separate populations of accelerated electrons. We use RHESSI spectroscopy and imaging to investigate a number of these flares in detail.

Electronic correlation in magnetic contributions to structural energies

NASA Astrophysics Data System (ADS)

Haydock, Roger

For interacting electrons the density of transitions [see http://arxiv.org/abs/1405.2288] replaces the density of states in calculations of structural energies. Extending previous work on paramagnetic metals, this approach is applied to correlation effects on the structural stability of magnetic transition metals. Supported by the H. V. Snyder Gift to the University of Oregon.

Low-energy effective Hamiltonians for correlated electron systems beyond density functional theory

NASA Astrophysics Data System (ADS)

Hirayama, Motoaki; Miyake, Takashi; Imada, Masatoshi; Biermann, Silke

2017-08-01

We propose a refined scheme of deriving an effective low-energy Hamiltonian for materials with strong electronic Coulomb correlations beyond density functional theory (DFT). By tracing out the electronic states away from the target degrees of freedom in a controlled way by a perturbative scheme, we construct an effective Hamiltonian for a restricted low-energy target space incorporating the effects of high-energy degrees of freedom in an effective manner. The resulting effective Hamiltonian can afterwards be solved by accurate many-body solvers. We improve this "multiscale ab initio scheme for correlated electrons" (MACE) primarily in two directions by elaborating and combining two frameworks developed by Hirayama et al. [M. Hirayama, T. Miyake, and M. Imada, Phys. Rev. B 87, 195144 (2013), 10.1103/PhysRevB.87.195144] and Casula et al. [M. Casula, P. Werner, L. Vaugier, F. Aryasetiawan, T. Miyake, A. J. Millis, and S. Biermann, Phys. Rev. Lett. 109, 126408 (2012), 10.1103/PhysRevLett.109.126408]: (1) Double counting of electronic correlations between the DFT and the low-energy solver is avoided by using the constrained G W scheme; and (2) the frequency dependent interactions emerging from the partial trace summation are successfully separated into a nonlocal part that is treated following ideas by Hirayama et al. and a local part treated nonperturbatively in the spirit of Casula et al. and are incorporated into the renormalization of the low-energy dispersion. The scheme is favorably tested on the example of SrVO3.

Short-range density functional correlation within the restricted active space CI method

NASA Astrophysics Data System (ADS)

Casanova, David

2018-03-01

In the present work, I introduce a hybrid wave function-density functional theory electronic structure method based on the range separation of the electron-electron Coulomb operator in order to recover dynamic electron correlations missed in the restricted active space configuration interaction (RASCI) methodology. The working equations and the computational algorithm for the implementation of the new approach, i.e., RAS-srDFT, are presented, and the method is tested in the calculation of excitation energies of organic molecules. The good performance of the RASCI wave function in combination with different short-range exchange-correlation functionals in the computation of relative energies represents a quantitative improvement with respect to the RASCI results and paves the path for the development of RAS-srDFT as a promising scheme in the computation of the ground and excited states where nondynamic and dynamic electron correlations are important.

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

Gledhill, Jonathan D.; Tozer, David J., E-mail: d.j.tozer@durham.ac.uk

Density scaling considerations are used to derive an exchange–correlation explicit density functional that is appropriate for the electron deficient side of the integer and which recovers the exact r → ∞ asymptotic behaviour of the exchange–correlation potential. The functional has an unconventional mathematical form with parameters that are system-dependent; the parameters for an N-electron system are determined in advance from generalised gradient approximation (GGA) calculations on the N- and (N − 1)-electron systems. Compared to GGA results, the functional yields similar exchange–correlation energies, but HOMO energies that are an order of magnitude closer to the negative of the vertical ionisationmore » potential; for anions, the HOMO energies are negative, as required. Rydberg excitation energies are also notably improved and the exchange–correlation potential is visibly lowered towards the near-exact potential. Further development is required to improve valence excitations, static isotropic polarisabilities, and the shape of the potential in non-asymptotic regions. The functional is fundamentally different to conventional approximations.« less

Energy Weighted Angular Correlations Between Hadrons Produced in Electron-Positron Annihilation.

NASA Astrophysics Data System (ADS)

Strharsky, Roger Joseph

Electron-positron annihilation at large center of mass energy produces many hadronic particles. Experimentalists then measure the energies of these particles in calorimeters. This study investigated correlations between the angular locations of one or two such calorimeters and the angular orientation of the electron beam in the laboratory frame of reference. The calculation of these correlations includes weighting by the fraction of the total center of mass energy which the calorimeter measures. Starting with the assumption that the reaction proceeeds through the intermediate production of a single quark/anti-quark pair, a simple statistical model was developed to provide a phenomenological description of the distribution of final state hadrons. The model distributions were then used to calculate the one- and two-calorimeter correlation functions. Results of these calculations were compared with available data and several predictions were made for those quantities which had not yet been measured. Failure of the model to reproduce all of the data was discussed in terms of quantum chromodynamics, a fundamental theory which includes quark interactions.

The interaction of low-energy electrons with fructose molecules

NASA Astrophysics Data System (ADS)

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

2017-11-01

Using a hypocycloidal electronic spectrometer, the interactions of low energy electrons (0-8.50 eV) with fructose molecules, namely, electron scattering and dissociative attachment, are studied. The results of these studies showed that the fragmentation of fructose molecules occurs effectively even at an electron energy close to zero. In the total electron-scattering cross section by molecules, resonance features (at energies 3.10 and 5.00 eV) were first observed near the formation thresholds of light ion fragments OH- and H-. The correlation of the features observed in the cross sections of electron scattering and dissociative attachment is analyzed.

Characteristic energy range of electron scattering due to plasmaspheric hiss

DOE PAGES

Ma, Q.; Li, W.; Thorne, R. M.; ...

2016-11-15

In this paper, we investigate the characteristic energy range of electron flux decay due to the interaction with plasmaspheric hiss in the Earth's inner magnetosphere. The Van Allen Probes have measured the energetic electron flux decay profiles in the Earth's outer radiation belt during a quiet period following the geomagnetic storm that occurred on 7 November 2015. The observed energy of significant electron decay increases with decreasing L shell and is well correlated with the energy band corresponding to the first adiabatic invariant μ = 4–200 MeV/G. The electron diffusion coefficients due to hiss scattering are calculated at L =more » 2–6, and the modeled energy band of effective pitch angle scattering is also well correlated with the constant μ lines and is consistent with the observed energy range of electron decay. Using the previously developed statistical plasmaspheric hiss model during modestly disturbed periods, we perform a 2-D Fokker-Planck simulation of the electron phase space density evolution at L = 3.5 and demonstrate that plasmaspheric hiss causes the significant decay of 100 keV–1 MeV electrons with the largest decay rate occurring at around 340 keV, forming anisotropic pitch angle distributions at lower energies and more flattened distributions at higher energies. Finally, our study provides reasonable estimates of the electron populations that can be most significantly affected by plasmaspheric hiss and the consequent electron decay profiles.« less

Correlation of intercalation potential with d-electron configurations for cathode compounds of lithium-ion batteries.

PubMed

Chen, Zhenlian; Zhang, Caixia; Zhang, Zhiyong; Li, Jun

2014-07-14

The d-electron localization is widely recognized as important to transport properties of transition metal compounds, but its role in the energy conversion of intercalation reactions of cathode compounds is still not fully explored. In this work, the correlation of intercalation potential with electron affinity, a key energy term controlling electron intercalation, then with d-electron configuration, is investigated. Firstly, we find that the change of the intercalation potential with respect to the transition metal cations within the same structure class is correlated in an approximately mirror relationship with the electron affinity, based on first-principles calculations on three typical categories of cathode compounds including layered oxides and polyoxyanions Then, by using a new model Hamiltonian based on the crystal-field theory, we reveal that the evolution is governed by the combination of the crystal-field splitting and the on-site d-d exchange interactions. Further, we show that the charge order in solid-solution composites and the compatibility of multi-electron redox steps could be inferred from the energy terms with the d-electron configuration alternations. These findings may be applied to rationally designing new chemistry for the lithium-ion batteries and other metal-ion batteries.

Nonequilibrium electron and lattice dynamics of strongly correlated Bi 2Sr 2CaCu 2O 8+δ single crystals

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

Konstantinova, Tatiana; Rameau, Jonathan D.; Reid, Alexander H.

Here, the interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped Bi 2Sr 2CaCu 2O 8+δ. Quantitative analysis of the lattice and electron subsystems’ dynamics provides a unified picturemore » of nonequilibrium electron-phonon interactions in the cuprates beyond the N-temperature model. The work provides new insights on the specific phonon branches involved in the nonequilibrium heat dissipation from the high-energy Cu–O bond stretching “hot” phonons to the lowest-energy acoustic phonons with correlated atomic motion along the <110> crystal directions and their characteristic time scales. It reveals a highly nonthermal phonon population during the first several picoseconds after the photoexcitation. The approach, taking advantage of the distinct nature of electrons and photons as probes, is applicable for studying energy relaxation in other strongly correlated electron systems.« less

Nonequilibrium electron and lattice dynamics of strongly correlated Bi 2Sr 2CaCu 2O 8+δ single crystals

DOE PAGES

Konstantinova, Tatiana; Rameau, Jonathan D.; Reid, Alexander H.; ...

2018-04-27

Here, the interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped Bi 2Sr 2CaCu 2O 8+δ. Quantitative analysis of the lattice and electron subsystems’ dynamics provides a unified picturemore » of nonequilibrium electron-phonon interactions in the cuprates beyond the N-temperature model. The work provides new insights on the specific phonon branches involved in the nonequilibrium heat dissipation from the high-energy Cu–O bond stretching “hot” phonons to the lowest-energy acoustic phonons with correlated atomic motion along the <110> crystal directions and their characteristic time scales. It reveals a highly nonthermal phonon population during the first several picoseconds after the photoexcitation. The approach, taking advantage of the distinct nature of electrons and photons as probes, is applicable for studying energy relaxation in other strongly correlated electron systems.« less

Electronic Structures of Anti-Ferromagnetic Tetraradicals: Ab Initio and Semi-Empirical Studies.

PubMed

Zhang, Dawei; Liu, Chungen

2016-04-12

The energy relationships and electronic structures of the lowest-lying spin states in several anti-ferromagnetic tetraradical model systems are studied with high-level ab initio and semi-empirical methods. The Full-CI method (FCI), the complete active space second-order perturbation theory (CASPT2), and the n-electron valence state perturbation theory (NEVPT2) are employed to obtain reference results. By comparing the energy relationships predicted from the Heisenberg and Hubbard models with ab initio benchmarks, the accuracy of the widely used Heisenberg model for anti-ferromagnetic spin-coupling in low-spin polyradicals is cautiously tested in this work. It is found that the strength of electron correlation (|U/t|) concerning anti-ferromagnetically coupled radical centers could range widely from strong to moderate correlation regimes and could become another degree of freedom besides the spin multiplicity. Accordingly, the Heisenberg-type model works well in the regime of strong correlation, which reproduces well the energy relationships along with the wave functions of all the spin states. In moderately spin-correlated tetraradicals, the results of the prototype Heisenberg model deviate severely from those of multi-reference electron correlation ab initio methods, while the extended Heisenberg model, containing four-body terms, can introduce reasonable corrections and maintains its accuracy in this condition. In the weak correlation regime, both the prototype Heisenberg model and its extended forms containing higher-order correction terms will encounter difficulties. Meanwhile, the Hubbard model shows balanced accuracy from strong to weak correlation cases and can reproduce qualitatively correct electronic structures, which makes it more suitable for the study of anti-ferromagnetic coupling in polyradical systems.

Density Functionals of Chemical Bonding

PubMed Central

Putz, Mihai V.

2008-01-01

The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems. PMID:19325846

Two-dimensional Electronic Double-Quantum Coherence Spectroscopy

PubMed Central

Kim, Jeongho; Mukamel, Shaul

2009-01-01

CONSPECTUS The theory of electronic structure of many-electron systems like molecules is extraordinarily complicated. A lot can be learned by considering how electron density is distributed, on average, in the average field of the other electrons in the system. That is, mean field theory. However, to describe quantitatively chemical bonds, reactions, and spectroscopy requires consideration of the way that electrons avoid each other by the way they move; this is called electron correlation (or in physics, the many-body problem for fermions). While great progress has been made in theory, there is a need for incisive experimental tests that can be undertaken for large molecular systems in the condensed phase. Here we report a two-dimensional (2D) optical coherent spectroscopy that correlates the double excited electronic states to constituent single excited states. The technique, termed two-dimensional double-coherence spectroscopy (2D-DQCS), makes use of multiple, time-ordered ultrashort coherent optical pulses to create double- and single-quantum coherences over time intervals between the pulses. The resulting two-dimensional electronic spectrum maps the energy correlation between the first excited state and two-photon allowed double-quantum states. The principle of the experiment is that when the energy of the double-quantum state, viewed in simple models as a double HOMO to LUMO excitation, equals twice that of a single excitation, then no signal is radiated. However, electron-electron interactions—a combination of exchange interactions and electron correlation—in real systems generates a signal that reveals precisely how the energy of the double-quantum resonance differs from twice the single-quantum resonance. The energy shift measured in this experiment reveals how the second excitation is perturbed by both the presence of the first excitation and the way that the other electrons in the system have responded to the presence of that first excitation. We compare a series of organic dye molecules and find that the energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of milli-electronvolts, and it depends quite sensitively on molecular geometry. These results demonstrate the effectiveness of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wavefunctions, and electron correlation in electronic excited states and excitons. PMID:19552412

Constraint on the second functional derivative of the exchange-correlation energy

NASA Astrophysics Data System (ADS)

Joubert, D. P.

2012-09-01

Using the density functional adiabatic connection approach for an N-electron system it is shown that ? γ is the coupling constant that scales the electron-electron interaction strength. For the non-interacting Kohn-Sham Hamiltonian γ = 0 and for the fully interacting system γ = 1. ? is the Hartree plus exchange-correlation energy while f 0(r) and fγ(r) are the Fukui functions of the non-interacting and interacting systems, respectively. This identity can serve to test the internal self-consistency or quality of approximate functionals. The quality of some popular approximate exchange and correlation functionals are tested for a simple model system.

Self-Consistent Theory of Shot Noise Suppression in Ballistic Conductors

NASA Astrophysics Data System (ADS)

Bulashenko, O. M.; Rubí, J. M.; Kochelap, V. A.

Shot-noise measurements become a fundamental tool to probe carrier interactions in mesoscopic systems [1]. A matter of particular interest is the significance of Coulomb interaction which may keep nearby electrons more regularly spaced rather than strictly at random and lead to the noise reduction. That effect occurs in different physical situations. Among them are charge-limited ballistic transport, resonant tunneling, single-electron tunneling, etc. In this communication we address the problem of Coulomb correlations in ballistic conductors under the space-charge-limited transport conditions, and present for the first time a semiclassical self-consistent theory of shot noise in these conductors by solving analytically the kinetic equation coupled self-consistently with a Poisson equation. Basing upon this theory, exact results for current noise in a two-terminal ballistic conductor under the action of long-range Coulomb correlations has been derived. The noise reduction factor (in respect to the uncorrelated value) is obtained in a closed analytical form for a full range of biases ranging from thermal to shot-noise limits which describe perfectly the results of the Monte Carlo simulations for a nondegenerate electron gas [2]. The magnitude of the noise reduction exceeds 0.01, which is of interest from the point of view of possible applications. Using these analytical results one may estimate a relative contribution to the noise from different groups of carriers (in energy space and/or real space) and to investigate in great detail the correlations between different groups of carriers. This leads us to suggest an electron energy spectroscopy experiment to probe the Coulomb correlations in ballistic conductors. Indeed, while the injected carriers are uncorrelated, those in the volume of the conductor are strongly correlated, as follows from the derived formulas for the fluctuation of the distribution function. Those correlations may be observed experimentally by making use of a combination of two already realized techniques: a hot-electron spectrometer [3,4] which allows one to analyze different energy groups of electrons collected at the contact and shot-noise measurements [5,6]. Such "shot noise reduction spectroscopy" allows one to measure the novel phenomena. In particular, we predict the (anti)correlation of the "tangent" electrons having the energy close to the potential barrier height, to all other electron energy groups collected at the receiving contact.

Energy conversion modeling of the intrinsic persistent luminescence of solids via energy transfer paths between transition levels.

PubMed

Huang, Bolong; Sun, Mingzi

2017-04-05

An energy conversion model has been established for the intrinsic persistent luminescence in solids related to the native point defect levels, formations, and transitions. In this study, we showed how the recombination of charge carriers between different defect levels along the zero phonon line (ZPL) can lead to energy conversions supporting the intrinsic persistent phosphorescence in solids. This suggests that the key driving force for this optical phenomenon is the pair of electrons hopping between different charged defects with negative-U eff . Such a negative correlation energy will provide a sustainable energy source for electron-holes to further recombine in a new cycle with a specific quantum yield. This will help us to understand the intrinsic persistent luminescence with respect to native point defect levels as well as the correlations of electronics and energetics.

Metal-insulator transition in a doubly orbitally degenerate model with correlated hopping

NASA Astrophysics Data System (ADS)

Didukh, L.; Skorenkyy, Yu.; Dovhopyaty, Yu.; Hankevych, V.

2000-03-01

In the present paper, we propose a doubly orbitally degenerate narrow-band model with correlated hopping. The peculiarity of the model is taking into account the matrix element of electron-electron interaction, which describes intersite hoppings of electrons. In particular, this leads to the concentration dependence of the effective hopping integral. The cases of the strong and weak Hund's coupling are considered. By means of a generalized mean-field approximation the single-particle Green function and quasiparticle energy spectrum are calculated. Metal-insulator transition is studied in the model at different integer values of the electron concentration. With the help of the obtained energy spectrum, we find energy gap width and criteria of metal-insulator transition.

Correlation energy extrapolation by many-body expansion

DOE PAGES

Boschen, Jeffery S.; Theis, Daniel; Ruedenberg, Klaus; ...

2017-01-09

Accounting for electron correlation is required for high accuracy calculations of molecular energies. The full configuration interaction (CI) approach can fully capture the electron correlation within a given basis, but it does so at a computational expense that is impractical for all but the smallest chemical systems. In this work, a new methodology is presented to approximate configuration interaction calculations at a reduced computational expense and memory requirement, namely, the correlation energy extrapolation by many-body expansion (CEEMBE). This method combines a MBE approximation of the CI energy with an extrapolated correction obtained from CI calculations using subsets of the virtualmore » orbitals. The extrapolation approach is inspired by, and analogous to, the method of correlation energy extrapolation by intrinsic scaling. Benchmark calculations of the new method are performed on diatomic fluorine and ozone. Finally, the method consistently achieves agreement with CI calculations to within a few mhartree and often achieves agreement to within ~1 millihartree or less, while requiring significantly less computational resources.« less

Correlation energy extrapolation by many-body expansion

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

Boschen, Jeffery S.; Theis, Daniel; Ruedenberg, Klaus

Accounting for electron correlation is required for high accuracy calculations of molecular energies. The full configuration interaction (CI) approach can fully capture the electron correlation within a given basis, but it does so at a computational expense that is impractical for all but the smallest chemical systems. In this work, a new methodology is presented to approximate configuration interaction calculations at a reduced computational expense and memory requirement, namely, the correlation energy extrapolation by many-body expansion (CEEMBE). This method combines a MBE approximation of the CI energy with an extrapolated correction obtained from CI calculations using subsets of the virtualmore » orbitals. The extrapolation approach is inspired by, and analogous to, the method of correlation energy extrapolation by intrinsic scaling. Benchmark calculations of the new method are performed on diatomic fluorine and ozone. Finally, the method consistently achieves agreement with CI calculations to within a few mhartree and often achieves agreement to within ~1 millihartree or less, while requiring significantly less computational resources.« less

Development of an electron-ion coincidence apparatus for molecular-frame electron energy loss spectroscopy studies

NASA Astrophysics Data System (ADS)

Watanabe, Noboru; Hirayama, Tsukasa; Yamada, So; Takahashi, Masahiko

2018-04-01

We report details of an electron-ion coincidence apparatus, which has been developed for molecular-frame electron energy loss spectroscopy studies. The apparatus is mainly composed of a pulsed electron gun, an energy-dispersive electron spectrometer, and an ion momentum imaging spectrometer. Molecular-orientation dependence of the high-energy electron scattering cross section can be examined by conducting measurements of vector correlation between the momenta of the scattered electron and fragment ion. Background due to false coincidences is significantly reduced by introducing a pulsed electron beam and pulsing scheme of ion extraction. The experimental setup has been tested by measuring the inner-shell excitation of N2 at an incident electron energy of 1.5 keV and a scattering angle of 10.2°.

Correlated electron-nuclear dynamics in above-threshold multiphoton ionization of asymmetric molecule.

PubMed

Wang, Zhuo; Li, Min; Zhou, Yueming; Lan, Pengfei; Lu, Peixiang

2017-02-20

The partition of the photon energy into the subsystems of molecules determines many photon-induced chemical and physical dynamics in laser-molecule interactions. The electron-nuclear energy sharing from multiphoton ionization of molecules has been used to uncover the correlated dynamics of the electron and fragments. However, most previous studies focus on symmetric molecules. Here we study the electron-nuclear energy sharing in strong-field photoionization of HeH 2+ by solving the one-dimensional time-dependent Schrödinger equation (TDSE). Compared with symmetric molecules, the joint electron-nuclear energy spectrum (JES) of HeH 2+ reveals an anomalous energy shift at certain nuclear energies, while it disappears at higher and lower nuclear energies. Through tracing the time evolution of the wavepacket of bound states, we identify that this energy shift originates from the joint effect of the Stark shift, associated with the permanent dipole, and the Autler-Townes effect due to the coupling of the 2pσ and 2sσ states in strong fields. The energy shift in the JES appears at certain nuclear distances only when both Stark effect and Autler-Townes effect play important roles. We further demonstrate that the electron-nuclei energy sharing can be controlled by varying laser intensity for asymmetric molecules, providing alternative approaches to manipulate photochemical reactions for more complex molecules.

Extended screened exchange functional derived from transcorrelated density functional theory.

PubMed

Umezawa, Naoto

2017-09-14

We propose a new formulation of the correlation energy functional derived from the transcorrelated method in use in density functional theory (TC-DFT). An effective Hamiltonian, H TC , is introduced by a similarity transformation of a many-body Hamiltonian, H, with respect to a complex function F: H TC =1FHF. It is proved that an expectation value of H TC for a normalized single Slater determinant, D n , corresponds to the total energy: E[n] = ⟨Ψ n |H|Ψ n ⟩/⟨Ψ n |Ψ n ⟩ = ⟨D n |H TC |D n ⟩ under the two assumptions: (1) The electron density nr associated with a trial wave function Ψ n = D n F is v-representable and (2) Ψ n and D n give rise to the same electron density nr. This formulation, therefore, provides an alternative expression of the total energy that is useful for the development of novel correlation energy functionals. By substituting a specific function for F, we successfully derived a model correlation energy functional, which resembles the functional form of the screened exchange method. The proposed functional, named the extended screened exchange (ESX) functional, is described within two-body integrals and is parametrized for a numerically exact correlation energy of the homogeneous electron gas. The ESX functional does not contain any ingredients of (semi-)local functionals and thus is totally free from self-interactions. The computational cost for solving the self-consistent-field equation is comparable to that of the Hartree-Fock method. We apply the ESX functional to electronic structure calculations for a solid silicon, H - ion, and small atoms. The results demonstrate that the TC-DFT formulation is promising for the systematic improvement of the correlation energy functional.

The water-water cycle is a major electron sink in Camellia species when CO2 assimilation is restricted.

PubMed

Cai, Yan-Fei; Yang, Qiu-Yun; Li, Shu-Fa; Wang, Ji-Hua; Huang, Wei

2017-03-01

The water-water cycle (WWC) is thought to dissipate excess excitation energy and balance the ATP/NADPH energy budget under some conditions. However, the importance of the WWC in photosynthetic regulation remains controversy. We observed that three Camellia cultivars exhibited high rates of photosynthetic electron flow under high light when photosynthesis was restricted. We thus tested the hypothesis that the WWC is a major electron sink in the three Camellia cultivars when CO 2 assimilation is restricted. Light response curves indicated that the WWC was strongly increased with photorespiration and was positively correlated with extra ATP supplied from other flexible mechanisms excluding linear electron flow, implying that the WWC is an important alternative electron sink to balance ATP/NADPH energy demand for sustaining photorespiration in Camellia cultivars. Interestingly, when photosynthesis was depressed by the decreases in stomatal and mesophyll conductance, the rates of photosynthetic electron flow through photosystem II declined slightly and the rates of WWC was enhanced. Furthermore, the increased electron flow of WWC was positively correlated with the ratio of Rubisco oxygenation to carboxylation, supporting the involvement of alternative electron flow in balancing the ATP/NADPH energy budget. We propose that the WWC is a crucial electron sink to regulate ATP/NADPH energy budget and dissipate excess energy excitation in Camellia species when CO 2 assimilation is restricted. Copyright © 2017. Published by Elsevier B.V.

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

Generic expansion of the Jastrow correlation factor in polynomials satisfying symmetry and cusp conditions

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

Lüchow, Arne, E-mail: luechow@rwth-aachen.de; Jülich Aachen Research Alliance; Sturm, Alexander

2015-02-28

Jastrow correlation factors play an important role in quantum Monte Carlo calculations. Together with an orbital based antisymmetric function, they allow the construction of highly accurate correlation wave functions. In this paper, a generic expansion of the Jastrow correlation function in terms of polynomials that satisfy both the electron exchange symmetry constraint and the cusp conditions is presented. In particular, an expansion of the three-body electron-electron-nucleus contribution in terms of cuspless homogeneous symmetric polynomials is proposed. The polynomials can be expressed in fairly arbitrary scaling function allowing a generic implementation of the Jastrow factor. It is demonstrated with a fewmore » examples that the new Jastrow factor achieves 85%–90% of the total correlation energy in a variational quantum Monte Carlo calculation and more than 90% of the diffusion Monte Carlo correlation energy.« less

Fluctuation Diagnostics of the Electron Self-Energy: Origin of the Pseudogap Physics.

PubMed

Gunnarsson, O; Schäfer, T; LeBlanc, J P F; Gull, E; Merino, J; Sangiovanni, G; Rohringer, G; Toschi, A

2015-06-12

We demonstrate how to identify which physical processes dominate the low-energy spectral functions of correlated electron systems. We obtain an unambiguous classification through an analysis of the equation of motion for the electron self-energy in its charge, spin, and particle-particle representations. Our procedure is then employed to clarify the controversial physics responsible for the appearance of the pseudogap in correlated systems. We illustrate our method by examining the attractive and repulsive Hubbard model in two dimensions. In the latter, spin fluctuations are identified as the origin of the pseudogap, and we also explain why d-wave pairing fluctuations play a marginal role in suppressing the low-energy spectral weight, independent of their actual strength.

Observation of fast and slow interatomic Coulombic decay in argon dimers induced by electron-impact ionization

NASA Astrophysics Data System (ADS)

Ren, Xueguang; Miteva, Tsveta; Kolorenč, Přemysl; Gokhberg, Kirill; Kuleff, Alexander I.; Cederbaum, Lorenz S.; Dorn, Alexander

2017-09-01

We investigate the interatomic Coulombic decay (ICD) in argon dimers induced by electron-impact ionization (E0=90 eV ) using a multiparticle coincidence experiment in which the momentum vectors and, consequently, the kinetic energies for electrons and fragment ions are determined. The signature of the ICD process is obtained from a correlation map between ejected electron energy and kinetic energy release (KER) for Ar++Ar+ fragment ions where low-energy ICD electrons can be identified. Furthermore, two types of ICD processes, termed fast and slow interatomic decay, are separated by the ICD initial-state energies and projectile energy losses. The dependence of the energies of emitted low-energy ICD electrons on the initial-state energy is studied. ICD electron energy spectra and KER spectra are obtained separately for fast and slow decay processes where the KER spectra for the slow decay channel are strongly influenced by nuclear motion. The KER and ICD electron energy spectra are well reproduced by ab initio calculations.

DNA-based nanobiostructured devices: The role of quasiperiodicity and correlation effects

NASA Astrophysics Data System (ADS)

Albuquerque, E. L.; Fulco, U. L.; Freire, V. N.; Caetano, E. W. S.; Lyra, M. L.; de Moura, F. A. B. F.

2014-02-01

The purpose of this review is to present a comprehensive and up-to-date account of the main physical properties of DNA-based nanobiostructured devices, stressing the role played by their quasi-periodicity arrangement and correlation effects. Although the DNA-like molecule is usually described as a short-ranged correlated random ladder, artificial segments can be grown following quasiperiodic sequences as, for instance, the Fibonacci and Rudin-Shapiro ones. They have interesting properties like a complex fractal spectra of energy, which can be considered as their indelible mark, and collective properties that are not shared by their constituents. These collective properties are due to the presence of long-range correlations, which are expected to be reflected somehow in their various spectra (electronic transmission, density of states, etc.) defining another description of disorder. Although long-range correlations are responsible for the effective electronic transport at specific resonant energies of finite DNA segments, much of the anomalous spread of an initially localized electron wave-packet can be accounted by short-range pair correlations, suggesting that an approach based on the inclusion of further short-range correlations on the nucleotide distribution leads to an adequate description of the electronic properties of DNA segments. The introduction of defects may generate states within the gap, and substantially improves the conductance, specially of finite branches. They usually become exponentially localized for any amount of disorder, and have the property to tailor the electronic transport properties of DNA-based nanoelectronic devices. In particular, symmetric and antisymmetric correlations have quite distinct influence on the nature of the electronic states, and a diluted distribution of defects lead to an anomalous diffusion of the electronic wave-packet. Nonlinear contributions, arising from the coupling between electrons and the molecular vibrations, promote an electronic self-trapping, thus opening up the possibility of controlling the spreading of the electronic density by an external field. The main features of DNA-based nanobiostructured devices presented in this review will include their electronic density of states, energy profiles, thermodynamic properties, localization, correlation effects, scale laws, fractal and multifractal analysis, and anhydrous crystals of their bases, among others. New features, like other nanobiostructured devices, as well as the future directions in this field are also presented and discussed.

Quiet-Time Suprathermal ( 0.1-1.5 keV) Electrons in the Solar Wind

NASA Astrophysics Data System (ADS)

Wang, L.; Tao, J.; Zong, Q.; Li, G.; Salem, C. S.; Wimmer-Schweingruber, R. F.; He, J.; Tu, C.; Bale, S. D.

2016-12-01

We present a statistical survey of the energy spectrum of solar wind suprathermal (˜0.1-1.5 keV) electrons measured by the WIND/3DP instrument at 1 AU during quiet times at the minimum and maximum of solar cycles 23 and 24. After separating (beaming) strahl electrons from (isotropic) halo electrons according to their different behaviors in the angular distribution, we fit the observed energy spectrum of both strahl and halo electrons at ˜0.1-1.5 keV to a Kappa distribution function with an index κ and effective temperature Teff. We also calculate the number density n and average energy Eavg of strahl and halo electrons by integrating the electron measurements between ˜0.1 and 1.5 keV. We find a strong positive correlation between κ and Teff for both strahl and halo electrons, and a strong positive correlation between the strahl n and halo n, likely reflecting the nature of the generation of these suprathermal electrons. In both solar cycles, κ is larger at solar minimum than at solar maximum for both strahl and halo electrons. The halo κ is generally smaller than the strahl κ (except during the solar minimum of cycle 23). The strahl n is larger at solar maximum, but the halo n shows no difference between solar minimum and maximum. Both the strahl n and halo n have no clear association with the solar wind core population, but the density ratio between the strahl and halo roughly anti-correlates (correlates) with the solar wind density (velocity).

Quiet-time Suprathermal (~0.1-1.5 keV) Electrons in the Solar Wind

NASA Astrophysics Data System (ADS)

Tao, Jiawei; Wang, Linghua; Zong, Qiugang; Li, Gang; Salem, Chadi S.; Wimmer-Schweingruber, Robert F.; He, Jiansen; Tu, Chuanyi; Bale, Stuart D.

2016-03-01

We present a statistical survey of the energy spectrum of solar wind suprathermal (˜0.1-1.5 keV) electrons measured by the WIND 3DP instrument at 1 AU during quiet times at the minimum and maximum of solar cycles 23 and 24. After separating (beaming) strahl electrons from (isotropic) halo electrons according to their different behaviors in the angular distribution, we fit the observed energy spectrum of both strahl and halo electrons at ˜0.1-1.5 keV to a Kappa distribution function with an index κ and effective temperature Teff. We also calculate the number density n and average energy Eavg of strahl and halo electrons by integrating the electron measurements between ˜0.1 and 1.5 keV. We find a strong positive correlation between κ and Teff for both strahl and halo electrons, and a strong positive correlation between the strahl n and halo n, likely reflecting the nature of the generation of these suprathermal electrons. In both solar cycles, κ is larger at solar minimum than at solar maximum for both strahl and halo electrons. The halo κ is generally smaller than the strahl κ (except during the solar minimum of cycle 23). The strahl n is larger at solar maximum, but the halo n shows no difference between solar minimum and maximum. Both the strahl n and halo n have no clear association with the solar wind core population, but the density ratio between the strahl and halo roughly anti-correlates (correlates) with the solar wind density (velocity).

Dynamic Electron Correlation Effects on the Ground State Potential Energy Surface of a Retinal Chromophore Model.

PubMed

Gozem, Samer; Huntress, Mark; Schapiro, Igor; Lindh, Roland; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

2012-11-13

The ground state potential energy surface of the retinal chromophore of visual pigments (e.g., bovine rhodopsin) features a low-lying conical intersection surrounded by regions with variable charge-transfer and diradical electronic structures. This implies that dynamic electron correlation may have a large effect on the shape of the force fields driving its reactivity. To investigate this effect, we focus on mapping the potential energy for three paths located along the ground state CASSCF potential energy surface of the penta-2,4-dieniminium cation taken as a minimal model of the retinal chromophore. The first path spans the bond length alternation coordinate and intercepts a conical intersection point. The other two are minimum energy paths along two distinct but kinetically competitive thermal isomerization coordinates. We show that the effect of introducing the missing dynamic electron correlation variationally (with MRCISD) and perturbatively (with the CASPT2, NEVPT2, and XMCQDPT2 methods) leads, invariably, to a stabilization of the regions with charge transfer character and to a significant reshaping of the reference CASSCF potential energy surface and suggesting a change in the dominating isomerization mechanism. The possible impact of such a correction on the photoisomerization of the retinal chromophore is discussed.

The source of multi spectral energy of solar energetic electron

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

Herdiwijaya, Dhani

2015-04-16

We study the solar energetic electron distribution obtained from ACE and GOES satellites which have different altitudes and electron spectral energy during the year 1997 to 2011. The electron spectral energies were 0.038–0.315 MeV from EPAM instrument onboard ACE satellite and >2 MeV from GOES satellite. We found that the low electron energy has no correlation with high energy. In spite of we have corrected to the altitude differences. It implied that they originated from time dependent events with different sources and physical processes at the solar atmosphere. The sources of multi spectral energetic electron were related to flare andmore » CME phenomena. However, we also found that high energetic electron comes from coronal hole.« less

Study of Charm and Beauty using electron-D{sup 0} azimuthal correlations in the STAR experiment at RHIC

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

Kabana, Sonia

The energy loss of heavy quarks in the hot and dense matter created in high-energy nuclear collisions at RHIC, can be used to probe the properties of the medium. Both charm and beauty quarks contribute to the non-photonic electrons through their semi-leptonic decays. It is essential to determine experimentally the relative contributions of charm and beauty quarks to understand the observed suppression of non-photonic electrons at high p{sub T} in central Au+Au collisions. The azimuthal angular correlations of non-photonic electrons with hadrons as well as with the reconstructed D{sup 0} allow to disentangle the contributions of charm and beauty tomore » the electron spectrum. We discuss the STAR measurement of non-photonic electron-D{sup 0} and non-photonic electron-hadron azimuthal correlations in p+p collisions at 200 GeV and explore the consequences for the heavy flavour suppression in heavy ion collisions at RHIC.« less

Correlations with Non-Photonic Electrons in√ sNN = 200 GeV Au+Au Collisions in STAR

NASA Astrophysics Data System (ADS)

Dunkelberger, Lloyd Edward, Jr.

At sufficiently high temperatures and densities quarks and gluons exist in a deconfined state called Quark Gluon Plasma (QGP). QGP existed in the Universe shortly after the Big Bang, and today is created in accelerator based experiments which collide heavy nuclei at high energies. Results from these experiments point to a hot, dense and strongly interacting state of deconfined quarks and gluons. The study of heavy flavor probes (those originating from c and b quarks) is an active area of research in heavy ion collisions. Heavy quarks are produced in the initial hard scatterings of collisions and thus are sensitive to the entire evolution of the medium. They also potentially have different sensitivity to medium induced energy loss compared to light flavors. This dissertation investigates the interactions of heavy flavor quarks with the medium by studying correlations between electrons from heavy flavor decays and hadrons. At high transverse momentum, the direction of the electron is highly correlated with the direction of the parent heavy flavor meson. We look for evidence of energy loss in the QGP as well as jet induced effects on the medium. We present electron-hadron correlations from Au+Au collisions in a wide range of centrality bins as well as correlations from p+p. The datasets used are the best currently available due to high statistics and low material in the detector. We also investigate the dependence on the orientation of the trigger particle to the event plane to look for path length dependent effects on the correlation as well as non-flow contributions to electron electron v2.

A Distributed Lag Autoregressive Model of Geostationary Relativistic Electron Fluxes: Comparing the Influences of Waves, Seed and Source Electrons, and Solar Wind Inputs

NASA Astrophysics Data System (ADS)

Simms, Laura; Engebretson, Mark; Clilverd, Mark; Rodger, Craig; Lessard, Marc; Gjerloev, Jesper; Reeves, Geoffrey

2018-05-01

Relativistic electron flux at geosynchronous orbit depends on enhancement and loss processes driven by ultralow frequency (ULF) Pc5, chorus, and electromagnetic ion cyclotron (EMIC) waves, seed electron flux, magnetosphere compression, the "Dst effect," and substorms, while solar wind inputs such as velocity, number density, and interplanetary magnetic field Bz drive these factors and thus correlate with flux. Distributed lag regression models show the time delay of highest influence of these factors on log10 high-energy electron flux (0.7-7.8 MeV, Los Alamos National Laboratory satellites). Multiple regression with an autoregressive term (flux persistence) allows direct comparison of the magnitude of each effect while controlling other correlated parameters. Flux enhancements due to ULF Pc5 and chorus waves are of equal importance. The direct effect of substorms on high-energy electron flux is strong, possibly due to injection of high-energy electrons by the substorms themselves. Loss due to electromagnetic ion cyclotron waves is less influential. Southward Bz shows only moderate influence when correlated processes are accounted for. Adding covariate compression effects (pressure and interplanetary magnetic field magnitude) allows wave-driven enhancements to be more clearly seen. Seed electrons (270 keV) are most influential at lower relativistic energies, showing that such a population must be available for acceleration. However, they are not accelerated directly to the highest energies. Source electrons (31.7 keV) show no direct influence when other factors are controlled. Their action appears to be indirect via the chorus waves they generate. Determination of specific effects of each parameter when studied in combination will be more helpful in furthering modeling work than studying them individually.

Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

PubMed

Lee, Mi Kyung; Coker, David F

2016-08-18

An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation.

On-top density functionals for the short-range dynamic correlation between electrons of opposite and parallel spin

NASA Astrophysics Data System (ADS)

Hollett, Joshua W.; Pegoretti, Nicholas

2018-04-01

Separate, one-parameter, on-top density functionals are derived for the short-range dynamic correlation between opposite and parallel-spin electrons, in which the electron-electron cusp is represented by an exponential function. The combination of both functionals is referred to as the Opposite-spin exponential-cusp and Fermi-hole correction (OF) functional. The two parameters of the OF functional are set by fitting the ionization energies and electron affinities, of the atoms He to Ar, predicted by ROHF in combination with the OF functional to the experimental values. For ionization energies, the overall performance of ROHF-OF is better than completely renormalized coupled-cluster [CR-CC(2,3)] and better than, or as good as, conventional density functional methods. For electron affinities, the overall performance of ROHF-OF is less impressive. However, for both ionization energies and electron affinities of third row atoms, the mean absolute error of ROHF-OF is only 3 kJ mol-1.

Self-amplified photo-induced gap quenching in a correlated electron material

PubMed Central

Mathias, S.; Eich, S.; Urbancic, J.; Michael, S.; Carr, A. V.; Emmerich, S.; Stange, A.; Popmintchev, T.; Rohwer, T.; Wiesenmayer, M.; Ruffing, A.; Jakobs, S.; Hellmann, S.; Matyba, P.; Chen, C.; Kipp, L.; Bauer, M.; Kapteyn, H. C.; Schneider, H. C.; Rossnagel, K.; Murnane, M. M.; Aeschlimann, M.

2016-01-01

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. We show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically depends on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation. PMID:27698341

Electron-beam conditioning by thomson scattering.

PubMed

Schroeder, C B; Esarey, E; Leemans, W P

2004-11-05

A method is proposed for conditioning electron beams via Thomson scattering. The conditioning provides a quadratic correlation between the electron energy deviation and the betatron amplitude of the electrons, which results in enhanced gain in free-electron lasers. Quantum effects imply conditioning must occur at high laser fluence and moderate electron energy. Conditioning of x-ray free-electron lasers should be achievable with present laser technology, leading to significant size and cost reductions of these large-scale facilities.

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.

A study of accurate exchange-correlation functionals through adiabatic connection

NASA Astrophysics Data System (ADS)

Singh, Rabeet; Harbola, Manoj K.

2017-10-01

A systematic way of improving exchange-correlation energy functionals of density functional theory has been to make them satisfy more and more exact relations. Starting from the initial generalized gradient approximation (GGA) functionals, this has culminated into the recently proposed SCAN (strongly constrained and appropriately normed) functional that satisfies several known constraints and is appropriately normed. The ultimate test for the functionals developed is the accuracy of energy calculated by employing them. In this paper, we test these exchange-correlation functionals—the GGA hybrid functionals B3LYP and PBE0 and the meta-GGA functional SCAN—from a different perspective. We study how accurately these functionals reproduce the exchange-correlation energy when electron-electron interaction is scaled as αVee with α varying between 0 and 1. Our study reveals interesting comparison between these functionals and the associated difference Tc between the interacting and the non-interacting kinetic energy for the same density.

The correcting method for the estimation of correlation energies of MF2 (M = Be, Mg, Ca) set molecules

NASA Astrophysics Data System (ADS)

Zhuo, Shuping; Wei, Jichong; Ju, Guanzhi

The intrapair and interpair correlation energies of MF2 (M = Be, Mg, Ca) set molecules are calculated and analysed, and the transferability of inner core correlation effects of Mδ+ are investigated. A detailed analysis of the comparison of correlation energies of neutral atoms with their corresponding ions of Mδ+ and Fδ-/2 is given in terms of the correlation contribution of this component. The study reveals that the total correlation energy of MF2 molecules can be obtained by summing the correlation contributions of Mδ+ and two Fδ-/2 components. This simple estimation method does shed light on the importance of searching useful means for the calculation of electron correlation energy for large biological systems.

Theoretical study of electron correlation effects in transition metal dimers

NASA Technical Reports Server (NTRS)

Das, G. P.; Jaffe, R. L.

1984-01-01

Introduction of partially localized orbitals is shown to reduce the number of terms needed to describe the bonding in transition metal clusters. Using this formalism, it is possible to compute the various intra- and inter-atomic electron correlation contributions to the bond energy. Calculations demonstrate the relative importance of several kinds of electron correlation terms involving the 3p, 3d, and 4s electrons. Improved interaction potentials are obtained for the dimers V(2) and Cr(2) when additional correlation is added to the CAS SCF results of Walch, Bauschlicher, Roos, and Nelin (1983).

Photoemission study of the electronic structure and charge density waves of Na₂Ti₂Sb₂O

DOE PAGES

Tan, S. Y.; Jiang, J.; Ye, Z. R.; ...

2015-04-30

The electronic structure of Na₂Ti₂Sb₂O single crystal is studied by photon energy and polarization dependent angle-resolved photoemission spectroscopy (ARPES). The obtained band structure and Fermi surface agree well with the band structure calculation of Na₂Ti₂Sb₂O in the non-magnetic state, which indicates that there is no magnetic order in Na₂Ti₂Sb₂O and the electronic correlation is weak. Polarization dependent ARPES results suggest the multi-band and multi-orbital nature of Na₂Ti₂Sb₂O. Photon energy dependent ARPES results suggest that the electronic structure of Na₂Ti₂Sb₂O is rather two-dimensional. Moreover, we find a density wave energy gap forms below the transition temperature and reaches 65 meV atmore » 7 K, indicating that Na₂Ti₂Sb₂O is likely a weakly correlated CDW material in the strong electron-phonon interaction regime. (author)« less

Core-core and core-valence correlation energy atomic and molecular benchmarks for Li through Ar

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

Ranasinghe, Duminda S.; Frisch, Michael J.; Petersson, George A., E-mail: gpetersson@wesleyan.edu

2015-12-07

We have established benchmark core-core, core-valence, and valence-valence absolute coupled-cluster single double (triple) correlation energies (±0.1%) for 210 species covering the first- and second-rows of the periodic table. These species provide 194 energy differences (±0.03 mE{sub h}) including ionization potentials, electron affinities, and total atomization energies. These results can be used for calibration of less expensive methodologies for practical routine determination of core-core and core-valence correlation energies.

Monte Carlo Study of the abBA Experiment: Detector Response and Physics Analysis.

PubMed

Frlež, E

2005-01-01

The abBA collaboration proposes to conduct a comprehensive program of precise measurements of neutron β-decay coefficients a (the correlation between the neutrino momentum and the decay electron momentum), b (the electron energy spectral distortion term), A (the correlation between the neutron spin and the decay electron momentum), and B (the correlation between the neutron spin and the decay neutrino momentum) at a cold neutron beam facility. We have used a GEANT4-based code to simulate the propagation of decay electrons and protons in the electromagnetic spectrometer and study the energy and timing response of a pair of Silicon detectors. We used these results to examine systematic effects and find the uncertainties with which the physics parameters a, b, A, and B can be extracted from an over-determined experimental data set.

Calculating electronic correlation effects from densities of transitions

NASA Astrophysics Data System (ADS)

Haydock, Roger

Adding a localized electron to a system of interacting electrons induces a density of transitions described by the time-independent Heisenberg equation. Sequences of these transitions generate interacting states whose total energy is the sum of energies of the constituent transitions. A calculation of magnetic moments for itinerant electrons with Ising interactions illustrates this method. supported by the H. V. Snyder Gift to the University of Oregon.

QUIET-TIME SUPRATHERMAL (∼0.1–1.5 keV) ELECTRONS IN THE SOLAR WIND

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

Tao, Jiawei; Wang, Linghua; Zong, Qiugang

2016-03-20

We present a statistical survey of the energy spectrum of solar wind suprathermal (∼0.1–1.5 keV) electrons measured by the WIND 3DP instrument at 1 AU during quiet times at the minimum and maximum of solar cycles 23 and 24. After separating (beaming) strahl electrons from (isotropic) halo electrons according to their different behaviors in the angular distribution, we fit the observed energy spectrum of both strahl and halo electrons at ∼0.1–1.5 keV to a Kappa distribution function with an index κ and effective temperature T{sub eff}. We also calculate the number density n and average energy E{sub avg} of strahl andmore » halo electrons by integrating the electron measurements between ∼0.1 and 1.5 keV. We find a strong positive correlation between κ and T{sub eff} for both strahl and halo electrons, and a strong positive correlation between the strahl n and halo n, likely reflecting the nature of the generation of these suprathermal electrons. In both solar cycles, κ is larger at solar minimum than at solar maximum for both strahl and halo electrons. The halo κ is generally smaller than the strahl κ (except during the solar minimum of cycle 23). The strahl n is larger at solar maximum, but the halo n shows no difference between solar minimum and maximum. Both the strahl n and halo n have no clear association with the solar wind core population, but the density ratio between the strahl and halo roughly anti-correlates (correlates) with the solar wind density (velocity)« less

On the Progress of Scanning Transmission Electron Microscopy (STEM) Imaging in a Scanning Electron Microscope.

PubMed

Sun, Cheng; Müller, Erich; Meffert, Matthias; Gerthsen, Dagmar

2018-04-01

Transmission electron microscopy (TEM) with low-energy electrons has been recognized as an important addition to the family of electron microscopies as it may avoid knock-on damage and increase the contrast of weakly scattering objects. Scanning electron microscopes (SEMs) are well suited for low-energy electron microscopy with maximum electron energies of 30 keV, but they are mainly used for topography imaging of bulk samples. Implementation of a scanning transmission electron microscopy (STEM) detector and a charge-coupled-device camera for the acquisition of on-axis transmission electron diffraction (TED) patterns, in combination with recent resolution improvements, make SEMs highly interesting for structure analysis of some electron-transparent specimens which are traditionally investigated by TEM. A new aspect is correlative SEM, STEM, and TED imaging from the same specimen region in a SEM which leads to a wealth of information. Simultaneous image acquisition gives information on surface topography, inner structure including crystal defects and qualitative material contrast. Lattice-fringe resolution is obtained in bright-field STEM imaging. The benefits of correlative SEM/STEM/TED imaging in a SEM are exemplified by structure analyses from representative sample classes such as nanoparticulates and bulk materials.

Signatures of van der Waals binding: A coupling-constant scaling analysis

NASA Astrophysics Data System (ADS)

Jiao, Yang; Schröder, Elsebeth; Hyldgaard, Per

2018-02-01

The van der Waals (vdW) density functional (vdW-DF) method [Rep. Prog. Phys. 78, 066501 (2015), 10.1088/0034-4885/78/6/066501] describes dispersion or vdW binding by tracking the effects of an electrodynamic coupling among pairs of electrons and their associated exchange-correlation holes. This is done in a nonlocal-correlation energy term Ecnl, which permits density functional theory calculation in the Kohn-Sham scheme. However, to map the nature of vdW forces in a fully interacting materials system, it is necessary to also account for associated kinetic-correlation energy effects. Here, we present a coupling-constant scaling analysis, which permits us to compute the kinetic-correlation energy Tcnl that is specific to the vdW-DF account of nonlocal correlations. We thus provide a more complete spatially resolved analysis of the electrodynamical-coupling nature of nonlocal-correlation binding, including vdW attraction, in both covalently and noncovalently bonded systems. We find that kinetic-correlation energy effects play a significant role in the account of vdW or dispersion interactions among molecules. Furthermore, our mapping shows that the total nonlocal-correlation binding is concentrated to pockets in the sparse electron distribution located between the material fragments.

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.

Electron energy-loss spectra in molecular fluorine

NASA Technical Reports Server (NTRS)

Nishimura, H.; Cartwright, D. C.; Trajmar, S.

1979-01-01

Electron energy-loss spectra in molecular fluorine, for energy losses from 0 to 17.0 eV, have been taken at incident electron energies of 30, 50, and 90 eV and scattering angles from 5 to 140 deg. Features in the spectra above 11.5 eV energy loss agree well with the assignments recently made from optical spectroscopy. Excitations of many of the eleven repulsive valence excited electronic states are observed and their location correlates reasonably well with recent theoretical results. Several of these excitations have been observed for the first time and four features, for which there are no identifications, appear in the spectra.

Partitioning dynamic electron correlation energy: Viewing Møller-Plesset correlation energies through Interacting Quantum Atom (IQA) energy partitioning

NASA Astrophysics Data System (ADS)

McDonagh, James L.; Vincent, Mark A.; Popelier, Paul L. A.

2016-10-01

Here MP2, MP3 and MP4(SDQ) are energy-partitioned for the first time within the Interacting Quantum Atoms (IQA) context, as proof-of-concept for H2, He2 and HF. Energies are decomposed into four primary energy contributions: (i) atomic self-energies, and atomic interaction energies comprising of (ii) Coulomb, (iii) exchange and (iv) dynamic election correlation terms. We generate and partition one- and two-particle density-matrices to obtain all atomic energy components. This work suggests that, in terms of Van der Waals dispersion, the correlation energies represent an atomic stabilisation, by proximity to other atoms, as opposed to direct interactions with other nearby atoms.

A Statistical Correlation Between Low L-shell Electrons Measured by NOAA Satellites and Strong Earthquakes

NASA Astrophysics Data System (ADS)

Fidani, C.

2015-12-01

More than 11 years of the Medium Energy Protons Electrons Detector data from the NOAA polar orbiting satellites were analyzed. Significant electron counting rate fluctuations were evidenced during geomagnetic quiet periods by using a set of adiabatic coordinates. Electron counting rates were compared to earthquakes by defining a seismic event L-shell obtained radially projecting the epicenter geographical positions to a given altitude. Counting rate fluctuations were grouped in every satellite semi-orbit together with strong seismic events and these were chosen with the L-shell coordinates close to each other. Electron data from July 1998 to December 2011 were compared for nearly 1,800 earthquakes with magnitudes larger than or equal to 6, occurring worldwide. When considering 30 - 100 keV energy channels by the vertical NOAA telescopes and earthquake epicenter projections at altitudes greater that 1,300 km, a 4 sigma correlation appeared where time of particle precipitations Tpp occurred 2 - 3 hour prior time of large seismic events Teq. This was in physical agreement with different correlation times obtained from past studies that considered particles with greater energies. The correlation suggested a 4-8 hour advance in preparedness of strong earthquakes influencing the ionosphere. Considering this strong correlation between earthquakes and electron rate fluctuations, and the hypothesis that such fluctuations originated with magnetic disturbances generated underground, a small scale experiment with low cost at ground level is advisable. Plans exists to perform one or more unconventional experiments around an earthquake affected area by private investor in Italy.

Wave-Particle Interactions Involving Correlated Electron Bursts and Whistler Chorus in Earth's Radiation Belts

NASA Astrophysics Data System (ADS)

Echterling, N.; Schriver, D.; Roeder, J. L.; Fennell, J. F.

2017-12-01

During the recovery phase of substorm plasma injections, the Van Allen Probes commonly observe events of quasi-periodic energetic electron bursts correlating with simultaneously detected upper-band, whistler-mode chorus emissions. These electron bursts exhibit narrow ranges of pitch angles (75-80° and 100-105°) and energies (20-40 keV). Electron cyclotron harmonic (ECH) emissions are also commonly detected, but typically do not display correlation with the electron bursts. To examine sources of free energy and the generation of these wave emissions, an observed electron velocity distribution on January 13, 2013 is used as the starting condition for a particle in cell (PIC) simulation. Effects of temperature anisotropy (perpendicular temperature greater than parallel temperature), the presence of a loss cone and a cold electron population on the generation of whistler and ECH waves are examined to understand wave generation and nonlinear interactions with the particle population. These nonlinear interactions produce energy diffusion along with strong pitch angle scattering into the loss cone on the order of milliseconds, which is faster than a typical bounce period of seconds. To examine the quasi-periodic nature of the electron bursts, a loss-cone recycling technique is implemented to model the effects of the periodic emptying of the loss cone and electron injection on the growth of whistler and ECH waves. The results of the simulations are compared to the Van Allen Probe observations to determine electron acceleration, heating and transport in Earth's radiation belts due to wave-particle interactions.

Application of Multipurpose Cadastre to Evaluate Energy Security of Land Parcel (Case Study: Gedung A and Gedung B, Institut Teknologi Sumatra)

NASA Astrophysics Data System (ADS)

Alif, S. M.; Nugroho, A. P.; Leksono, B. E.

2018-03-01

Energy security has one of its dimensions: Short-term energy security which focuses on the ability of the energy system to react promptly to sudden changes within the supply-demand balance. Non-energy components (such as land parcel) that comprise an energy system are analysed comprehensively with other component to measure energy security related to energy supply. Multipurpose cadastre which is an integrated land information system containing legal, physical, and cultural is used to evaluate energy (electrical energy) security of land parcel. The fundamental component of multipurpose cadastre used to evaluate energy security is attribute data which is the value of land parcel facilities. Other fundamental components (geographic control data, base map data, cadastral data) are used as position information and provide weight in room (part of land parcel) valuation. High value-room means the room is comfortable and/or used productively by its occupant. The method of valuation is by comparing one facility to other facilities. Facilities included in room valuation are relatively static items (such as chair, desk, and cabinet) except lamps and other electronic devices. The room value and number of electronic devices which consume electrical energy are correlated with each other. Consumption of electrical energy of electronic devices in the room with average value remains constant while consumption in other room needs to be evaluated to save the energy. The result of this research shows that room value correlate weakly with number of electronic device in corresponding room. It shows excess energy consumed in low-value room. Although numbers of electronic devices do not always mean the consumption of electrical energy and there are plenty electronic devices, it is recommended for occupant to be careful in utilizing electronic devices in low-value room to minimize energy consumption.

Boron difluoride dibenzoylmethane derivatives: Electronic structure and luminescence

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Vovna, Vitaliy I.; Osmushko, Ivan S.; Fedorenko, Elena V.; Mirochnik, Anatoliy G.

2018-01-01

Electronic structure and optical properties of boron difluoride dibenzoylmethanate and four of its derivatives have been studied by X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy and quantum chemistry (DFT, TDDFT). The relative quantum luminescence yields have been revealed to correlate with charge transfers of HOMO-LUMO transitions, energy barriers of aromatic substituents rotation and the lifetime of excited states in the investigated complexes. The bathochromic shift of intensive bands in the optical spectra has been observed to occur when the functional groups are introduced into p-positions of phenyl cycles due to destabilizing HOMO levels. Calculated energy intervals between electronic levels correlate well with XPS spectra structure of valence and core electrons.

Correlation between energy deposition and molecular damage from Auger electrons: A case study of ultra-low energy (5-18 eV) electron interactions with DNA.

PubMed

Rezaee, Mohammad; Hunting, Darel J; Sanche, Léon

2014-07-01

The present study introduces a new method to establish a direct correlation between biologically related physical parameters (i.e., stopping and damaging cross sections, respectively) for an Auger-electron emitting radionuclide decaying within a target molecule (e.g., DNA), so as to evaluate the efficacy of the radionuclide at the molecular level. These parameters can be applied to the dosimetry of Auger electrons and the quantification of their biological effects, which are the main criteria to assess the therapeutic efficacy of Auger-electron emitting radionuclides. Absorbed dose and stopping cross section for the Auger electrons of 5-18 eV emitted by(125)I within DNA were determined by developing a nanodosimetric model. The molecular damages induced by these Auger electrons were investigated by measuring damaging cross section, including that for the formation of DNA single- and double-strand breaks. Nanoscale films of pure plasmid DNA were prepared via the freeze-drying technique and subsequently irradiated with low-energy electrons at various fluences. The damaging cross sections were determined by employing a molecular survival model to the measured exposure-response curves for induction of DNA strand breaks. For a single decay of(125)I within DNA, the Auger electrons of 5-18 eV deposit the energies of 12.1 and 9.1 eV within a 4.2-nm(3) volume of a hydrated or dry DNA, which results in the absorbed doses of 270 and 210 kGy, respectively. DNA bases have a major contribution to the deposited energies. Ten-electronvolt and high linear energy transfer 100-eV electrons have a similar cross section for the formation of DNA double-strand break, while 100-eV electrons are twice as efficient as 10 eV in the induction of single-strand break. Ultra-low-energy electrons (<18 eV) substantially contribute to the absorbed dose and to the molecular damage from Auger-electron emitting radionuclides; hence, they should be considered in the dosimetry calculation of such radionuclides. Moreover, absorbed dose is not an appropriate physical parameter for nanodosimetry. Instead, stopping cross section, which describes the probability of energy deposition in a target molecule can be an appropriate nanodosimetric parameter. The stopping cross section is correlated with a damaging cross section (e.g., cross section for the double-strand break formation) to quantify the number of each specific lesion in a target molecule for each nuclear decay of a single Auger-electron emitting radionuclide.

Nuclear quantum effects in electronically adiabatic quantum time correlation functions: Application to the absorption spectrum of a hydrated electron

NASA Astrophysics Data System (ADS)

Turi, László; Hantal, György; Rossky, Peter J.; Borgis, Daniel

2009-07-01

A general formalism for introducing nuclear quantum effects in the expression of the quantum time correlation function of an operator in a multilevel electronic system is presented in the adiabatic limit. The final formula includes the nuclear quantum time correlation functions of the operator matrix elements, of the energy gap, and their cross terms. These quantities can be inferred and evaluated from their classical analogs obtained by mixed quantum-classical molecular dynamics simulations. The formalism is applied to the absorption spectrum of a hydrated electron, expressed in terms of the time correlation function of the dipole operator in the ground electronic state. We find that both static and dynamic nuclear quantum effects distinctly influence the shape of the absorption spectrum, especially its high energy tail related to transitions to delocalized electron states. Their inclusion does improve significantly the agreement between theory and experiment for both the low and high frequency edges of the spectrum. It does not appear sufficient, however, to resolve persistent deviations in the slow Lorentzian-like decay part of the spectrum in the intermediate 2-3 eV region.

Communication: Near-locality of exchange and correlation density functionals for 1- and 2-electron systems

NASA Astrophysics Data System (ADS)

Sun, Jianwei; Perdew, John P.; Yang, Zenghui; Peng, Haowei

2016-05-01

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin density approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.

Feasibility of antihydrogen atom containment in helium: a problem of electron-positron correlation investigated by the Monte Carol method

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

Jackman, T.M.

1987-01-01

A theoretical investigation of the interaction potential between the helium atom and the antihydrogen atom was performed for the purpose of determining the feasibility of antihydrogen atom containment. The interaction potential showed an energy barrier to collapse of this system. A variational estimate of the height of this energy barrier and estimates of lifetime with respect to electron-positron annihilation were determined by the Variational Monte Carlo method. This calculation allowed for an improvement over an SCF result through the inclusion of explicit correlation factors in the trial wave function. An estimate of the correlation energy of this system was determinedmore » by the Green's Function Monte Carlo (GFMC) method.« less

Electron correlation contribution to the physisorption of CO on MgF2(110).

PubMed

Hammerschmidt, Lukas; Müller, Carsten; Paulus, Beate

2012-03-28

We have performed CCSD(T), MP2, and DF-LMP2 calculations of the interaction energy of CO on the MgF(2)(110) surface by applying the method of increments and an embedded cluster model. In addition, we performed periodic HF, B3LYP, and DF-LMP2 calculations and compare them to the cluster results. The incremental CCSD(T) calculations predict an interaction energy of E(int) = -0.37 eV with a C-down orientation of CO above a Mg(2+) ion at the surface with a basis set of VTZ quality. We find that electron correlation constitutes about 50% of the binding energy and a detailed evaluation of the increments shows that the largest contribution to the correlation energy originates from the CO interaction with the closest F ions on the second layer.

Self-energy behavior away from the Fermi surface in doped Mott insulators.

PubMed

Merino, J; Gunnarsson, O; Kotliar, G

2016-02-03

We analyze self-energies of electrons away from the Fermi surface in doped Mott insulators using the dynamical cluster approximation to the Hubbard model. For large onsite repulsion, U, and hole doping, the magnitude of the self-energy for imaginary frequencies at the top of the band ([Formula: see text]) is enhanced with respect to the self-energy magnitude at the bottom of the band ([Formula: see text]). The self-energy behavior at these two [Formula: see text]-points is switched for electron doping. Although the hybridization is much larger for (0, 0) than for [Formula: see text], we demonstrate that this is not the origin of this difference. Isolated clusters under a downward shift of the chemical potential, [Formula: see text], at half-filling reproduce the overall self-energy behavior at (0, 0) and [Formula: see text] found in low hole doped embedded clusters. This happens although there is no change in the electronic structure of the isolated clusters. Our analysis shows that a downward shift of the chemical potential which weakly hole dopes the Mott insulator can lead to a large enhancement of the [Formula: see text] self-energy for imaginary frequencies which is not associated with electronic correlation effects, even in embedded clusters. Interpretations of the strength of electronic correlations based on self-energies for imaginary frequencies are, in general, misleading for states away from the Fermi surface.

Single-stage plasma-based correlated energy spread compensation for ultrahigh 6D brightness electron beams

PubMed Central

Manahan, G. G.; Habib, A. F.; Scherkl, P.; Delinikolas, P.; Beaton, A.; Knetsch, A.; Karger, O.; Wittig, G.; Heinemann, T.; Sheng, Z. M.; Cary, J. R.; Bruhwiler, D. L.; Rosenzweig, J. B.; Hidding, B.

2017-01-01

Plasma photocathode wakefield acceleration combines energy gains of tens of GeV m−1 with generation of ultralow emittance electron bunches, and opens a path towards 5D-brightness orders of magnitude larger than state-of-the-art. This holds great promise for compact accelerator building blocks and advanced light sources. However, an intrinsic by-product of the enormous electric field gradients inherent to plasma accelerators is substantial correlated energy spread—an obstacle for key applications such as free-electron-lasers. Here we show that by releasing an additional tailored escort electron beam at a later phase of the acceleration, when the witness bunch is relativistically stable, the plasma wave can be locally overloaded without compromising the witness bunch normalized emittance. This reverses the effective accelerating gradient, and counter-rotates the accumulated negative longitudinal phase space chirp of the witness bunch. Thereby, the energy spread is reduced by an order of magnitude, thus enabling the production of ultrahigh 6D-brightness beams. PMID:28580954

Single-stage plasma-based correlated energy spread compensation for ultrahigh 6D brightness electron beams

NASA Astrophysics Data System (ADS)

Manahan, G. G.; Habib, A. F.; Scherkl, P.; Delinikolas, P.; Beaton, A.; Knetsch, A.; Karger, O.; Wittig, G.; Heinemann, T.; Sheng, Z. M.; Cary, J. R.; Bruhwiler, D. L.; Rosenzweig, J. B.; Hidding, B.

2017-06-01

Plasma photocathode wakefield acceleration combines energy gains of tens of GeV m-1 with generation of ultralow emittance electron bunches, and opens a path towards 5D-brightness orders of magnitude larger than state-of-the-art. This holds great promise for compact accelerator building blocks and advanced light sources. However, an intrinsic by-product of the enormous electric field gradients inherent to plasma accelerators is substantial correlated energy spread--an obstacle for key applications such as free-electron-lasers. Here we show that by releasing an additional tailored escort electron beam at a later phase of the acceleration, when the witness bunch is relativistically stable, the plasma wave can be locally overloaded without compromising the witness bunch normalized emittance. This reverses the effective accelerating gradient, and counter-rotates the accumulated negative longitudinal phase space chirp of the witness bunch. Thereby, the energy spread is reduced by an order of magnitude, thus enabling the production of ultrahigh 6D-brightness beams.

Ultrahigh-Power Pseudocapacitors Based on Ordered Porous Heterostructures of Electron-Correlated Oxides.

PubMed

Lang, Xing-You; Liu, Bo-Tian; Shi, Xiang-Mei; Li, Ying-Qi; Wen, Zi; Jiang, Qing

2016-05-01

Nanostructured transition-metal oxides can store high-density energy in fast surface redox reactions, but their poor conductivity causes remarkable reductions in the energy storage of most pseudocapacitors at high power delivery (fast charge/discharge rates). Here it is shown that electron-correlated oxide hybrid electrodes made of nanocrystalline vanadium sesquioxide and manganese dioxide with 3D and bicontinuous nanoporous architecture (NP V 2 O 3 /MnO 2 ) have enhanced conductivity because of metallization of electron-correlated V 2 O 3 skeleton via insulator-to-metal transition. The conductive V 2 O 3 skeleton at ambient temperature enables fast electron and ion transports in the entire electrode and facilitates charge transfer at abundant V 2 O 3 /MnO 2 interface. These merits significantly improve the pseudocapacitive behavior and rate capability of the constituent MnO 2 . Symmetric pseudocapacitors assembled with binder-free NP V 2 O 3 /MnO 2 electrodes deliver ultrahigh electrical powers (up to ≈422 W cm 23 ) while maintaining the high volumetric energy of thin-film lithium battery with excellent stability.

Efficient and accurate treatment of electron correlations with correlation matrix renormalization theory

DOE PAGES

Yao, Y. X.; Liu, J.; Liu, C.; ...

2015-08-28

We present an efficient method for calculating the electronic structure and total energy of strongly correlated electron systems. The method extends the traditional Gutzwiller approximation for one-particle operators to the evaluation of the expectation values of two particle operators in the many-electron Hamiltonian. The method is free of adjustable Coulomb parameters, and has no double counting issues in the calculation of total energy, and has the correct atomic limit. We demonstrate that the method describes well the bonding and dissociation behaviors of the hydrogen and nitrogen clusters, as well as the ammonia composed of hydrogen and nitrogen atoms. We alsomore » show that the method can satisfactorily tackle great challenging problems faced by the density functional theory recently discussed in the literature. The computational workload of our method is similar to the Hartree-Fock approach while the results are comparable to high-level quantum chemistry calculations.« less

Quantum-mechanical parameters for the risk assessment of multi-walled carbon-nanotubes: A study using adsorption of probe compounds and its application to biomolecules.

PubMed

Chayawan; Vikas

2016-11-01

This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Non-Local, Energy-Optimized Kernel: Recovering Second-Order Exchange and Beyond in Extended Systems

NASA Astrophysics Data System (ADS)

Bates, Jefferson; Laricchia, Savio; Ruzsinszky, Adrienn

The Random Phase Approximation (RPA) is quickly becoming a standard method beyond semi-local Density Functional Theory that naturally incorporates weak interactions and eliminates self-interaction error. RPA is not perfect, however, and suffers from self-correlation error as well as an incorrect description of short-ranged correlation typically leading to underbinding. To improve upon RPA we introduce a short-ranged, exchange-like kernel that is one-electron self-correlation free for one and two electron systems in the high-density limit. By tuning the one free parameter in our model to recover an exact limit of the homogeneous electron gas correlation energy we obtain a non-local, energy-optimized kernel that reduces the errors of RPA for both homogeneous and inhomogeneous solids. To reduce the computational cost of the standard kernel-corrected RPA, we also implement RPA renormalized perturbation theory for extended systems, and demonstrate its capability to describe the dominant correlation effects with a low-order expansion in both metallic and non-metallic systems. Furthermore we stress that for norm-conserving implementations the accuracy of RPA and beyond RPA structural properties compared to experiment is inherently limited by the choice of pseudopotential. Current affiliation: King's College London.

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

PubMed Central

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

2017-01-01

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

Exploiting the spatial locality of electron correlation within the parametric two-electron reduced-density-matrix method

NASA Astrophysics Data System (ADS)

DePrince, A. Eugene; Mazziotti, David A.

2010-01-01

The parametric variational two-electron reduced-density-matrix (2-RDM) method is applied to computing electronic correlation energies of medium-to-large molecular systems by exploiting the spatial locality of electron correlation within the framework of the cluster-in-molecule (CIM) approximation [S. Li et al., J. Comput. Chem. 23, 238 (2002); J. Chem. Phys. 125, 074109 (2006)]. The 2-RDMs of individual molecular fragments within a molecule are determined, and selected portions of these 2-RDMs are recombined to yield an accurate approximation to the correlation energy of the entire molecule. In addition to extending CIM to the parametric 2-RDM method, we (i) suggest a more systematic selection of atomic-orbital domains than that presented in previous CIM studies and (ii) generalize the CIM method for open-shell quantum systems. The resulting method is tested with a series of polyacetylene molecules, water clusters, and diazobenzene derivatives in minimal and nonminimal basis sets. Calculations show that the computational cost of the method scales linearly with system size. We also compute hydrogen-abstraction energies for a series of hydroxyurea derivatives. Abstraction of hydrogen from hydroxyurea is thought to be a key step in its treatment of sickle cell anemia; the design of hydroxyurea derivatives that oxidize more rapidly is one approach to devising more effective treatments.

Self-amplified photo-induced gap quenching in a correlated electron material

DOE PAGES

Mathias, S.; Eich, S.; Urbancic, J.; ...

2016-10-04

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. Here, we show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically dependsmore » on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe 2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation.« less

Test of GET Electronics for the CHIMERA and FARCOS multi-detectors

NASA Astrophysics Data System (ADS)

De Luca, S.; Acosta, L.; Auditore, L.; Boiano, C.; Cardella, G.; Castoldi, A.; D'Andrea, M.; De Filippo, E.; Dell'Aquila, D.; Fichera, F.; Gnoffo, B.; Guazzoni, C.; Lanzalone, G.; Lombardo, I.; Martorana, N. S.; Minniti, T.; Norella, S.; Pagano, A.; Pagano, E. V.; Papa, M.; Pirrone, S.; Politi, G.; Quattrocchi, L.; Rizzo, F.; Russotto, P.; Saccà, G.; Trifirò, A.; Trimarchi, M.; Verde, G.; Vigilante, M.

2017-11-01

In this paper we present the results of the tests on the new digital electronics GET (General Electronics for Tpc), which will be used for the readout of the CsI(Tl) detectors of CHIMERA (Charged Heavy Ion Mass and Energy Resolving Array) and for the new correlator FARCOS (Femtoscope ARray for COrrelations and Spectroscopy). The new electronics allows us to digitize the full waveform of the signals produced by the detector. Among its features it is worth noticing the compactness and low power consumption (5W for 256 channels). Tests have been performed with pulsers, radioactive sources and ion beams. With such electronics very good results in energy resolution and isotope separation of the detected fragments were obtained, by using both hardware and software filters.

Energy-energy correlation in electron-positron annihilation at NNLL + NNLO accuracy

NASA Astrophysics Data System (ADS)

Tulipánt, Zoltán; Kardos, Adam; Somogyi, Gábor

2017-11-01

We present the computation of energy-energy correlation in e^+e^- collisions in the back-to-back region at next-to-next-to-leading logarithmic accuracy matched with the next-to-next-to-leading order perturbative prediction. We study the effect of the fixed higher-order corrections in a comparison of our results to LEP and SLC data. The next-to-next-to-leading order correction has a sizable impact on the extracted value of α S(M_Z), hence its inclusion is mandatory for a precise measurement of the strong coupling using energy-energy correlation.

Towards an exact correlated orbital theory for electrons

NASA Astrophysics Data System (ADS)

Bartlett, Rodney J.

2009-12-01

The formal and computational attraction of effective one-particle theories like Hartree-Fock and density functional theory raise the question of how far such approaches can be taken to offer exact results for selected properties of electrons in atoms, molecules, and solids. Some properties can be exactly described within an effective one-particle theory, like principal ionization potentials and electron affinities. This fact can be used to develop equations for a correlated orbital theory (COT) that guarantees a correct one-particle energy spectrum. They are built upon a coupled-cluster based frequency independent self-energy operator presented here, which distinguishes the approach from Dyson theory. The COT also offers an alternative to Kohn-Sham density functional theory (DFT), whose objective is to represent the electronic density exactly as a single determinant, while paying less attention to the energy spectrum. For any estimate of two-electron terms COT offers a litmus test of its accuracy for principal Ip's and Ea's. This feature for approximating the COT equations is illustrated numerically.

Photoemission study of the electronic structure and charge density waves of Na2Ti2Sb2O.

PubMed

Tan, S Y; Jiang, J; Ye, Z R; Niu, X H; Song, Y; Zhang, C L; Dai, P C; Xie, B P; Lai, X C; Feng, D L

2015-04-30

The electronic structure of Na2Ti2Sb2O single crystal is studied by photon energy and polarization dependent angle-resolved photoemission spectroscopy (ARPES). The obtained band structure and Fermi surface agree well with the band structure calculation of Na2Ti2Sb2O in the non-magnetic state, which indicates that there is no magnetic order in Na2Ti2Sb2O and the electronic correlation is weak. Polarization dependent ARPES results suggest the multi-band and multi-orbital nature of Na2Ti2Sb2O. Photon energy dependent ARPES results suggest that the electronic structure of Na2Ti2Sb2O is rather two-dimensional. Moreover, we find a density wave energy gap forms below the transition temperature and reaches 65 meV at 7 K, indicating that Na2Ti2Sb2O is likely a weakly correlated CDW material in the strong electron-phonon interaction regime.

Influence of lattice vibrations on the field driven electronic transport in chains with correlated disorder

NASA Astrophysics Data System (ADS)

da Silva, L. D.; Sales, M. O.; Ranciaro Neto, A.; Lyra, M. L.; de Moura, F. A. B. F.

2016-12-01

We investigate electronic transport in a one-dimensional model with four different types of atoms and long-ranged correlated disorder. The latter was attained by choosing an adequate distribution of on-site energies. The wave-packet dynamics is followed by taking into account effects due to a static electric field and electron-phonon coupling. In the absence of electron-phonon coupling, the competition between correlated disorder and the static electric field promotes the occurrence of wave-packet oscillations in the regime of strong correlations. When the electron-lattice coupling is switched on, phonon scattering degrades the Bloch oscillations. For weak electron-phonon couplings, a coherent oscillatory-like dynamics of the wave-packet centroid persists for short periods of time. For strong couplings the wave-packet acquires a diffusive-like displacement and spreading. A slower sub-diffusive spreading takes place in the regime of weak correlations.

Complex Correlation Kohn-T Method of Calculating Total and Elastic Cross Sections. Part 1; Electron-Hydrogen Elastic Scattering

NASA Technical Reports Server (NTRS)

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

2001-01-01

We report on the first part of a study of electron-hydrogen scattering, using a method which allows for the ab initio calculation of total and elastic cross sections at higher energies. In its general form the method uses complex 'radial' correlation functions, in a (Kohn) T-matrix formalism. The titled method, abbreviated Complex Correlation Kohn T (CCKT) method, is reviewed, in the context of electron-hydrogen scattering, including the derivation of the equation for the (complex) scattering function, and the extraction of the scattering information from the latter. The calculation reported here is restricted to S-waves in the elastic region, where the correlation functions can be taken, without loss of generality, to be real. Phase shifts are calculated using Hylleraas-type correlation functions with up to 95 terms. Results are rigorous lower bounds; they are in general agreement with those of Schwartz, but they are more accurate and outside his error bounds at a couple of energies,

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes.

PubMed

Liu, Kexi; Lei, Yinkai; Wang, Guofeng

2013-11-28

Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

New parameter-free polarization potentials in low-energy positron collisions

NASA Technical Reports Server (NTRS)

Jain, Ashok

1990-01-01

The polarization potential plays a decisive role in shaping up the cross sections in low energy positron collisions with atoms and molecules. However, its inclusion without involving any adjustable parameter, is still a challenge. Various other techniques employed so far for positron collisions are summarized, and a new, nonadjustable and very simple form of the polarization potential for positron-atom (molecule) collisions below the threshold of positronium formation is discussed. This new recently proposed potential is based on the correlation energy of a single positron in a homogeneous electron gas. The correlation energy was calculated by solving the Schrodinger equation of the positron-electron system and fitted to an analytical form in various ranges of the density parameter. In the outside region, the correlation energy is joined smoothly with the correct asymptotic form. This new positron correlation polarization (PCOP) potential was tested on several atomic and molecular targets such as the Ar, CO, and CH4. The results on the total and differential cross sections on these targets are shown along with the experimental data where available.

A toy model to investigate the existence of excitons in the ground state of strongly-correlated semiconductor

NASA Astrophysics Data System (ADS)

Karima, H. R.; Majidi, M. A.

2018-04-01

Excitons, quasiparticles associated with bound states between an electron and a hole and are typically created when photons with a suitable energy are absorbed in a solid-state material. We propose to study a possible emergence of excitons, created not by photon absorption but the effect of strong electronic correlations. This study is motivated by a recent experimental study of a substrate material SrTiO3 (STO) that reveals strong exitonic signals in its optical conductivity. Here we conjecture that some excitons may already exist in the ground state as a result of the electronic correlations before the additional excitons being created later by photon absorption. To investigate the existence of excitons in the ground state, we propose to study a simple 4-energy-level model that mimics a situation in strongly-correlated semiconductors. The four levels are divided into two groups, lower and upper groups separated by an energy gap, Eg , mimicking the valence and the conduction bands, respectively. Further, we incorporate repulsive Coulomb interactions between the electrons. The model is then solved by exact diagonalization method. Our result shows that the toy model can demonstrate band gap widening or narrowing and the existence of exciton in the ground state depending on interaction parameter values.

Correlated Electrons in Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Odintsov, Arkadi A.; Yoshioka, Hideo

Single-wall carbon nanotubes are almost ideal systems for the investigation of exotic many-body effects due to non-Fermi liquid behavior of interacting electrons in one dimension. Recent theoretical and experimental results are reviewed with a focus on electron correlations. Starting from a microscopic lattice model we derive an effective phase Hamiltonian for conducting single-wall nanotubes with arbitrary chirality. The parameters of the Hamiltonian show very weak dependence on the chiral angle, which makes the low-energy physics of conducting nanotubes universal. The temperature-dependent resistivity and frequency-dependent optical conductivity of nanotubes with impurities are evaluated within the Luttinger-like model. Localization effects are studied. In particular, we found that intra-valley and inter-valley electron scattering can not coexist at low energies. Low-energy properties of clean nanotubes are studied beyond the Luttinger liquid approximation. The strongest Mott-like electron instability occurs at half filling. In the Mott insulating phase electrons at different atomic sublattices form characteristic bound states. The energy gaps occur in all modes of elementary excitations and estimate at 0.01-0.1 eV. We finally discuss observability of the Mott insulating phase in transport experiments. The accent is made on the charge transfer from external electrodes which results in a deviation of the electron density from half-filling.

aCORN Beta Spectrometer and Electrostatic Mirror

NASA Astrophysics Data System (ADS)

Hassan, Md; aCORN Collaboration

2013-10-01

aCORN uses a high efficiency backscatter suppressed beta spectrometer to measure the electron-antineutrino correlation in neutron beta decay. We measure the correlation by counting protons and beta electrons in coincidence with precisely determined electron energy. There are 19 photomultiplier tubes arranged in a hexagonal array coupled to a single phosphor doped polystyrene scintillator. The magnetic field is shaped so that electrons that backscatter without depositing their full energy strike a tulip-shaped array of scintillator paddles and these events are vetoed. The detailed construction, performance and calibration of this beta spectrometer will be presented. I will also present the simulation, construction, and features of our novel electrostatic mirror. This work was supported by the National Science Foundation and the NIST Center for Neutron Research.

Dynamical correlation effects on photoisomerization: Ab initio multiple spawning dynamics with MS-CASPT2 for a model trans-protonated Schiff base

DOE PAGES

Liu, Lihong; Liu, Jian; Martinez, Todd J.

2015-12-17

Here, we investigate the photoisomerization of a model retinal protonated Schiff base (trans-PSB3) using ab initio multiple spawning (AIMS) based on multi-state second order perturbation theory (MSPT2). Discrepancies between the photodynamical mechanism computed with three-root state-averaged complete active space self-consistent field (SA-3-CASSCF, which does not include dynamic electron correlation effects) and MSPT2 show that dynamic correlation is critical in this photoisomerization reaction. Furthermore, we show that the photodynamics of trans-PSB3 is not well described by predictions based on minimum energy conical intersections (MECIs) or minimum energy conical intersection (CI) seam paths. Instead, most of the CIs involved in the photoisomerizationmore » are far from MECIs and minimum energy CI seam paths. Thus, both dynamical nuclear effects and dynamic electron correlation are critical to understanding the photochemical mechanism.« less

Hartree-Fock theory of the inhomogeneous electron gas at a jellium metal surface: Rigorous upper bounds to the surface energy and accurate work functions

NASA Astrophysics Data System (ADS)

Sahni, V.; Ma, C. Q.

1980-12-01

The inhomogeneous electron gas at a jellium metal surface is studied in the Hartree-Fock approximation by Kohn-Sham density functional theory. Rigorous upper bounds to the surface energy are derived by application of the Rayleigh-Ritz variational principle for the energy, the surface kinetic, electrostatic, and nonlocal exchange energy functionals being determined exactly for the accurate linear-potential model electronic wave functions. The densities obtained by the energy minimization constraint are then employed to determine work-function results via the variationally accurate "displaced-profile change-in-self-consistent-field" expression. The theoretical basis of this non-self-consistent procedure and its demonstrated accuracy for the fully correlated system (as treated within the local-density approximation for exchange and correlation) leads us to conclude these results for the surface energies and work functions to be essentially exact. Work-function values are also determined by the Koopmans'-theorem expression, both for these densities as well as for those obtained by satisfaction of the constraint set on the electrostatic potential by the Budd-Vannimenus theorem. The use of the Hartree-Fock results in the accurate estimation of correlation-effect contributions to these surface properties of the nonuniform electron gas is also indicated. In addition, the original work and approximations made by Bardeen in this attempt at a solution of the Hartree-Fock problem are briefly reviewed in order to contrast with the present work.

The derivative discontinuity of the exchange-correlation functional.

PubMed

Mori-Sánchez, Paula; Cohen, Aron J

2014-07-28

The derivative discontinuity is a key concept in electronic structure theory in general and density functional theory in particular. The electronic energy of a quantum system exhibits derivative discontinuities with respect to different degrees of freedom that are a consequence of the integer nature of electrons. The classical understanding refers to the derivative discontinuity of the total energy as a function of the total number of electrons (N), but it can also manifest at constant N. Examples are shown in models including several hydrogen systems with varying numbers of electrons or nuclear charge (Z), as well as the 1-dimensional Hubbard model (1DHM). Two sides of the problem are investigated: first, the failure of currently used approximate exchange-correlation functionals in DFT and, second, the importance of the derivative discontinuity in the exact electronic structure of molecules, as revealed by full configuration interaction (FCI). Currently, all approximate functionals, including hybrids, miss the derivative discontinuity, leading to basic errors that can be seen in many ways: from the complete failure to give the total energy of H2 and H2(+), to the missing gap in Mott insulators such as stretched H2 and the thermodynamic limit of the 1DHM, or a qualitatively incorrect density in the HZ molecule with two electrons and incorrect electron transfer processes. Description of the exact particle behaviour of electrons is emphasised, which is key to many important physical processes in real systems, especially those involving electron transfer, and offers a challenge for the development of new exchange-correlation functionals.

Big Data Meets Quantum Chemistry Approximations: The Δ-Machine Learning Approach.

PubMed

Ramakrishnan, Raghunathan; Dral, Pavlo O; Rupp, Matthias; von Lilienfeld, O Anatole

2015-05-12

Chemically accurate and comprehensive studies of the virtual space of all possible molecules are severely limited by the computational cost of quantum chemistry. We introduce a composite strategy that adds machine learning corrections to computationally inexpensive approximate legacy quantum methods. After training, highly accurate predictions of enthalpies, free energies, entropies, and electron correlation energies are possible, for significantly larger molecular sets than used for training. For thermochemical properties of up to 16k isomers of C7H10O2 we present numerical evidence that chemical accuracy can be reached. We also predict electron correlation energy in post Hartree-Fock methods, at the computational cost of Hartree-Fock, and we establish a qualitative relationship between molecular entropy and electron correlation. The transferability of our approach is demonstrated, using semiempirical quantum chemistry and machine learning models trained on 1 and 10% of 134k organic molecules, to reproduce enthalpies of all remaining molecules at density functional theory level of accuracy.

Reduced electronic correlation effects in half substituted Ba(Fe1-xCox)2As2

NASA Astrophysics Data System (ADS)

Liu, Z.-H.; Yaresko, A. N.; Li, Y.; Evtushinsky, D. V.; Dai, P.-C.; Borisenko, S. V.

2018-06-01

We report a comprehensive study of the tridimensional nature and orbital character of the low-energy electronic structure in 50% Cobalt doped Ba(Fe1-xCox)2As2 (d6.5), by using polarization- and photon energy-dependent angle-resolved photoemission spectroscopy. An extra electron-like Fermi surface is observed around the Brillouin zone boundary compared with isoelectronic KyFe2-xSe2 (d6.5). The bands near the Fermi level (EF) are mainly derived from Fe/Co 3d t2g orbitals, revealing visible dispersions along the kz direction. In combination with the local density approximation and the dynamical mean-field theory calculations, we find that the As 4p bands are non-renormalized and the whole 3d band needs to be renormalized by a "single" factor of ˜1.6, indicating moderate electronic correlation effects. The "single" factor description of the correlation strength among the different 3d orbitals is also in sharp contrast to orbital-dependent correlation effects in BaFe2As2. Our findings indicate a remarkable reduction of correlation effects with little difference among 3d orbitals in BaFeCoAs2, due to the increased filling of the electronic 3d shell in the presence of significant Hund's coupling. The results support that the electronic correlation effects and multiple orbital physics play an important role in the superconductivity of the 122 system and in other ferropnictides.

Assessing the role of Hartree-Fock exchange, correlation energy and long range corrections in evaluating ionization potential, and electron affinity in density functional theory.

PubMed

Vikramaditya, Talapunur; Lin, Shiang-Tai

2017-06-05

Accurate determination of ionization potentials (IPs), electron affinities (EAs), fundamental gaps (FGs), and HOMO, LUMO energy levels of organic molecules play an important role in modeling and predicting the efficiencies of organic photovoltaics, OLEDs etc. In this work, we investigate the effects of Hartree Fock (HF) Exchange, correlation energy, and long range corrections in predicting IP and EA in Hybrid Functionals. We observe increase in percentage of HF exchange results in increase of IPs and decrease in EAs. Contrary to the general expectations inclusion of both HF exchange and correlation energy (from the second order perturbation theory MP2) leads to poor prediction. Range separated Hybrid Functionals are found to be more reliable among various DFT Functionals investigated. DFT Functionals predict accurate IPs whereas post HF methods predict accurate EAs. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Correlation of electron and proton irradiation-induced damage in InP solar cells

NASA Technical Reports Server (NTRS)

Walters, Robert J.; Summers, Geoffrey P.; Messenger, Scott R.; Burke, Edward A.

1995-01-01

When determining the best solar cell technology for a particular space flight mission, accurate prediction of solar cell performance in a space radiation environment is essential. The current methodology used to make such predictions requires extensive experimental data measured under both electron and proton irradiation. Due to the rising cost of accelerators and irradiation facilities, such extensive data sets are expensive to obtain. Moreover, with the rapid development of novel cell designs, the necessary data are often not available. Therefore, a method for predicting cell degradation based on limited data is needed. Such a method has been developed at the Naval Research Laboratory based on damage correlation using 'displacement damage dose' which is the product of the non-ionizing energy loss (NIEL) and the particle fluence. Displacement damage dose is a direct analog of the ionization dose used to correlate the effects of ionizing radiations. In this method, the performance of a solar cell in a complex radiation environment can be predicted from data on a single proton energy and two electron energies, or one proton energy, one electron energy, and Co(exp 60) gammas. This method has been used to accurately predict the extensive data set measured by Anspaugh on GaAs/Ge solar cells under a wide range of electron and proton energies. In this paper, the method is applied to InP solar cells using data measured under 1 MeV electron and 3 MeV proton irradiations, and the calculations are shown to agree well with the measured data. In addition to providing accurate damage predictions, this method also provides a basis for quantitative comparisons of the performance of different cell technologies. The performance of the present InP cells is compared to that published for GaAs/Ge cells. The results show InP to be inherently more resistant to displacement energy deposition than GaAs/Ge.

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

Kirschner, J.; Kerherve, G.; Winkler, C.

In this article, a novel time-of-flight spectrometer for two-electron-emission (e,2e/{gamma},2e) correlation spectroscopy from surfaces at low electron energies is presented. The spectrometer consists of electron optics that collect emitted electrons over a solid angle of approximately 1 sr and focus them onto a multichannel plate using a reflection technique. The flight time of an electron with kinetic energy of E{sub kin}{approx_equal}25 eV is around 100 ns. The corresponding time- and energy resolution are typically {approx_equal}1 ns and {approx_equal}0.65 eV, respectively. The first (e,2e) data obtained with the present setup from a LiF film are presented.

Hybrid Correlation Energy (HyCE): An Approach Based on Separate Evaluations of Internal and External Components.

PubMed

Ivanic, Joseph; Schmidt, Michael W

2018-06-04

A novel hybrid correlation energy (HyCE) approach is proposed that determines the total correlation energy via distinct computation of its internal and external components. This approach evolved from two related studies. First, rigorous assessment of the accuracies and size extensivities of a number of electron correlation methods, that include perturbation theory (PT2), coupled-cluster (CC), configuration interaction (CI), and coupled electron pair approximation (CEPA), shows that the CEPA(0) variant of the latter and triples-corrected CC methods consistently perform very similarly. These findings were obtained by comparison to near full CI results for four small molecules and by charting recovered correlation energies for six steadily growing chain systems. Second, by generating valence virtual orbitals (VVOs) and utilizing the CEPA(0) method, we were able to partition total correlation energies into internal (or nondynamic) and external (or dynamic) parts for the aforementioned six chain systems and a benchmark test bed of 36 molecules. When using triple-ζ basis sets it was found that per orbital internal correlation energies were appreciably larger than per orbital external energies and that the former showed far more chemical variation than the latter. Additionally, accumulations of external correlation energies were seen to proceed smoothly, and somewhat linearly, as the virtual space is gradually increased. Combination of these two studies led to development of the HyCE approach, whereby the internal and external correlation energies are determined separately by CEPA(0)/VVO and PT2/external calculations, respectively. When applied to the six chain systems and the 36-molecule benchmark test set it was found that HyCE energies followed closely those of triples-corrected CC and CEPA(0) while easily outperforming MP2 and CCSD. The success of the HyCE approach is more notable when considering that its cost is only slightly more than MP2 and significantly cheaper than the CC approaches.

Correlation matrix renormalization theory for correlated-electron materials with application to the crystalline phases of atomic hydrogen

DOE PAGES

Zhao, Xin; Liu, Jun; Yao, Yong-Xin; ...

2018-01-23

Developing accurate and computationally efficient methods to calculate the electronic structure and total energy of correlated-electron materials has been a very challenging task in condensed matter physics and materials science. Recently, we have developed a correlation matrix renormalization (CMR) method which does not assume any empirical Coulomb interaction U parameters and does not have double counting problems in the ground-state total energy calculation. The CMR method has been demonstrated to be accurate in describing both the bonding and bond breaking behaviors of molecules. In this study, we extend the CMR method to the treatment of electron correlations in periodic solidmore » systems. By using a linear hydrogen chain as a benchmark system, we show that the results from the CMR method compare very well with those obtained recently by accurate quantum Monte Carlo (QMC) calculations. We also study the equation of states of three-dimensional crystalline phases of atomic hydrogen. We show that the results from the CMR method agree much better with the available QMC data in comparison with those from density functional theory and Hartree-Fock calculations.« less

Correlation matrix renormalization theory for correlated-electron materials with application to the crystalline phases of atomic hydrogen

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

Zhao, Xin; Liu, Jun; Yao, Yong-Xin

Developing accurate and computationally efficient methods to calculate the electronic structure and total energy of correlated-electron materials has been a very challenging task in condensed matter physics and materials science. Recently, we have developed a correlation matrix renormalization (CMR) method which does not assume any empirical Coulomb interaction U parameters and does not have double counting problems in the ground-state total energy calculation. The CMR method has been demonstrated to be accurate in describing both the bonding and bond breaking behaviors of molecules. In this study, we extend the CMR method to the treatment of electron correlations in periodic solidmore » systems. By using a linear hydrogen chain as a benchmark system, we show that the results from the CMR method compare very well with those obtained recently by accurate quantum Monte Carlo (QMC) calculations. We also study the equation of states of three-dimensional crystalline phases of atomic hydrogen. We show that the results from the CMR method agree much better with the available QMC data in comparison with those from density functional theory and Hartree-Fock calculations.« less

Correlation between energy deposition and molecular damage from Auger electrons: A case study of ultra-low energy (5–18 eV) electron interactions with DNA

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

Rezaee, Mohammad, E-mail: Mohammad.Rezaee@USherbrooke.ca; Hunting, Darel J.; Sanche, Léon

2014-07-15

Purpose: The present study introduces a new method to establish a direct correlation between biologically related physical parameters (i.e., stopping and damaging cross sections, respectively) for an Auger-electron emitting radionuclide decaying within a target molecule (e.g., DNA), so as to evaluate the efficacy of the radionuclide at the molecular level. These parameters can be applied to the dosimetry of Auger electrons and the quantification of their biological effects, which are the main criteria to assess the therapeutic efficacy of Auger-electron emitting radionuclides. Methods: Absorbed dose and stopping cross section for the Auger electrons of 5–18 eV emitted by{sup 125}I withinmore » DNA were determined by developing a nanodosimetric model. The molecular damages induced by these Auger electrons were investigated by measuring damaging cross section, including that for the formation of DNA single- and double-strand breaks. Nanoscale films of pure plasmid DNA were prepared via the freeze-drying technique and subsequently irradiated with low-energy electrons at various fluences. The damaging cross sections were determined by employing a molecular survival model to the measured exposure–response curves for induction of DNA strand breaks. Results: For a single decay of{sup 125}I within DNA, the Auger electrons of 5–18 eV deposit the energies of 12.1 and 9.1 eV within a 4.2-nm{sup 3} volume of a hydrated or dry DNA, which results in the absorbed doses of 270 and 210 kGy, respectively. DNA bases have a major contribution to the deposited energies. Ten-electronvolt and high linear energy transfer 100-eV electrons have a similar cross section for the formation of DNA double-strand break, while 100-eV electrons are twice as efficient as 10 eV in the induction of single-strand break. Conclusions: Ultra-low-energy electrons (<18 eV) substantially contribute to the absorbed dose and to the molecular damage from Auger-electron emitting radionuclides; hence, they should be considered in the dosimetry calculation of such radionuclides. Moreover, absorbed dose is not an appropriate physical parameter for nanodosimetry. Instead, stopping cross section, which describes the probability of energy deposition in a target molecule can be an appropriate nanodosimetric parameter. The stopping cross section is correlated with a damaging cross section (e.g., cross section for the double-strand break formation) to quantify the number of each specific lesion in a target molecule for each nuclear decay of a single Auger-electron emitting radionuclide.« less

Correlation between energy deposition and molecular damage from Auger electrons: A case study of ultra-low energy (5–18 eV) electron interactions with DNA

PubMed Central

Rezaee, Mohammad; Hunting, Darel J.; Sanche, Léon

2015-01-01

Purpose The present study introduces a new method to establish a direct correlation between biologically related physical parameters (i.e., stopping and damaging cross sections, respectively) for an Auger-electron emitting radionuclide decaying within a target molecule (e.g., DNA), so as to evaluate the efficacy of the radionuclide at the molecular level. These parameters can be applied to the dosimetry of Auger electrons and the quantification of their biological effects, which are the main criteria to assess the therapeutic efficacy of Auger-electron emitting radionuclides. Methods Absorbed dose and stopping cross section for the Auger electrons of 5–18 eV emitted by 125I within DNA were determined by developing a nanodosimetric model. The molecular damages induced by these Auger electrons were investigated by measuring damaging cross section, including that for the formation of DNA single- and double-strand breaks. Nanoscale films of pure plasmid DNA were prepared via the freeze-drying technique and subsequently irradiated with low-energy electrons at various fluences. The damaging cross sections were determined by employing a molecular survival model to the measured exposure–response curves for induction of DNA strand breaks. Results For a single decay of 125I within DNA, the Auger electrons of 5–18 eV deposit the energies of 12.1 and 9.1 eV within a 4.2-nm3 volume of a hydrated or dry DNA, which results in the absorbed doses of 270 and 210 kGy, respectively. DNA bases have a major contribution to the deposited energies. Ten-electronvolt and high linear energy transfer 100-eV electrons have a similar cross section for the formation of DNA double-strand break, while 100-eV electrons are twice as efficient as 10 eV in the induction of single-strand break. Conclusions Ultra-low-energy electrons (<18 eV) substantially contribute to the absorbed dose and to the molecular damage from Auger-electron emitting radionuclides; hence, they should be considered in the dosimetry calculation of such radionuclides. Moreover, absorbed dose is not an appropriate physical parameter for nanodosimetry. Instead, stopping cross section, which describes the probability of energy deposition in a target molecule can be an appropriate nanodosimetric parameter. The stopping cross section is correlated with a damaging cross section (e.g., cross section for the double-strand break formation) to quantify the number of each specific lesion in a target molecule for each nuclear decay of a single Auger-electron emitting radionuclide. PMID:24989405

Electron energy boosting in laser-wake-field acceleration with external magnetic field Bapprox1 T and laser prepulses

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

Hosokai, Tomonao; Zhidkov, Alexei; Yamazaki, Atsushi

2010-03-22

Hundred-mega-electron-volt electron beams with quasi-monoenergetic distribution, and a transverse geometrical emittance as small as approx0.02 pi mm mrad are generated by low power (7 TW, 45 fs) laser pulses tightly focused in helium gas jets in an external static magnetic field, Bapprox1 T. Generation of monoenergetic beams strongly correlates with appearance of a straight, at least 2 mm length plasma channel in a short time before the main laser pulse and with the energy of copropagating picosecond pedestal pulses (PPP). For a moderate energy PPP, the multiple or staged electron self-injection in the channel gives several narrow peaks in themore » electron energy distribution.« less

Fourier-Legendre expansion of the one-electron density matrix of ground-state two-electron atoms.

PubMed

Ragot, Sébastien; Ruiz, María Belén

2008-09-28

The density matrix rho(r,r(')) of a spherically symmetric system can be expanded as a Fourier-Legendre series of Legendre polynomials P(l)(cos theta=rr(')rr(')). Application is here made to harmonically trapped electron pairs (i.e., Moshinsky's and Hooke's atoms), for which exact wavefunctions are known, and to the helium atom, using a near-exact wavefunction. In the present approach, generic closed form expressions are derived for the series coefficients of rho(r,r(')). The series expansions are shown to converge rapidly in each case, with respect to both the electron number and the kinetic energy. In practice, a two-term expansion accounts for most of the correlation effects, so that the correlated density matrices of the atoms at issue are essentially a linear functions of P(l)(cos theta)=cos theta. For example, in the case of Hooke's atom, a two-term expansion takes in 99.9% of the electrons and 99.6% of the kinetic energy. The correlated density matrices obtained are finally compared to their determinantal counterparts, using a simplified representation of the density matrix rho(r,r(')), suggested by the Legendre expansion. Interestingly, two-particle correlation is shown to impact the angular delocalization of each electron, in the one-particle space spanned by the r and r(') variables.

Scanning electron microscopy combined with image processing technique: Analysis of microstructure, texture and tenderness in Semitendinous and Gluteus Medius bovine muscles.

PubMed

Pieniazek, Facundo; Messina, Valeria

2016-11-01

In this study the effect of freeze drying on the microstructure, texture, and tenderness of Semitendinous and Gluteus Medius bovine muscles were analyzed applying Scanning Electron Microscopy combined with image analysis. Samples were analyzed by Scanning Electron Microscopy at different magnifications (250, 500, and 1,000×). Texture parameters were analyzed by Texture analyzer and by image analysis. Tenderness by Warner-Bratzler shear force. Significant differences (p < 0.05) were obtained for image and instrumental texture features. A linear trend with a linear correlation was applied for instrumental and image features. Image texture features calculated from Gray Level Co-occurrence Matrix (homogeneity, contrast, entropy, correlation and energy) at 1,000× in both muscles had high correlations with instrumental features (chewiness, hardness, cohesiveness, and springiness). Tenderness showed a positive correlation in both muscles with image features (energy and homogeneity). Combing Scanning Electron Microscopy with image analysis can be a useful tool to analyze quality parameters in meat.Summary SCANNING 38:727-734, 2016. © 2016 Wiley Periodicals, Inc. © Wiley Periodicals, Inc.

Towards a First-Principles Determination of Effective Coulomb Interactions in Correlated Electron Materials: Role of Intershell Interactions

NASA Astrophysics Data System (ADS)

Seth, Priyanka; Hansmann, Philipp; van Roekeghem, Ambroise; Vaugier, Loig; Biermann, Silke

2017-08-01

The determination of the effective Coulomb interactions to be used in low-energy Hamiltonians for materials with strong electronic correlations remains one of the bottlenecks for parameter-free electronic structure calculations. We propose and benchmark a scheme for determining the effective local Coulomb interactions for charge-transfer oxides and related compounds. Intershell interactions between electrons in the correlated shell and ligand orbitals are taken into account in an effective manner, leading to a reduction of the effective local interactions on the correlated shell. Our scheme resolves inconsistencies in the determination of effective interactions as obtained by standard methods for a wide range of materials, and allows for a conceptual understanding of the relation of cluster model and dynamical mean field-based electronic structure calculations.

Towards a First-Principles Determination of Effective Coulomb Interactions in Correlated Electron Materials: Role of Intershell Interactions.

PubMed

Seth, Priyanka; Hansmann, Philipp; van Roekeghem, Ambroise; Vaugier, Loig; Biermann, Silke

2017-08-04

The determination of the effective Coulomb interactions to be used in low-energy Hamiltonians for materials with strong electronic correlations remains one of the bottlenecks for parameter-free electronic structure calculations. We propose and benchmark a scheme for determining the effective local Coulomb interactions for charge-transfer oxides and related compounds. Intershell interactions between electrons in the correlated shell and ligand orbitals are taken into account in an effective manner, leading to a reduction of the effective local interactions on the correlated shell. Our scheme resolves inconsistencies in the determination of effective interactions as obtained by standard methods for a wide range of materials, and allows for a conceptual understanding of the relation of cluster model and dynamical mean field-based electronic structure calculations.

The electronic properties of potassium doped copper-phthalocyanine studied by electron energy-loss spectroscopy.

PubMed

Flatz, K; Grobosch, M; Knupfer, M

2007-06-07

The authors have studied the electronic structure of potassium doped copper-phthalocyanine using electron energy-loss spectroscopy. The evolution of the loss function indicates the formation of distinct KxCuPc phases. Taking into account the C1s and K2p core level excitations and recent results by Giovanelli et al. [J. Chem. Phys. 126, 044709 (2007)], they conclude that these are K2CuPc and K4CuPc. They discuss the changes in the electronic excitations upon doping on the basis of the molecular electronic levels and the presence of electronic correlations.

Natural occupation numbers in two-electron quantum rings.

PubMed

Tognetti, Vincent; Loos, Pierre-François

2016-02-07

Natural orbitals (NOs) are central constituents for evaluating correlation energies through efficient approximations. Here, we report the closed-form expression of the NOs of two-electron quantum rings, which are prototypical finite-extension systems and new starting points for the development of exchange-correlation functionals in density functional theory. We also show that the natural occupation numbers for these two-electron paradigms are in general non-vanishing and follow the same power law decay as atomic and molecular two-electron systems.

Natural occupation numbers in two-electron quantum rings

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

Tognetti, Vincent, E-mail: vincent.tognetti@univ-rouen.fr; Loos, Pierre-François

2016-02-07

Natural orbitals (NOs) are central constituents for evaluating correlation energies through efficient approximations. Here, we report the closed-form expression of the NOs of two-electron quantum rings, which are prototypical finite-extension systems and new starting points for the development of exchange-correlation functionals in density functional theory. We also show that the natural occupation numbers for these two-electron paradigms are in general non-vanishing and follow the same power law decay as atomic and molecular two-electron systems.

Optical-model potential for electron and positron elastic scattering by atoms

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

Salvat, Francesc

2003-07-01

An optical-model potential for systematic calculations of elastic scattering of electrons and positrons by atoms and positive ions is proposed. The electrostatic interaction is determined from the Dirac-Hartree-Fock self-consistent atomic electron density. In the case of electron projectiles, the exchange interaction is described by means of the local-approximation of Furness and McCarthy. The correlation-polarization potential is obtained by combining the correlation potential derived from the local density approximation with a long-range polarization interaction, which is represented by means of a Buckingham potential with an empirical energy-dependent cutoff parameter. The absorption potential is obtained from the local-density approximation, using the Born-Ochkurmore » approximation and the Lindhard dielectric function to describe the binary collisions with a free-electron gas. The strength of the absorption potential is adjusted by means of an empirical parameter, which has been determined by fitting available absolute elastic differential cross-section data for noble gases and mercury. The Dirac partial-wave analysis with this optical-model potential provides a realistic description of elastic scattering of electrons and positrons with energies in the range from {approx}100 eV up to {approx}5 keV. At higher energies, correlation-polarization and absorption corrections are small and the usual static-exchange approximation is sufficiently accurate for most practical purposes.« less

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

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

PubMed Central

Li, Zheng; Vendrell, Oriol

2016-01-01

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

Assessment of higher order correlation effects with the help of Moller-Plesset perturbation theory up to sixth order

NASA Astrophysics Data System (ADS)

He, Yuan; Cremer, Dieter

For 30 molecules and two atoms, MP n correlation energies up to n = 6 are computed and used to analyse higher order correlation effects and the initial convergence behaviour of the MP n series. Particularly useful is the analysis of correlation contributions E(n)XY ...( n = 4,5,6; X , Y ,... = S, D, T, Q denoting single, double, triple, and quadruple excitations) in the form of correlation energy spectra. Two classes of system are distinguished, namely class A systems possessing well separated electron pairs and class B systems which are characterized by electron clustering in certain regions of atomic and molecular space. For class A systems, electron pair correlation effects as described by D, Q, DD, DQ, QQ, DDD, etc., contributions are most important, which are stepwise included at MP n with n = 2,... ,6. Class A systems are reasonably described by MP n theory, which is reflected by the fact that convergence of the MP n series is monotonic (but relatively slow) for class A systems. The description of class B systems is difficult since three- and four-electron correlation effects and couplings between two-, three-, and four-electron correlation effects missing for lower order perturbation theory are significant. MP n methods, which do not cover these effects, simulate higher order with lower order correlation effects thus exaggerating the latter, which has to be corrected with increasing n. Consequently, the MP n series oscillates for class B systems at low orders. A possible divergence of the MP n series is mostly a consequence of an unbalanced basis set. For example, diffuse functions added to an unsaturated sp basis lead to an exaggeration of higher order correlation effects, which can cause enhanced oscillations and divergence of the MP n series.

The Energy Spectrum of Solar Energetic Electrons

NASA Astrophysics Data System (ADS)

Wang, L.; Yang, L.; Krucker, S.; Wimmer-Schweingruber, R. F.; Bale, S. D.

2015-12-01

Here we present a statistical survey of the energy spectrum of solar energetic electron events (SEEs) observed by the WIND 3DP instrument from 1995 though 2014. For SEEs with the minimum energy below 10 keV and the maximum energy above 100 keV, ~85% (~2%) have a double-power-law energy spectrum with a steepening (hardening) above the break energy, while ~13% have a single-power-law energy spectrum at all energies. The average spectral index is ~2.4 below the energy break and is ~4.0 above the energy break. For SEEs detected only at energies <10 keV (>20 keV), they generally show a single-power-law spectrum with the average index of ~3.0 (~3.3). The spectrum of SEEs detected only below 10 keV appears to get harder with increasing solar activity, but the spectrum of SEEs with higher-energy electrons shows no clear correlation with solar activity. We will also investigate whether the observed energy spectrum of SEEs at 1 AU mainly reflects the electron acceleration at the Sun or the electron transport in the interplanetary medium.

Electron correlation in Hooke's law atom in the high-density limit.

PubMed

Gill, P M W; O'Neill, D P

2005-03-01

Closed-form expressions for the first three terms in the perturbation expansion of the exact energy and Hartree-Fock energy of the lowest singlet and triplet states of the Hooke's law atom are found. These yield elementary formulas for the exact correlation energies (-49.7028 and -5.807 65 mE(h)) of the two states in the high-density limit and lead to a pair of necessary conditions on the exact correlation kernel G(w) in Hartree-Fock-Wigner theory.

A cumulant functional for static and dynamic correlation

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

Hollett, Joshua W., E-mail: j.hollett@uwinnipeg.ca; Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2; Hosseini, Hessam

A functional for the cumulant energy is introduced. The functional is composed of a pair-correction and static and dynamic correlation energy components. The pair-correction and static correlation energies are functionals of the natural orbitals and the occupancy transferred between near-degenerate orbital pairs, rather than the orbital occupancies themselves. The dynamic correlation energy is a functional of the statically correlated on-top two-electron density. The on-top density functional used in this study is the well-known Colle-Salvetti functional. Using the cc-pVTZ basis set, the functional effectively models the bond dissociation of H{sub 2}, LiH, and N{sub 2} with equilibrium bond lengths and dissociationmore » energies comparable to those provided by multireference second-order perturbation theory. The performance of the cumulant functional is less impressive for HF and F{sub 2}, mainly due to an underestimation of the dynamic correlation energy by the Colle-Salvetti functional.« less

Quiet-Time Suprathermal (˜0.1 - 200 keV) Electrons in the Solar Wind

NASA Astrophysics Data System (ADS)

Wang, Linghua; Yang, Liu; Tao, Jiawei; Zong, Qiugang; Li, Gang; Wimmer-Schweingruber, Robert; He, Jiansen; Tu, Chuanyi; Bale, Stuart

2017-04-01

We present a statistical survey of the energy spectrum of solar wind suprathermal (˜0.1-200 keV) electrons measured by the WIND 3DP instrument at 1 AU during quiet times at the minimum and maximum of solar cycles 23 and 24. The observed energy spectrum of both (beaming) strahl and (isotropic) halo electrons at ˜0.1-1.5 keV generally fits to a Kappa distribution function with an index κ and effective temperature Teff, while the observed energy spectrum of nearly isotropic superhalo electrons at ˜20-200 keV generally fits to a power-law function, J ˜ E-β. We find a strong positive correlation between κ and Teff for both strahl and halo electrons, and a strong positive correlation between the strahl density and halo density. In both solar cycles, κ is larger at solar minimum than at solar maximum for both strahl and halo electrons. For the superhalo population, the spectral index β ranges from ˜1.6 to ˜3.7 and the integrated density nsup ranges from 10-8 cm-3 to 10-5 cm-3, with no clear association with the sunspot number. In solar cycle 23 (24), the distribution of β has a broad maximum between 2.4 and 2.8 (2.0 and 2.4). All the strahl, halo and superhalo populations show no obvious correlation with the solar wind core population. These results reflect the nature of the generation of solar wind suprathermal electrons.

Single-stage plasma-based correlated energy spread compensation for ultrahigh 6D brightness electron beams

DOE PAGES

Manahan, Grace G.; Habib, A. F.; Scherkl, P.; ...

2017-06-05

Plasma photocathode wakefield acceleration combines energy gains of tens of GeV m –1 with generation of ultralow emittance electron bunches, and opens a path towards 5D-brightness orders of magnitude larger than state-of-the-art. This holds great promise for compact accelerator building blocks and advanced light sources. However, an intrinsic by-product of the enormous electric field gradients inherent to plasma accelerators is substantial correlated energy spread—an obstacle for key applications such as free-electron-lasers. Here we show that by releasing an additional tailored escort electron beam at a later phase of the acceleration, when the witness bunch is relativistically stable, the plasma wavemore » can be locally overloaded without compromising the witness bunch normalized emittance. Here, this reverses the effective accelerating gradient, and counter-rotates the accumulated negative longitudinal phase space chirp of the witness bunch. Thereby, the energy spread is reduced by an order of magnitude, thus enabling the production of ultrahigh 6D-brightness beams.« less

Understanding individual defects in CdTe thin-film solar cells via STEM: From atomic structure to electrical activity

DOE PAGES

Li, Chen; Poplawsky, Jonathan; Yan, Yanfa; ...

2017-07-01

Here in this paper we review a systematic study of the structure-property correlations of a series of defects in CdTe solar cells. A variety of experimental methods, including aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy, and electron-beam-induced current have been combined with density-functional theory. The research traces the connections between the structures and electrical activities of individual defects including intra-grain partial dislocations, grain boundaries and the CdTe/CdS interface. The interpretations of the physical origin underlying the structure-property correlation provide insights that should further the development of future CdTe solar cells.

Understanding individual defects in CdTe thin-film solar cells via STEM: From atomic structure to electrical activity

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

Li, Chen; Poplawsky, Jonathan; Yan, Yanfa

Here in this paper we review a systematic study of the structure-property correlations of a series of defects in CdTe solar cells. A variety of experimental methods, including aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy, and electron-beam-induced current have been combined with density-functional theory. The research traces the connections between the structures and electrical activities of individual defects including intra-grain partial dislocations, grain boundaries and the CdTe/CdS interface. The interpretations of the physical origin underlying the structure-property correlation provide insights that should further the development of future CdTe solar cells.

Dynamic correlations in the highly dilute 2D electron liquid: Loss function, critical wave vector and analytic plasmon dispersion

NASA Astrophysics Data System (ADS)

Drachta, Jürgen T.; Kreil, Dominik; Hobbiger, Raphael; Böhm, Helga M.

2018-03-01

Correlations, highly important in low-dimensional systems, are known to decrease the plasmon dispersion of two-dimensional electron liquids. Here we calculate the plasmon properties, applying the 'Dynamic Many-Body Theory', accounting for correlated two-particle-two-hole fluctuations. These dynamic correlations are found to significantly lower the plasmon's energy. For the data obtained numerically, we provide an analytic expression that is valid across a wide range both of densities and of wave vectors. Finally, we demonstrate how this can be invoked in determining the actual electron densities from measurements on an AlGaAs quantum well.

THE PHYSICS OF THE FAR-INFRARED-RADIO CORRELATION. I. CALORIMETRY, CONSPIRACY, AND IMPLICATIONS

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

Lacki, Brian C.; Thompson, Todd A.; Quataert, Eliot, E-mail: lacki@astronomy.ohio-state.ed

2010-07-01

The far-infrared (FIR) and radio luminosities of star-forming galaxies are linearly correlated over a very wide range in star formation rate, from normal spirals like the Milky Way to the most intense starbursts. Using one-zone models of cosmic ray (CR) injection, cooling, and escape in star-forming galaxies, we attempt to reproduce the observed FIR-radio correlation (FRC) over its entire span. The normalization and linearity of the FRC, together with constraints on the CR population in the Milky Way, have strong implications for the CR and magnetic energy densities in star-forming galaxies. We show that for consistency with the FRC, {approx}2%more » of the kinetic energy from supernova explosions must go into high-energy primary CR electrons and that {approx}10%-20% must go into high-energy primary CR protons. Secondary electrons and positrons are likely comparable to or dominate primary electrons in dense starburst galaxies. We discuss the implications of our models for the magnetic field strengths of starbursts, the detectability of starbursts by Fermi, and CR feedback. Overall, our models indicate that both CR protons and electrons escape from low surface density galaxies, but lose most of their energy before escaping dense starbursts. The FRC is caused by a combination of the efficient cooling of CR electrons (calorimetry) in starbursts and a conspiracy of several factors. For lower surface density galaxies, the decreasing radio emission caused by CR escape is balanced by the decreasing FIR emission caused by the low effective UV dust opacity. In starbursts, bremsstrahlung, ionization, and inverse Compton cooling decrease the radio emission, but they are countered by secondary electrons/positrons and the dependence of synchrotron frequency on energy, both of which increase the radio emission. Our conclusions hold for a broad range of variations in our fiducial model, such as those including winds, different magnetic field strengths, and different diffusive escape times.« less

Relativistic Electron Precipitation in the Auroral Zone. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Simons, D. J.

1975-01-01

The energy spectra and pitch angle distributions of electrons in the energy range from 50 keV to 2 MeV were determined by a solid state electron energy spectrometer during the Relativistic Electron Precipitation (REP) event of 31 May 1972. The pitch angle distributions were determined from a knowledge of the rocket aspect and the direction in space of the earth's magnetic field. The rocket aspect determination was therefore treated in depth and a method was developed to compensate for the malfunctioning of the aspect magnetometer. The electron fluxes during the REP event were highly variable demonstrating correlated energy, flux, and pitch angle pulsations with time periods of less than one second. A theoretical model for the production of relativistic electrons was proposed. It follows from this model that, at comparatively low background electron densities, the anomalous Doppler resonance leads to the acceleration of near relativistic particles.

Inhomogeneity induced and appropriately parameterized semilocal exchange and correlation energy functionals in two-dimensions.

PubMed

Patra, Abhilash; Jana, Subrata; Samal, Prasanjit

2018-04-07

The construction of meta generalized gradient approximations based on the density matrix expansion (DME) is considered as one of the most accurate techniques to design semilocal exchange energy functionals in two-dimensional density functional formalism. The exchange holes modeled using DME possess unique features that make it a superior entity. Parameterized semilocal exchange energy functionals based on the DME are proposed. The use of different forms of the momentum and flexible parameters is to subsume the non-uniform effects of the density in the newly constructed semilocal functionals. In addition to the exchange functionals, a suitable correlation functional is also constructed by working upon the local correlation functional developed for 2D homogeneous electron gas. The non-local effects are induced into the correlation functional by a parametric form of one of the newly constructed exchange energy functionals. The proposed functionals are applied to the parabolic quantum dots with a varying number of confined electrons and the confinement strength. The results obtained with the aforementioned functionals are quite satisfactory, which indicates why these are suitable for two-dimensional quantum systems.

Inhomogeneity induced and appropriately parameterized semilocal exchange and correlation energy functionals in two-dimensions

NASA Astrophysics Data System (ADS)

Patra, Abhilash; Jana, Subrata; Samal, Prasanjit

2018-04-01

The construction of meta generalized gradient approximations based on the density matrix expansion (DME) is considered as one of the most accurate techniques to design semilocal exchange energy functionals in two-dimensional density functional formalism. The exchange holes modeled using DME possess unique features that make it a superior entity. Parameterized semilocal exchange energy functionals based on the DME are proposed. The use of different forms of the momentum and flexible parameters is to subsume the non-uniform effects of the density in the newly constructed semilocal functionals. In addition to the exchange functionals, a suitable correlation functional is also constructed by working upon the local correlation functional developed for 2D homogeneous electron gas. The non-local effects are induced into the correlation functional by a parametric form of one of the newly constructed exchange energy functionals. The proposed functionals are applied to the parabolic quantum dots with a varying number of confined electrons and the confinement strength. The results obtained with the aforementioned functionals are quite satisfactory, which indicates why these are suitable for two-dimensional quantum systems.

Measurements of the ground-state Lamb shift and electron-correlation effects in hydrogenlike and heliumlike uranium

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

Lupton, J.H.; Dietrich, D.D.; Hailey, C.J.

1994-09-01

We report measurements of transition energies for highly ionized uranium. For hydrogenic uranium we have measured 102 130[plus minus]92 eV for the 2[ital p][sub 3/2-]1[ital s][sub 1/2] transition. This measurement is sensitive to the 1[ital s] Lamb shift, probing the electron self-energy in high-field QED. In addition, we have measured the (1[ital s]2[ital p])[sup 1][ital P][sub 1],[sup 3][ital P][sub 2-](1[ital s][sup 2])[sup 1][ital S][sub 0] transition in heliumlike uranium as 100 598[plus minus]111 eV, probing relativistic electron-electron correlation effects. Both measurements were obtained with a Doppler spectrometer, a proven technique which we have adapted to the field of high-[ital Z]more » precision atomic transition-energy measurements. These measurements demonstrate the potential of this technique to attain [similar to]1 eV uncertainties.« less

Remote control of the dissociative ionization of H2 based on electron-H2 + entanglement

NASA Astrophysics Data System (ADS)

Wang, Jun-Ping; He, Feng

2018-04-01

The single ionization of H2 in strong laser fields creates the correlated electron-H2 + pair. Based on such a correlation, we conceive a strategy to control the energy spectra of the freed electron or dissociative fragments by simulating the time-dependent Schrödinger equation. Two attosecond pulses in a train produce the replica of electron-H2 + pairs, which are to be steered by a time-delayed phase-stabilized (mid)infrared laser pulse. By controlling the behavior of the freed electron, the dissociation of H2 + can be controlled even though there is no direct laser-H2 + coupling. On the other hand, the photoelectron energy spectra can be manipulated via laser-H2 + coupling. This study demonstrates the entanglement of molecular quantum wave packets, and affords a route to remotely control molecular dissociative ionization.

Robust validation of approximate 1-matrix functionals with few-electron harmonium atoms

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

Cioslowski, Jerzy, E-mail: jerzy@wmf.univ.szczecin.pl; Piris, Mario; Matito, Eduard

2015-12-07

A simple comparison between the exact and approximate correlation components U of the electron-electron repulsion energy of several states of few-electron harmonium atoms with varying confinement strengths provides a stringent validation tool for 1-matrix functionals. The robustness of this tool is clearly demonstrated in a survey of 14 known functionals, which reveals their substandard performance within different electron correlation regimes. Unlike spot-testing that employs dissociation curves of diatomic molecules or more extensive benchmarking against experimental atomization energies of molecules comprising some standard set, the present approach not only uncovers the flaws and patent failures of the functionals but, even moremore » importantly, also allows for pinpointing their root causes. Since the approximate values of U are computed at exact 1-densities, the testing requires minimal programming and thus is particularly suitable for rapid screening of new functionals.« less

Electron detachment of the hydrogen-bonded amino acid side-chain guanine complexes

NASA Astrophysics Data System (ADS)

Wang, Jing; Gu, Jiande; Leszczynski, Jerzy

2007-07-01

The photoelectron spectra of the hydrogen-bonded amino acid side-chain-guanine complexes has been studied at the partial third order (P3) self-energy approximation of the electron propagator theory. The correlation between the vertical electron detachment energy and the charge distributions on the guanine moiety reveals that the vertical electron detachment energy (VDE) increases as the positive charge distribution on the guanine increases. The low VDE values determined for the negatively charged complexes of the guanine-side-chain-group of Asp/Glu suggest that the influence of the H-bonded anionic groups on the VDE of guanine could be more important than that of the anionic backbone structure. The even lower vertical electron detachment energy for guanine is thus can be expected in the H-bonded protein-DNA systems.

Dispersion- and Exchange-Corrected Density Functional Theory for Sodium Ion Hydration.

PubMed

Soniat, Marielle; Rogers, David M; Rempe, Susan B

2015-07-14

A challenge in density functional theory is developing functionals that simultaneously describe intermolecular electron correlation and electron delocalization. Recent exchange-correlation functionals address those two issues by adding corrections important at long ranges: an atom-centered pairwise dispersion term to account for correlation and a modified long-range component of the electron exchange term to correct for delocalization. Here we investigate how those corrections influence the accuracy of binding free energy predictions for sodium-water clusters. We find that the dual-corrected ωB97X-D functional gives cluster binding energies closest to high-level ab initio methods (CCSD(T)). Binding energy decomposition shows that the ωB97X-D functional predicts the smallest ion-water (pairwise) interaction energy and larger multibody contributions for a four-water cluster than most other functionals - a trend consistent with CCSD(T) results. Also, ωB97X-D produces the smallest amounts of charge transfer and the least polarizable waters of the density functionals studied, which mimics the lower polarizability of CCSD. When compared with experimental binding free energies, however, the exchange-corrected CAM-B3LYP functional performs best (error <1 kcal/mol), possibly because of its parametrization to experimental formation enthalpies. For clusters containing more than four waters, "split-shell" coordination must be considered to obtain accurate free energies in comparison with experiment.

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(+).

Dependence of structure factor and correlation energy on the width of electron wires

NASA Astrophysics Data System (ADS)

Ashokan, Vinod; Bala, Renu; Morawetz, Klaus; Pathak, Kare Narain

2018-02-01

The structure factor and correlation energy of a quantum wire of thickness b ≪ a B are studied in random phase approximation (RPA) and for the less investigated region r s < 1. Using the single-loop approximation, analytical expressions of the structure factor are obtained. The exact expressions for the exchange energy are also derived for a cylindrical and harmonic wire. The correlation energy in RPA is found to be represented by ɛ c ( b, r s ) = α( r s )/ b + β( r s ) ln( b) + η( r s ), for small b and high densities. For a pragmatic width of the wire, the correlation energy is in agreement with the quantum Monte Carlo simulation data.

Relativistic calculation of correlational energy for a helium-like atom

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

Palchikov, V.G.

This paper presents an analytical method for calculating the firstorder correlational energy from the electron interaction, taking account of lag effects. Explicit analytical expressions are obtained for radial matrix elements. The nonrelativistic limit is investigated. The given method may be used to calculate correlation effects in higher orders of perturbation theory (second and higher orders with respect to 1/z) using the Strum expansion for the Coulomb Green's functions.

Plasma instabilities in the terrestrial magnetosphere - A review of recent theoretical research

NASA Technical Reports Server (NTRS)

Gary, S. Peter

1987-01-01

This paper reviews recent theoretical research on plasma instabilities in the terrestrial magnetosphere. This paper is organized with respect to particle free energies: electron-ion currents, electron beams, ion beams, electron anisotropies and ion anisotropies are successively considered. For each free energy, the associated instability properties are summarized, and their applications to magnetospheric physics are briefly described. Theory and simulations which have established close correlations with observations are emphasized.

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

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

Li, Zheng; Vendrell, Oriol

2016-01-13

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

Uniform quantized electron gas

NASA Astrophysics Data System (ADS)

Høye, Johan S.; Lomba, Enrique

2016-10-01

In this work we study the correlation energy of the quantized electron gas of uniform density at temperature T  =  0. To do so we utilize methods from classical statistical mechanics. The basis for this is the Feynman path integral for the partition function of quantized systems. With this representation the quantum mechanical problem can be interpreted as, and is equivalent to, a classical polymer problem in four dimensions where the fourth dimension is imaginary time. Thus methods, results, and properties obtained in the statistical mechanics of classical fluids can be utilized. From this viewpoint we recover the well known RPA (random phase approximation). Then to improve it we modify the RPA by requiring the corresponding correlation function to be such that electrons with equal spins can not be on the same position. Numerical evaluations are compared with well known results of a standard parameterization of Monte Carlo correlation energies.

Renormalization group method based on the ionization energy theory

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

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

2011-03-15

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

Self-consistent many-electron theory of electron work functions and surface potential characteristics for selected metals

NASA Technical Reports Server (NTRS)

Smith, J. R.

1969-01-01

Electron work functions, surface potentials, and electron number density distributions and electric fields in the surface region of 26 metals were calculated from first principles within the free electron model. Calculation proceeded from an expression of the total energy as a functional of the electron number density, including exchange and correlation energies, as well as a first inhomogeneity term. The self-consistent solution was obtained via a variational procedure. Surface barriers were due principally to many-body effects; dipole barriers were small only for some alkali metals, becoming quite large for the transition metals. Surface energies were inadequately described by this model, which neglects atomistic effects. Reasonable results were obtained for electron work functions and surface potential characteristics, maximum electron densities varying by a factor of over 60.

An ab initio study of the C3(+) cation using multireference methods

NASA Technical Reports Server (NTRS)

Taylor, Peter R.; Martin, J. M. L.; Francois, J. P.; Gijbels, R.

1991-01-01

The energy difference between the linear 2 sigma(sup +, sub u) and cyclic 2B(sub 2) structures of C3(+) has been investigated using large (5s3p2d1f) basis sets and multireference electron correlation treatments, including complete active space self consistent fields (CASSCF), multireference configuration interaction (MRCI), and averaged coupled-pair functional (ACPF) methods, as well as the single-reference quadratic configuration interaction (QCISD(T)) method. Our best estimate, including a correction for basis set incompleteness, is that the linear form lies above the cyclic from by 5.2(+1.5 to -1.0) kcal/mol. The 2 sigma(sup +, sub u) state is probably not a transition state, but a local minimum. Reliable computation of the cyclic/linear energy difference in C3(+) is extremely demanding of the electron correlation treatment used: of the single-reference methods previously considered, CCSD(T) and QCISD(T) perform best. The MRCI + Q(0.01)/(4s2p1d) energy separation of 1.68 kcal/mol should provide a comparison standard for other electron correlation methods applied to this system.

Moments of the electron energy spectrum and partial branching fraction of B{yields}X{sub c}e{nu} decays at the Belle detector

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

Urquijo, P.; Barberio, E.; Dalseno, J.

2007-02-01

We report a measurement of the inclusive electron energy spectrum for charmed semileptonic decays of B mesons in a 140 fb{sup -1} data sample collected at the {upsilon}(4S) resonance with the Belle detector at the KEKB asymmetric energy e{sup +}e{sup -} collider. We determine the first four moments of the electron energy spectrum for threshold values of the electron energy between 0.4 and 2.0 GeV. In addition, we provide values of the partial branching fraction (zeroth moment) for the same electron threshold energies, and independent measurements of the B{sup +} and B{sup 0} partial branching fractions at 0.4 GeV andmore » 0.6 GeV electron threshold energies. We measure the independent B{sup +} and B{sup 0} partial branching fractions with electron threshold energies of 0.4 GeV to be {delta}B(B{sup +}{yields}X{sub c}e{nu})=(10.79{+-}0.25(stat.){+-}0.27(sys.))% and {delta}B(B{sup 0}{yields}X{sub c}e{nu})=(10.08{+-}0.30(stat.){+-}0.22(sys.))%. Full correlations between all measurements are evaluated.« less

Ionization energies and electron affinities from a random-phase-approximation many-body Green's-function method including exchange interactions

NASA Astrophysics Data System (ADS)

Heßelmann, Andreas

2017-06-01

A many-body Green's-function method employing an infinite order summation of ring and exchange-ring contributions to the self-energy is presented. The individual correlation and relaxation contributions to the quasiparticle energies are calculated using an iterative scheme which utilizes density fitting of the particle-hole, particle-particle and hole-hole densities. It is shown that the ionization energies and electron affinities of this approach agree better with highly accurate coupled-cluster singles and doubles with perturbative triples energy difference results than those obtained with second-order Green's-function approaches. An analysis of the correlation and relaxation terms of the self-energy for the direct- and exchange-random-phase-approximation (RPA) Green's-function methods shows that the inclusion of exchange interactions leads to a reduction of the two contributions in magnitude. These differences, however, strongly cancel each other when summing the individual terms to the quasiparticle energies. Due to this, the direct- and exchange-RPA methods perform similarly for the description of ionization energies (IPs) and electron affinities (EAs). The coupled-cluster reference IPs and EAs, if corrected to the adiabatic energy differences between the neutral and charged molecules, were shown to be in very good agreement with experimental measurements.

Stochastic evaluation of second-order many-body perturbation energies.

PubMed

Willow, Soohaeng Yoo; Kim, Kwang S; Hirata, So

2012-11-28

With the aid of the Laplace transform, the canonical expression of the second-order many-body perturbation correction to an electronic energy is converted into the sum of two 13-dimensional integrals, the 12-dimensional parts of which are evaluated by Monte Carlo integration. Weight functions are identified that are analytically normalizable, are finite and non-negative everywhere, and share the same singularities as the integrands. They thus generate appropriate distributions of four-electron walkers via the Metropolis algorithm, yielding correlation energies of small molecules within a few mE(h) of the correct values after 10(8) Monte Carlo steps. This algorithm does away with the integral transformation as the hotspot of the usual algorithms, has a far superior size dependence of cost, does not suffer from the sign problem of some quantum Monte Carlo methods, and potentially easily parallelizable and extensible to other more complex electron-correlation theories.

Atropisomerization of di-para-substituted propyl-bridged biphenyl cyclophanes.

PubMed

Rotzler, Jürgen; Gsellinger, Heiko; Bihlmeier, Angela; Gantenbein, Markus; Vonlanthen, David; Häussinger, Daniel; Klopper, Wim; Mayor, Marcel

2013-01-07

The influence of electron donors and electron acceptors of variable strength in the 4 and 4' position of 2 and 2' propyl-bridged axial chiral biphenyl cyclophanes on their atropisomerization process was studied. Estimated free energies ΔG(‡)(T) of the rotation around the central biphenyl bond which were obtained from (1)H-NMR coalescence measurements were correlated to the Hammett parameters σ(p) as a measure for electron donor and acceptor strength. It is demonstrated that the resulting nice linear correlation is mainly based on the influence of the different substituents on the π-system of the biphenyl cyclophanes. By lineshape analysis the rate constants were calculated and by the use of the Eyring equation the enthalpic and entropic contributions were evaluated. Density functional theory calculations show a planar transition state of the isomerization process and the calculated energy barriers based on this reaction mechanism are in good agreement with the experimentally obtained free energies.

Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn-Sham Theory.

PubMed

Sharpe, Daniel J; Levy, Mel; Tozer, David J

2018-02-13

Levy and Zahariev [Phys. Rev. Lett. 113 113002 (2014)] have proposed a new approach for performing density functional theory calculations, termed direct energy Kohn-Sham (DEKS) theory. In this approach, the electronic energy equals the sum of orbital energies, obtained from Kohn-Sham-like orbital equations involving a shifted Hartree-exchange-correlation potential, which must be approximated. In the present study, density scaling homogeneity considerations are used to facilitate DEKS calculations on a series of atoms and molecules, leading to three nonlocal approximations to the shifted potential. The first two rely on preliminary Kohn-Sham calculations using a standard generalized gradient approximation (GGA) exchange-correlation functional and the results illustrate the benefit of describing the dominant Hartree component of the shift exactly. A uniform electron gas analysis is used to eliminate the need for these preliminary Kohn-Sham calculations, leading to a potential with an unconventional form that yields encouraging results, providing strong motivation for further research in DEKS theory.

Energy dependence of the spin excitation anisotropy in uniaxial-strained BaFe 1.9Ni 0.1As 2

DOE PAGES

Song, Yu; Lu, Xingye; Abernathy, Douglas L.; ...

2015-11-06

In this study, we use inelastic neutron scattering to study the temperature and energy dependence of the spin excitation anisotropy in uniaxial-strained electron-doped iron pnictide BaFe 1.9Ni 0.1As 2 near optimal superconductivity (T c = 20K). Our work has been motivated by the observation of in-plane resistivity anisotropy in the paramagnetic tetragonal phase of electron-underdoped iron pnictides under uniaxial pressure, which has been attributed to a spin-driven Ising-nematic state or orbital ordering. Here we show that the spin excitation anisotropy, a signature of the spin-driven Ising-nematic phase, exists for energies below 60 meV in uniaxial-strained BaFe 1.9Ni 0.1As 2. Sincemore » this energy scale is considerably larger than the energy splitting of the d xz and d yz bands of uniaxial-strained Ba(Fe 1–xCox) 2As 2 near optimal superconductivity, spin Ising-nematic correlations are likely the driving force for the resistivity anisotropy and associated electronic nematic correlations.« less

Correlation of electron and proton irradiation-induced damage in InP solar cells

NASA Technical Reports Server (NTRS)

Walters, Robert J.; Summers, Geoffrey P.; Messenger, Scott R.; Burke, Edward A.

1996-01-01

The measured degradation of epitaxial shallow homojunction n(+)/p InP solar cells under 1 MeV electron irradiation is correlated with that measured under 3 MeV proton irradiation based on 'displacement damage dose'. The measured data is analyzed as a function of displacement damage dose from which an electron to proton dose equivalency ratio is determined which enables the electron and proton degradation data to be described by a single degradation curve. It is discussed how this single curve can be used to predict the cell degradation under irradiation by any particle energy. The degradation curve is used to compare the radiation response of InP and GaAs/Ge cells on an absolute damage energy scale. The comparison shows InP to be inherently more resistant to displacement damage deposition than the GaAs/Ge.

The scattering of low energy positrons by helium

NASA Technical Reports Server (NTRS)

Humberston, J. W.

1973-01-01

Kohn's variational method is used to calculate the positron-helium scattering length and low energy S-wave phase shifts for a quite realistic Hylleraas type of helium function containing an electron-electron correlation term. The zero energy wavefunction is used to calculate the value of the annihilation rate parameter Z sub eff. All the results are significantly different from those for Drachman's helium model B, but are in better agreement with the available experimental data.

Simultaneous analytical optimization of variational parameters in Gaussian-type functions with full configuration interaction of multicomponent molecular orbital method by elimination of translational and rotational motions: application to isotopomers of the hydrogen molecule.

PubMed

Ishimoto, Takayoshi; Tachikawa, Masanori; Nagashima, Umpei

2008-04-28

We have extended the multicomponent molecular orbital (MCMO) method to the full-configuration interaction (full-CI) fully variational molecular orbital method by elimination of translational and rotational motion components from total Hamiltonian. In the MCMO scheme, the quantum effects of protons and deuterons as well as electrons can be directly taken into account. All variational parameters in the full-CI scheme, i.e., exponents and centers (alpha and R) in the Gaussian-type function (GTF) basis set as well as the CI coefficients, are simultaneously optimized by using their analytical gradients. The total energy of the H(2) molecule calculated using the electronic [6s3p2d1f] and nuclear [1s1p1d1f] GTFs is -1.161 726 hartree, which can be compared to the energy of -1.164 025 hartree reported using a 512 term-explicitly correlated GTF calculation. Although the d- and f-type nuclear GTFs contribute to the improvement of energy convergence, the convergence of electron-nucleus correlation energy is slower than that of electron-electron one. The nuclear wave functions are delocalized due to the electron-nucleus correlation effect compared to the result of Hartree-Fock level of MCMO method. In addition, the average internuclear distances of all diatomic molecules are within 0.001 A of the previously reported experimental results. The dipole moment of the HD molecule estimated by our method is 8.4 x 10(-4) D, which is in excellent agreement with the experimental result of (8-10) x 10(-4) D.

Two-body Schrödinger wave functions in a plane-wave basis via separation of dimensions

NASA Astrophysics Data System (ADS)

Jerke, Jonathan; Poirier, Bill

2018-03-01

Using a combination of ideas, the ground and several excited electronic states of the helium atom and the hydrogen molecule are computed to chemical accuracy—i.e., to within 1-2 mhartree or better. The basic strategy is very different from the standard electronic structure approach in that the full two-electron six-dimensional (6D) problem is tackled directly, rather than starting from a single-electron Hartree-Fock approximation. Electron correlation is thus treated exactly, even though computational requirements remain modest. The method also allows for exact wave functions to be computed, as well as energy levels. From the full-dimensional 6D wave functions computed here, radial distribution functions and radial correlation functions are extracted—as well as a 2D probability density function exhibiting antisymmetry for a single Cartesian component. These calculations support a more recent interpretation of Hund's rule, which states that the lower energy of the higher spin-multiplicity states is actually due to reduced screening, rather than reduced electron-electron repulsion. Prospects for larger systems and/or electron dynamics applications appear promising.

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

Sun, Jianwei; Yang, Zenghui; Peng, Haowei

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin densitymore » approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.« less

Two-body Schrödinger wave functions in a plane-wave basis via separation of dimensions.

PubMed

Jerke, Jonathan; Poirier, Bill

2018-03-14

Using a combination of ideas, the ground and several excited electronic states of the helium atom and the hydrogen molecule are computed to chemical accuracy-i.e., to within 1-2 mhartree or better. The basic strategy is very different from the standard electronic structure approach in that the full two-electron six-dimensional (6D) problem is tackled directly, rather than starting from a single-electron Hartree-Fock approximation. Electron correlation is thus treated exactly, even though computational requirements remain modest. The method also allows for exact wave functions to be computed, as well as energy levels. From the full-dimensional 6D wave functions computed here, radial distribution functions and radial correlation functions are extracted-as well as a 2D probability density function exhibiting antisymmetry for a single Cartesian component. These calculations support a more recent interpretation of Hund's rule, which states that the lower energy of the higher spin-multiplicity states is actually due to reduced screening, rather than reduced electron-electron repulsion. Prospects for larger systems and/or electron dynamics applications appear promising.

Uniform electron gases. III. Low-density gases on three-dimensional spheres.

PubMed

Agboola, Davids; Knol, Anneke L; Gill, Peter M W; Loos, Pierre-François

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGF centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids - the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) - and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.

Means and method for calibrating a photon detector utilizing electron-photon coincidence

NASA Technical Reports Server (NTRS)

Srivastava, S. K. (Inventor)

1984-01-01

An arrangement for calibrating a photon detector particularly applicable for the ultraviolet and vacuum ultraviolet regions is based on electron photon coincidence utilizing crossed electron beam atom beam collisions. Atoms are excited by electrons which lose a known amount of energy and scatter with a known remaining energy, while the excited atoms emit photons of known radiation. Electrons of the known remaining energy are separated from other electrons and are counted. Photons emitted in a direction related to the particular direction of scattered electrons are detected to serve as a standard. Each of the electrons is used to initiate the measurements of a time interval which terminates with the arrival of a photon exciting the photon detector. Only the number of time intervals related to the coincidence correlation and of electrons scattered in the particular direction with the known remaining energy and photons of a particular radiation level emitted due to the collisions of such scattered electrons are counted. The detector calibration is related to the number of counted electrons and photons.

Correlation between morphology, electron band structure, and resistivity of Pb atomic chains on the Si(5 5 3)-Au surface

NASA Astrophysics Data System (ADS)

Jałochowski, M.; Kwapiński, T.; Łukasik, P.; Nita, P.; Kopciuszyński, M.

2016-07-01

Structural and electron transport properties of multiple Pb atomic chains fabricated on the Si(5 5 3)-Au surface are investigated using scanning tunneling spectroscopy, reflection high electron energy diffraction, angular resolved photoemission electron spectroscopy and in situ electrical resistance. The study shows that Pb atomic chains growth modulates the electron band structure of pristine Si(5 5 3)-Au surface and hence changes its sheet resistivity. Strong correlation between chains morphology, electron band structure and electron transport properties is found. To explain experimental findings a theoretical tight-binding model of multiple atomic chains interacting on effective substrate is proposed.

Spatial distribution of fluorescent light emitted from neon and nitrogen excited by low energy electron beams

NASA Astrophysics Data System (ADS)

Morozov, A.; Krücken, R.; Ulrich, A.; Wieser, J.

2006-11-01

Side-view intensity profiles of fluorescent light were measured for neon and nitrogen excited with 12keV electron beams at gas pressures from 250to1400hPa. The intensity profiles were compared with theoretical profiles calculated using the CASINO program which performs Monte Carlo simulations of electron scattering. It was assumed that the spatial distribution of fluorescent intensity is directly proportional to the spatial distribution of energy loss by primary electrons. The comparison shows good correlation of experimental data and the results of numeric simulations.

Inclusion of electron correlation for the target wave function in low- to intermediate-energy e-N2 scattering

NASA Technical Reports Server (NTRS)

Weatherford, C. A.; Brown, F. B.; Temkin, A.

1987-01-01

In a recent calculation, an exact exchange method was developed for use in the partial-differential-equation approach to electron-molecule scattering and was applied to e-N2 scattering in the fixed-nuclei approximation with an adiabatic polarization potential at low energies (0-10 eV). Integrated elastic cross sections were calculated and found to be lower than experiment at energies both below and above the Pi(g) resonance. It was speculated at that time that improved experimental agreement could be obtained if a correlated target representation were used in place of the uncorrelated one. The present paper implements this suggestion and demonstrates the improved agreement. These calculations are also extended to higher energies (0-30 eV) so asd to include the Sigma(u) resonance. Some discrepancies among the experiments and between experiment and the various calculations at very low energy are noted.

Solar Wind 0.1-1 keV Electrons in the Corotating Interaction Regions

NASA Astrophysics Data System (ADS)

Wang, L.; Tao, J.; Li, G.; Wimmer-Schweingruber, R. F.; Jian, L. K.; He, J.; Tu, C.; Tian, H.; Bale, S. D.

2017-12-01

Here we present a statistical study of the 0.1-1 keV suprathermal electrons in the undisturbed and compressed slow/fast solar wind, for the 71 corotating interaction regions (CIRs) with good measurements from the WIND 3DP and MFI instruments from 1995 to 1997. For each of these CIRs, we separate the strahl and halo electrons based on their different behaviors in pitch angle distributions in the undisturbed and compressed solar wind. We fit both the strahl and halo energy spectra to a kappa function with an index κ index and effective temperature Teff, and calculate the pitch-angle width at half-maximum (PAHM) of the strahl population. We also integrate the electron measurements between 0.1 and 1.0 keV to obtain the number density n and average energy Eavg for the strahl and halo populations. We find that for both the strahl and halo populations within and around these CIRs, the fitted κ index strongly correlates with Teff, similar to the quiet-time solar wind (Tao et al., ApJ, 2016). The number density of both the strahl and halo shows a strong positive correlation with the electron core temperature. The strahl number density ns is correlated with the magnitude of interplanetary magnetic field, and the strahl PAHM width is anti-correlated with the solar wind speed. These results suggest that the origin of strahl electrons from the solar corona is likely related to the electron core temperature and magnetic field strength, while the production of halo electrons in the interplanetary medium could depend on the solar wind velocity.

Density-functional theory based on the electron distribution on the energy coordinate

NASA Astrophysics Data System (ADS)

Takahashi, Hideaki

2018-03-01

We developed an electronic density functional theory utilizing a novel electron distribution n(ɛ) as a basic variable to compute ground state energy of a system. n(ɛ) is obtained by projecting the electron density n({\\boldsymbol{r}}) defined on the space coordinate {\\boldsymbol{r}} onto the energy coordinate ɛ specified with the external potential {\\upsilon }ext}({\\boldsymbol{r}}) of interest. It was demonstrated that the Kohn-Sham equation can also be formulated with the exchange-correlation functional E xc[n(ɛ)] that employs the density n(ɛ) as an argument. It turned out an exchange functional proposed in our preliminary development suffices to describe properly the potential energies of several types of chemical bonds with comparable accuracies to the corresponding functional based on local density approximation. As a remarkable feature of the distribution n(ɛ) it inherently involves the spatially non-local information of the exchange hole at the bond dissociation limit in contrast to conventional approximate functionals. By taking advantage of this property we also developed a prototype of the static correlation functional E sc including no empirical parameters, which showed marked improvements in describing the dissociations of covalent bonds in {{{H}}}2,{{{C}}}2{{{H}}}4 and {CH}}4 molecules.

Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole

NASA Astrophysics Data System (ADS)

Li, Shaohong L.; Truhlar, Donald G.

2017-02-01

Analytic potential energy surfaces (PESs) and state couplings of the ground and two lowest singlet excited states of thioanisole (C6H5SCH3) are constructed in a diabatic representation based on electronic structure calculations including dynamic correlation. They cover all 42 internal degrees of freedom and a wide range of geometries including the Franck-Condon region and the reaction valley along the breaking S-CH3 bond with the full ranges of the torsion angles. The parameters in the PESs and couplings are fitted to the results of smooth diabatic electronic structure calculations including dynamic electron correlation by the extended multi-configurational quasi-degenerate perturbation theory method for the adiabatic state energies followed by diabatization by the fourfold way. The fit is accomplished by the anchor points reactive potential method with two reactive coordinates and 40 nonreactive degrees of freedom, where the anchor-point force fields are obtained with a locally modified version of the QuickFF package. The PESs and couplings are suitable for study of the topography of the trilayer potential energy landscape and for electronically nonadiabatic molecular dynamics simulations of the photodissociation of the S-CH3 bond.

Particle precipitation prior to large earthquakes of both the Sumatra and Philippine Regions: A statistical analysis

NASA Astrophysics Data System (ADS)

Fidani, Cristiano

2015-12-01

A study of statistical correlation between low L-shell electrons precipitating into the atmosphere and strong earthquakes is presented. More than 11 years of the Medium Energy Protons Electrons Detector data from the NOAA-15 Sun-synchronous polar orbiting satellite were analysed. Electron fluxes were analysed using a set of adiabatic coordinates. From this, significant electron counting rate fluctuations were evidenced during geomagnetic quiet periods. Electron counting rates were compared to earthquakes by defining a seismic event L-shell obtained radially projecting the epicentre geographical positions to a given altitude towards the zenith. Counting rates were grouped in every satellite semi-orbit together with strong seismic events and these were chosen with the L-shell coordinates close to each other. NOAA-15 electron data from July 1998 to December 2011 were compared for nearly 1800 earthquakes with magnitudes larger than or equal to 6, occurring worldwide. When considering 30-100 keV precipitating electrons detected by the vertical NOAA-15 telescope and earthquake epicentre projections at altitudes greater that 1300 km, a significant correlation appeared where a 2-3 h electron precipitation was detected prior to large events in the Sumatra and Philippine Regions. This was in physical agreement with different correlation times obtained from past studies that considered particles with greater energies. The Discussion below of satellite orbits and detectors is useful for future satellite missions for earthquake mitigation.

Effective Hamiltonians for correlated narrow energy band systems and magnetic insulators: Role of spin-orbit interactions in metal-insulator transitions and magnetic phase transitions

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

Chakraborty, Subrata; Vijay, Amrendra, E-mail: avijay@iitm.ac.in

Using a second-quantized many-electron Hamiltonian, we obtain (a) an effective Hamiltonian suitable for materials whose electronic properties are governed by a set of strongly correlated bands in a narrow energy range and (b) an effective spin-only Hamiltonian for magnetic materials. The present Hamiltonians faithfully include phonon and spin-related interactions as well as the external fields to study the electromagnetic response properties of complex materials and they, in appropriate limits, reduce to the model Hamiltonians due to Hubbard and Heisenberg. With the Hamiltonian for narrow-band strongly correlated materials, we show that the spin-orbit interaction provides a mechanism for metal-insulator transition, whichmore » is distinct from the Mott-Hubbard (driven by the electron correlation) and the Anderson mechanism (driven by the disorder). Next, with the spin-only Hamiltonian, we demonstrate the spin-orbit interaction to be a reason for the existence of antiferromagnetic phase in materials which are characterized by a positive isotropic spin-exchange energy. This is distinct from the Néel-VanVleck-Anderson paradigm which posits a negative spin-exchange for the existence of antiferromagnetism. We also find that the Néel temperature increases as the absolute value of the spin-orbit coupling increases.« less

Exploring the boundary between aromatic and olefinic character: Bad news for second-order perturbation theory and density functional schemes

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

Sulzbach, H.M.; Schaefer, H.F. III; Klopper, W.

1996-04-10

The question whether [10]annulene prefers olefinic structures with alternate single and double bonds or aromatic structures like all other small to medium sized uncharged (4n + 2){pi} electron homologs (e.g. benzene, [14]annulene) has been controversial for more than 20 years. Our new results suggest that only the high-order correlated methods will be able to correctly predict the [10]annulene potential energy surface. The UNO-CAS results and the strong oscillation of the MP series show that nondynamical electron correlation is important. Consequently, reliable results can only be expected at the highest correlated levels like CCSD(T) method, which predicts the olefinic twist structuremore » to be lower in energy by 3-7 kcal/mol. This prediction that the twist structure is lower in energy is supported by (a) the MP2-R12 method, which shows that large basis sets favor the olefinic structure relative to the aromatic, and (b) the fact that both structures are about equally affected by nondynamical electron correlation. We conclude that [10]annulene is a system which cannot be described adequately by either second-order Moller-Plesset perturbation theory or density functional methods. 13 refs., 3 tabs.« less

Improving Density Functionals with Quantum Harmonic Oscillators

NASA Astrophysics Data System (ADS)

Tkatchenko, Alexandre

2013-03-01

Density functional theory (DFT) is the most widely used and successful approach for electronic structure calculations. However, one of the pressing challenges for DFT is developing efficient functionals that can accurately capture the omnipresent long-range electron correlations, which determine the structure and stability of many molecules and materials. Here we show that, under certain conditions, the problem of computing the long-range correlation energy of interacting electrons can be mapped to a system of coupled quantum harmonic oscillators (QHOs). The proposed model allows us to synergistically combine concepts from DFT, quantum chemistry, and the widely discussed random-phase approximation for the correlation energy. In the dipole limit, the interaction energy for a system of coupled QHOs can be calculated exactly, thereby leading to an efficient and accurate model for the many-body dispersion energy of complex molecules and materials. The studied examples include intermolecular binding energies, the conformational hierarchy of DNA structures, the geometry and stability of molecular crystals, and supramolecular host-guest complexes (A. Tkatchenko, R. A. DiStasio Jr., R. Car, M. Scheffler, Phys. Rev. Lett. 108, 236402 (2012); R. A. DiStasio Jr., A. von Lilienfeld, A. Tkatchenko, PNAS 109, 14791 (2012); A. Tkatchenko, D. Alfe, K. S. Kim, J. Chem. Theory and Comp. (2012), doi: 10.1021/ct300711r; A. Tkatchenko, A. Ambrosetti, R. A. DiStasio Jr., arXiv:1210.8343v1).

Nonlocal correlations in the orbital selective Mott phase of a one-dimensional multiorbital Hubbard model

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

Li, S.; Kaushal, N.; Wang, Y.

Here, we study nonlocal correlations in a three-orbital Hubbard model defined on an extended one-dimensional chain using determinant quantum Monte Carlo and density matrix renormalization group methods. We focus on a parameter regime with robust Hund's coupling, which produces an orbital selective Mott phase (OSMP) at intermediate values of the Hubbard U, as well as an orbitally ordered ferromagnetic insulating state at stronger coupling. An examination of the orbital- and spin-correlation functions indicates that the orbital ordering occurs before the onset of magnetic correlations in this parameter regime as a function of temperature. In the OSMP, we find that themore » self-energy for the itinerant electrons is momentum dependent, indicating a degree of nonlocal correlations while the localized electrons have largely momentum independent self-energies. These nonlocal correlations also produce relative shifts of the holelike and electronlike bands within our model. The overall momentum dependence of these quantities is strongly suppressed in the orbitally ordered insulating phase.« less

Nonlocal correlations in the orbital selective Mott phase of a one-dimensional multiorbital Hubbard model

DOE PAGES

Li, S.; Kaushal, N.; Wang, Y.; ...

2016-12-12

Here, we study nonlocal correlations in a three-orbital Hubbard model defined on an extended one-dimensional chain using determinant quantum Monte Carlo and density matrix renormalization group methods. We focus on a parameter regime with robust Hund's coupling, which produces an orbital selective Mott phase (OSMP) at intermediate values of the Hubbard U, as well as an orbitally ordered ferromagnetic insulating state at stronger coupling. An examination of the orbital- and spin-correlation functions indicates that the orbital ordering occurs before the onset of magnetic correlations in this parameter regime as a function of temperature. In the OSMP, we find that themore » self-energy for the itinerant electrons is momentum dependent, indicating a degree of nonlocal correlations while the localized electrons have largely momentum independent self-energies. These nonlocal correlations also produce relative shifts of the holelike and electronlike bands within our model. The overall momentum dependence of these quantities is strongly suppressed in the orbitally ordered insulating phase.« less

Frequency distributions and correlations of solar X-ray flare parameters

NASA Technical Reports Server (NTRS)

Crosby, Norma B.; Aschwanden, Markus J.; Dennis, Brian R.

1993-01-01

Frequency distributions of flare parameters are determined from over 12,000 solar flares. The flare duration, the peak counting rate, the peak hard X-ray flux, the total energy in electrons, and the peak energy flux in electrons are among the parameters studied. Linear regression fits, as well as the slopes of the frequency distributions, are used to determine the correlations between these parameters. The relationship between the variations of the frequency distributions and the solar activity cycle is also investigated. Theoretical models for the frequency distribution of flare parameters are dependent on the probability of flaring and the temporal evolution of the flare energy build-up. The results of this study are consistent with stochastic flaring and exponential energy build-up. The average build-up time constant is found to be 0.5 times the mean time between flares.

Immediate estimation of correlation energy for molecular systems from the partial charges on atoms in the molecule

NASA Astrophysics Data System (ADS)

Kristyán, Sándor

1997-11-01

In the author's previous work (Chem. Phys. Lett. 247 (1995) 101 and Chem. Phys. Lett. 256 (1996) 229) a simple quasi-linear relationship was introduced between the number of electrons, N, participating in any molecular system and the correlation energy: -0.035 ( N - 1) > Ecorr[hartree] > - 0.045( N -1). This relationship was developed to estimate more accurately correlation energy immediately in ab initio calculations by using the partial charges of atoms in the molecule, easily obtained after Hartree-Fock self-consistent field (HF-SCF) calculations. The method is compared to the well-known B3LYP, MP2, CCSD and G2M methods. Correlation energy estimations for negatively (-1) charged atomic ions are also reported.

Importance of σ Bonding Electrons for the Accurate Description of Electron Correlation in Graphene.

PubMed

Zheng, Huihuo; Gan, Yu; Abbamonte, Peter; Wagner, Lucas K

2017-10-20

Electron correlation in graphene is unique because of the interplay between the Dirac cone dispersion of π electrons and long-range Coulomb interaction. Because of the zero density of states at Fermi level, the random phase approximation predicts no metallic screening at long distance and low energy, so one might expect that graphene should be a poorly screened system. However, empirically graphene is a weakly interacting semimetal, which leads to the question of how electron correlations take place in graphene at different length scales. We address this question by computing the equal time and dynamic structure factor S(q) and S(q,ω) of freestanding graphene using ab initio fixed-node diffusion Monte Carlo simulations and the random phase approximation. We find that the σ electrons contribute strongly to S(q,ω) for relevant experimental values of ω even at distances up to around 80 Å. These findings illustrate how the emergent physics from underlying Coulomb interactions results in the observed weakly correlated semimetal.

Gamma-ray momentum reconstruction from Compton electron trajectories by filtered back-projection

DOE PAGES

Haefner, A.; Gunter, D.; Plimley, B.; ...

2014-11-03

Gamma-ray imaging utilizing Compton scattering has traditionally relied on measuring coincident gamma-ray interactions to map directional information of the source distribution. This coincidence requirement makes it an inherently inefficient process. We present an approach to gamma-ray reconstruction from Compton scattering that requires only a single electron tracking detector, thus removing the coincidence requirement. From the Compton scattered electron momentum distribution, our algorithm analytically computes the incident photon's correlated direction and energy distributions. Because this method maps the source energy and location, it is useful in applications, where prior information about the source distribution is unknown. We demonstrate this method withmore » electron tracks measured in a scientific Si charge coupled device. While this method was demonstrated with electron tracks in a Si-based detector, it is applicable to any detector that can measure electron direction and energy, or equivalently the electron momentum. For example, it can increase the sensitivity to obtain energy and direction in gas-based systems that suffer from limited efficiency.« less

Fundamental edge broadening effects during focused electron beam induced nanosynthesis

DOE PAGES

Schmied, Roland; Fowlkes, Jason Davidson; Winkler, Robert; ...

2015-02-16

In this study, we explore lateral broadening effects of 3D structures fabricated through focused electron beam induced deposition using MeCpPt(IV)Me 3 precursor. In particular, the scaling behavior of proximity effects as a function of the primary electron energy and the deposit height is investigated through experiments and validated through simulations. Correlated Kelvin force microscopy and conductive atomic force microscopy measurements identified conductive and non-conductive proximity regions. It was determined that the highest primary electron energies enable the highest edge sharpness while lower energies contain a complex convolution of broadening effects. In addition, it is demonstrated that intermediate energies lead tomore » even more complex proximity effects that significantly reduce lateral edge sharpness and thus should be avoided if desiring high lateral resolution.« less

MN15-L: A New Local Exchange-Correlation Functional for Kohn-Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids.

PubMed

Yu, Haoyu S; He, Xiao; Truhlar, Donald G

2016-03-08

Kohn-Sham density functional theory is widely used for applications of electronic structure theory in chemistry, materials science, and condensed-matter physics, but the accuracy depends on the quality of the exchange-correlation functional. Here, we present a new local exchange-correlation functional called MN15-L that predicts accurate results for a broad range of molecular and solid-state properties including main-group bond energies, transition metal bond energies, reaction barrier heights, noncovalent interactions, atomic excitation energies, ionization potentials, electron affinities, total atomic energies, hydrocarbon thermochemistry, and lattice constants of solids. The MN15-L functional has the same mathematical form as a previous meta-nonseparable gradient approximation exchange-correlation functional, MN12-L, but it is improved because we optimized it against a larger database, designated 2015A, and included smoothness restraints; the optimization has a much better representation of transition metals. The mean unsigned error on 422 chemical energies is 2.32 kcal/mol, which is the best among all tested functionals, with or without nonlocal exchange. The MN15-L functional also provides good results for test sets that are outside the training set. A key issue is that the functional is local (no nonlocal exchange or nonlocal correlation), which makes it relatively economical for treating large and complex systems and solids. Another key advantage is that medium-range correlation energy is built in so that one does not need to add damped dispersion by molecular mechanics in order to predict accurate noncovalent binding energies. We believe that the MN15-L functional should be useful for a wide variety of applications in chemistry, physics, materials science, and molecular biology.

Scaling Laws of the Two-Electron Sum-Energy Spectrum in Strong-Field Double Ionization.

PubMed

Ye, Difa; Li, Min; Fu, Libin; Liu, Jie; Gong, Qihuang; Liu, Yunquan; Ullrich, J

2015-09-18

The sum-energy spectrum of two correlated electrons emitted in nonsequential strong-field double ionization (SFDI) of Ar was studied for intensities of 0.3 to 2×10^{14} W/cm^{2}. We find the mean sum energy, the maximum of the distributions as well as the high-energy tail of the scaled (to the ponderomotive energy) spectra increase with decreasing intensity below the recollision threshold (BRT). At higher intensities the spectra collapse into a single distribution. This behavior can be well explained within a semiclassical model providing clear evidence of the importance of multiple recollisions in the BRT regime. Here, ultrafast thermalization between both electrons is found occurring within three optical cycles only and leaving its clear footprint in the sum-energy spectra.

Correlated Optical Spectroscopy and Transmission Electron Microscopy of Individual Hollow Nanoparticles and their Dimers

PubMed Central

Yang, Linglu; Yan, Bo; Reinhard, Björn M.

2009-01-01

The optical spectra of individual Ag-Au alloy hollow particles were correlated with the particles’ structures obtained by transmission electron microscopy (TEM). The TEM provided direct experimental access to the dimension of the cavity, thickness of the metal shell, and the interparticle distance of hollow particle dimers with high spatial resolution. The analysis of correlated spectral and structural information enabled the quantification of the influence of the core-shell structure on the resonance energy, plasmon lifetime, and plasmon coupling efficiency. Electron beam exposure during TEM inspection was observed to affect plasmon wavelength and lifetime, making optical inspection prior to structural characterization mandatory. PMID:19768108

Correlational and thermodynamic properties of finite-temperature electron liquids in the hypernetted-chain approximation.

PubMed

Tanaka, Shigenori

2016-12-07

Correlational and thermodynamic properties of homogeneous electron liquids at finite temperatures are theoretically analyzed in terms of dielectric response formalism with the hypernetted-chain (HNC) approximation and its modified version. The static structure factor and the local-field correction to describe the strong Coulomb-coupling effects beyond the random-phase approximation are self-consistently calculated through solution to integral equations in the paramagnetic (spin unpolarized) and ferromagnetic (spin polarized) states. In the ground state with the normalized temperature θ=0, the present HNC scheme well reproduces the exchange-correlation energies obtained by quantum Monte Carlo (QMC) simulations over the whole fluid phase (the coupling constant r s ≤100), i.e., within 1% and 2% deviations from putative best QMC values in the paramagnetic and ferromagnetic states, respectively. As compared with earlier studies based on the Singwi-Tosi-Land-Sjölander and modified convolution approximations, some improvements on the correlation energies and the correlation functions including the compressibility sum rule are found in the intermediate to strong coupling regimes. When applied to the electron fluids at intermediate Fermi degeneracies (θ≈1), the static structure factors calculated in the HNC scheme show good agreements with the results obtained by the path integral Monte Carlo (PIMC) simulation, while a small negative region in the radial distribution function is observed near the origin, which may be associated with a slight overestimation for the exchange-correlation hole in the HNC approximation. The interaction energies are calculated for various combinations of density and temperature parameters ranging from strong to weak degeneracy and from weak to strong coupling, and the HNC values are then parametrized as functions of r s and θ. The HNC exchange-correlation free energies obtained through the coupling-constant integration show reasonable agreements with earlier results including the PIMC-based fitting over the whole fluid region at finite degeneracies in the paramagnetic state. In contrast, a systematic difference between the HNC and PIMC results is observed in the ferromagnetic state, which suggests a necessity of further studies on the exchange-correlation free energies from both aspects of analytical theory and simulation.

Algorithms for calculating mass-velocity and Darwin relativistic corrections with n-electron explicitly correlated Gaussians with shifted centers

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

Stanke, Monika, E-mail: monika@fizyka.umk.pl; Palikot, Ewa, E-mail: epalikot@doktorant.umk.pl; Adamowicz, Ludwik, E-mail: ludwik@email.arizona.edu

2016-05-07

Algorithms for calculating the leading mass-velocity (MV) and Darwin (D) relativistic corrections are derived for electronic wave functions expanded in terms of n-electron explicitly correlated Gaussian functions with shifted centers and without pre-exponential angular factors. The algorithms are implemented and tested in calculations of MV and D corrections for several points on the ground-state potential energy curves of the H{sub 2} and LiH molecules. The algorithms are general and can be applied in calculations of systems with an arbitrary number of electrons.

Accuracy of electron densities obtained via Koopmans-compliant hybrid functionals

NASA Astrophysics Data System (ADS)

Elmaslmane, A. R.; Wetherell, J.; Hodgson, M. J. P.; McKenna, K. P.; Godby, R. W.

2018-04-01

We evaluate the accuracy of electron densities and quasiparticle energy gaps given by hybrid functionals by directly comparing these to the exact quantities obtained from solving the many-electron Schrödinger equation. We determine the admixture of Hartree-Fock exchange to approximate exchange-correlation in our hybrid functional via one of several physically justified constraints, including the generalized Koopmans' theorem. We find that hybrid functionals yield strikingly accurate electron densities and gaps in both exchange-dominated and correlated systems. We also discuss the role of the screened Fock operator in the success of hybrid functionals.

Inelastic cross sections for low-energy electrons in liquid water: exchange and correlation effects.

PubMed

Emfietzoglou, Dimitris; Kyriakou, Ioanna; Garcia-Molina, Rafael; Abril, Isabel; Nikjoo, Hooshang

2013-11-01

Low-energy electrons play a prominent role in radiation therapy and biology as they are the largest contributor to the absorbed dose. However, no tractable theory exists to describe the interaction of low-energy electrons with condensed media. This article presents a new approach to include exchange and correlation (XC) effects in inelastic electron scattering at low energies (below ∼10 keV) in the context of the dielectric theory. Specifically, an optical-data model of the dielectric response function of liquid water is developed that goes beyond the random phase approximation (RPA) by accounting for XC effects using the concept of the many-body local-field correction (LFC). It is shown that the experimental energy-loss-function of liquid water can be reproduced by including into the RPA dispersion relations XC effects (up to second order) calculated in the time-dependent local-density approximation with the addition of phonon-induced broadening in N. D. Mermin's relaxation-time approximation. Additional XC effects related to the incident and/or struck electrons are included by means of the vertex correction calculated by a modified Hubbard formula for the exchange-only LFC. Within the first Born approximation, the present XC corrections cause a significantly larger reduction (∼10-50%) to the inelastic cross section compared to the commonly used Mott and Ochkur approximations, while also yielding much better agreement with the recent experimental data for amorphous ice. The current work offers a manageable, yet rigorous, approach for including non-Born effects in the calculation of inelastic cross sections for low-energy electrons in liquid water, which due to its generality, can be easily extended to other condensed media.

Coupled electronic and atomic effects on defect evolution in silicon carbide under ion irradiation

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

Zhang, Yanwen; Xue, Haizhou; Zarkadoula, Eva

Understanding energy dissipation processes in electronic/atomic subsystems and subsequent non-equilibrium defect evolution is a long-standing challenge in materials science. In the intermediate energy regime, energetic particles simultaneously deposit a significant amount of energy to both electronic and atomic subsystems of silicon carbide (SiC). Here we show that defect evolution in SiC closely depends on the electronic-to-nuclear energy loss ratio (S e/S n), nuclear stopping powers ( dE/dx nucl), electronic stopping powers ( dE/dx ele), and the temporal and spatial coupling of electronic and atomic subsystem for energy dissipation. The integrated experiments and simulations reveal that: (1) increasing S e/S nmore » slows damage accumulation; (2) the transient temperatures during the ionization-induced thermal spike increase with dE/dx ele, which causes efficient damage annealing along the ion trajectory; and (3) for more condensed displacement damage within the thermal spike, damage production is suppressed due to the coupled electronic and atomic dynamics. Ionization effects are expected to be more significant in materials with covalent/ionic bonding involving predominantly well-localized electrons. Here, insights into the complex electronic and atomic correlations may pave the way to better control and predict SiC response to extreme energy deposition« less

Method for Trace Oxygen Detection

NASA Technical Reports Server (NTRS)

Man, Kim Fung (Inventor); Boumsellek, Said (Inventor); Chutjian, Ara (Inventor)

1997-01-01

Trace levels of molecular oxygen are measured by introducing a gas containing the molecular oxygen into a target zone, and impacting the molecular oxygen in the target zone with electrons at the O(-) resonant energy level for dissociative electron attachment to produce O(-) ions. Preferably, the electrons have an energy of about 4 to about 10 eV. The amount of O(-) ions produced is measured, and is correlated with the molecular oxygen content in the target zone. The technique is effective for measuring levels of oxygen below 50 ppb. and even less than 1 ppb. The amount of O(-) can be measured in a quadrupole mass analyzer. Best results are obtained when the electrons have an energy of about 6 to about 8 eV. and preferably about 6.8 eV. The method can be used for other species by selecting the appropriate electron energy level.

Qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes: an approach to effectively assign their absolute configuration.

PubMed

Zheng, Shuang; Chang, Ming-Liang; Zhou, Jing; Fu, Jing-Wei; Zhang, Qing-Wei; Li, Shao-Yong; Qiao, Wei; Liu, Jun-Min

2014-06-03

For all microhelices on aromatic rings of inherently chiral calix[4]arene, an expression was derived from one approximation and one hypothesis on the basis of the electron-on-a-helix model of Tinoco and Woody as follows: 1/E = μ(H - KΔα2), where μ = 1 for the right-handed microhelix and μ = -1 for the left-handed microhelix; and H and K are constant and greater than zero. The expression correlates microhelical electronic energy (E) with the atom polarizability difference (Δα) on both microhelix ends, which intuitively and clearly shows the impact of helical substituent polarizability on helical electronic energy. The case analysis almost entirely proves that the qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes with the expression is scientific and can be used to effectively assign their absolute configuration.

ON THE NONTHERMAL κ-DISTRIBUTED ELECTRONS IN PLANETARY NEBULAE AND H ii REGIONS: THE κ INDEX AND ITS CORRELATIONS WITH OTHER NEBULAR PROPERTIES

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

Zhang, Yong; Zhang, Bing; Liu, Xiao-Wei, E-mail: zhangy96@hku.hk

2016-01-20

Recently, a suspicion arose that the free electrons in planetary nebulae (PNs) and H ii regions might have nonthermal energy distributions. In this scenario, a κ index is introduced to characterize the electron energy distributions, with smaller κ values indicating larger deviations from Maxwell–Boltzmann distributions. Assuming that this is the case, we determine the κ values for a sample of PNs and H ii regions by comparing the intensities of [O iii] collisionally excited lines and the hydrogen Balmer jump. We find the average κ indices of PNs and H ii regions to be 27 and 32, respectively. Correlations betweenmore » the resultant κ values and various physical properties of the nebulae are examined to explore the potential origin of nonthermal electrons in photoionized gaseous nebulae. However, no positive result is obtained. Thus, the current analysis does not lend support to the idea that κ-distributed electrons are present in PNs and H ii regions.« less

Strongly-correlated crystal-field approach to heavy-fermion compounds and to 3d oxides

NASA Astrophysics Data System (ADS)

Radwanski, Ryszard; Ropka, Zofia

2005-03-01

The description of electronic and magnetic properties of real compounds like LaMnO3, LaCoO3, Na2V3O7, FeO, NdAl2 and ErNi5 as well as heavy-fermion superconductor UPd2Al3 and heavy-fermion metal YbRh2Si2, both zero-temperature ground state properties and thermodynamics, will be presented pointing out the existence of a discrete atomic-like low-energy, in the meV scale, electronic structure. This low-energy many-electron discrete atomic-like electronic structure is governed by very strong electron correlations, predominantly on-site, by the intra-atomic spin-orbit coupling and by details of the local surrounding (crystal-field interactions), but later is modified by inter-site interactions. Our studies indicate that there is the highest time to ``unquench'' the orbital moment in solid state physics in description of 3d-/4f-/5f-atom containing compounds and that heavy-fermion phenomena are of the relativistic origin.

Acceleration of electrons in strong beam-plasma interactions

NASA Technical Reports Server (NTRS)

Wilhelm, K.; Bernstein, W.; Kellogg, P. J.; Whalen, B. A.

1984-01-01

The effects of strong beam-plasma interactions on the electron population of the upper atmosphere have been investigated in an electron acceleration experiment performed with a sounding rocket. The rocket carried the Several Complex Experiments (SCEX) payload which included an electron accelerator, three disposable 'throwaway' detectors (TADs), and a stepped electron energy analyzer. The payload was launched in an auroral arc over the rocket at altitudes of 157 and 178 km, respectively. The performance characteristics of the instruments are discussed in detail. The data are combined with the results of laboratory measurements and show that electrons with energies of at least two and probably four times the injection energy of 2 keV were observed during strong beam-plasma interaction events. The interaction events occurred at pitch angles of 54 and 126 degrees. On the basis of the data it is proposed that the superenergization of the electrons is correlated with the length of the beam-plasma interaction region.

Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Constantin, Lucian A; Sun, Jianwei; Csonka, Gábor I

2009-04-14

Some fundamental issues in ground-state density functional theory are discussed without equations: (1) The standard Hohenberg-Kohn and Kohn-Sham theorems were proven for a Hamiltonian that is not quite exact for real atoms, molecules, and solids. (2) The density functional for the exchange-correlation energy, which must be approximated, arises from the tendency of electrons to avoid one another as they move through the electron density. (3) In the absence of a magnetic field, either spin densities or total electron density can be used, although the former choice is better for approximations. (4) "Spin contamination" of the determinant of Kohn-Sham orbitals for an open-shell system is not wrong but right. (5) Only to the extent that symmetries of the interacting wave function are reflected in the spin densities should those symmetries be respected by the Kohn-Sham noninteracting or determinantal wave function. Functionals below the highest level of approximations should however sometimes break even those symmetries, for good physical reasons. (6) Simple and commonly used semilocal (lower-level) approximations for the exchange-correlation energy as a functional of the density can be accurate for closed systems near equilibrium and yet fail for open systems of fluctuating electron number. (7) The exact Kohn-Sham noninteracting state need not be a single determinant, but common approximations can fail when it is not. (8) Over an open system of fluctuating electron number, connected to another such system by stretched bonds, semilocal approximations make the exchange-correlation energy and hole-density sum rule too negative. (9) The gap in the exact Kohn-Sham band structure of a crystal underestimates the real fundamental gap but may approximate the first exciton energy in the large-gap limit. (10) Density functional theory is not really a mean-field theory, although it looks like one. The exact functional includes strong correlation, and semilocal approximations often overestimate the strength of static correlation through their semilocal exchange contributions. (11) Only under rare conditions can excited states arise directly from a ground-state theory.

Relativistic-Electron-Dominated Solar Flares Observed by Fermi/GBM

NASA Astrophysics Data System (ADS)

Shih, A. Y.; Schwartz, R. A.; Dennis, B. R.

2013-12-01

Up to tens of percent of the energy released in solar flares goes into accelerating electrons above ~10 keV and ions above ~1 MeV, and the impulsive heating of the ambient solar atmosphere by these particles is partially or wholly responsible for the production of hot flare plasmas (up to ~50 MK). Although flares can accelerate electrons to relativistic energies, in even large flares the typical falling power-law energy spectrum means that the plasma is primarily heated by the much larger number of low-energy electrons. However, there have been flares observed where the electron energy spectra have high low-energy cutoffs (well above ~100 keV), which significantly changes the electron energies responsible for heating and modifies the usual conception of energy transport in a flare. A systematic study of a range of relativistic-electron-dominated flares can improve our understanding of the relevant acceleration processes and how they may differ from those in "typical" flares. We search the Fermi/GBM data set for such flares based on the electron-associated X-ray/gamma-ray bremsstrahlung emission, making use of an improved background-subtraction approach to improve the ability to detect weaker flares. We present the fitted parameters for the relativistic-electron spectrum and their evolution over time, and compare against RHESSI observations and other instruments when available. We also discuss these events in the context of previously observed correlations between relativistic-electron acceleration and ion acceleration in flares.

DROPOUT OF DIRECTIONAL ELECTRON INTENSITIES IN LARGE SOLAR ENERGETIC PARTICLE EVENTS

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

Tan, Lun C.; Reames, Donald V., E-mail: ltan@umd.edu

2016-01-10

In the “gradual” solar energetic particle (SEP) event during solar cycle 23 we have observed the dispersionless modulation (“dropout”) in directional intensities of nonrelativistic electrons. The average duration of dropout periods is ∼0.8 hr, which is consistent with the correlation scale of solar wind turbulence. During the dropout period electrons could display scatter-free transport in an intermittent way. Also, we have observed a decrease in the anisotropic index of incident electrons with increasing electron energy (E{sub e}), while the index of scattered/reflected electrons is nearly independent of E{sub e}. We hence perform an observational examination of the correlation between the anisotropicmore » index of low-energy scattered/reflected electrons and the signature of the locally measured solar wind turbulence in the dissipation range, which is responsible for resonant scattering of nonrelativistic electrons. Since during the dropout period the slab turbulence fraction is dominant (0.8 ± 0.1), we pay close attention to the effect of slab fraction on the correlation examined. Our observation is consistent with the simulation result that in the dominance of the slab turbulence component there should exist a dispatched structure of magnetic flux tubes, along which electrons could be transported in a scatter-free manner. Since a similar phenomenon is exhibited in the “impulsive” SEP event, electron dropout should be a transport effect. Therefore, being different from most ion dropout events, which are due to a compact flare source, the dropout of directional electron intensities should be caused by the change of turbulence status in the solar wind.« less

Quantum-chemical investigation of the structures and electronic spectra of the nucleic acid bases at the coupled cluster CC2 level.

PubMed

Fleig, Timo; Knecht, Stefan; Hättig, Christof

2007-06-28

We study the ground-state structures and singlet- and triplet-excited states of the nucleic acid bases by applying the coupled cluster model CC2 in combination with a resolution-of-the-identity approximation for electron interaction integrals. Both basis set effects and the influence of dynamic electron correlation on the molecular structures are elucidated; the latter by comparing CC2 with Hartree-Fock and Møller-Plesset perturbation theory to second order. Furthermore, we investigate basis set and electron correlation effects on the vertical excitation energies and compare our highest-level results with experiment and other theoretical approaches. It is shown that small basis sets are insufficient for obtaining accurate results for excited states of these molecules and that the CC2 approach to dynamic electron correlation is a reliable and efficient tool for electronic structure calculations on medium-sized molecules.

Experimental Evidence of Radiation Reaction in the Collision of a High-Intensity Laser Pulse with a Laser-Wakefield Accelerated Electron Beam

NASA Astrophysics Data System (ADS)

Cole, J. M.; Behm, K. T.; Gerstmayr, E.; Blackburn, T. G.; Wood, J. C.; Baird, C. D.; Duff, M. J.; Harvey, C.; Ilderton, A.; Joglekar, A. S.; Krushelnick, K.; Kuschel, S.; Marklund, M.; McKenna, P.; Murphy, C. D.; Poder, K.; Ridgers, C. P.; Samarin, G. M.; Sarri, G.; Symes, D. R.; Thomas, A. G. R.; Warwick, J.; Zepf, M.; Najmudin, Z.; Mangles, S. P. D.

2018-02-01

The dynamics of energetic particles in strong electromagnetic fields can be heavily influenced by the energy loss arising from the emission of radiation during acceleration, known as radiation reaction. When interacting with a high-energy electron beam, today's lasers are sufficiently intense to explore the transition between the classical and quantum radiation reaction regimes. We present evidence of radiation reaction in the collision of an ultrarelativistic electron beam generated by laser-wakefield acceleration (ɛ >500 MeV ) with an intense laser pulse (a0>10 ). We measure an energy loss in the postcollision electron spectrum that is correlated with the detected signal of hard photons (γ rays), consistent with a quantum description of radiation reaction. The generated γ rays have the highest energies yet reported from an all-optical inverse Compton scattering scheme, with critical energy ɛcrit>30 MeV .

Electronic structures and geometries of the XF{sub 3} (X = Cl, Br, I, At) fluorides

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

Sergentu, Dumitru-Claudiu; CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3; Amaouch, Mohamed

The potential energy surfaces of the group 17 XF{sub 3} (X = Cl, Br, I, At) fluorides have been investigated for the first time with multiconfigurational wave function theory approaches. In agreement with experiment, bent T-shaped C{sub 2v} structures are computed for ClF{sub 3}, BrF{sub 3}, and IF{sub 3}, while we predict that an average D{sub 3h} structure would be experimentally observed for AtF{sub 3}. Electron correlation and scalar relativistic effects strongly reduce the energy difference between the D{sub 3h} geometry and the C{sub 2v} one, along the XF{sub 3} series, and in the X = At case, spin-orbit couplingmore » also slightly reduces this energy difference. AtF{sub 3} is a borderline system where the D{sub 3h} structure becomes a minimum, i.e., the pseudo-Jahn-Teller effect is inhibited since electron correlation and scalar-relativistic effects create small energy barriers leading to the global C{sub 2v} minima, although both types of effects interfere.« less

Ab initio approaches for the determination of heavy element energetics: Ionization energies of trivalent lanthanides (Ln = La-Eu)

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

Peterson, Charles; Penchoff, Deborah A.; Wilson, Angela K., E-mail: wilson@chemistry.msu.edu

2015-11-21

An effective approach for the determination of lanthanide energetics, as demonstrated by application to the third ionization energy (in the gas phase) for the first half of the lanthanide series, has been developed. This approach uses a combination of highly correlated and fully relativistic ab initio methods to accurately describe the electronic structure of heavy elements. Both scalar and fully relativistic methods are used to achieve an approach that is both computationally feasible and accurate. The impact of basis set choice and the number of electrons included in the correlation space has also been examined.

REVIEW ARTICLE: On correlation effects in electron spectroscopies and the GW approximation

NASA Astrophysics Data System (ADS)

Hedin, Lars

1999-10-01

The GW approximation (GWA) extends the well-known Hartree-Fock approximation (HFA) for the self-energy (exchange potential), by replacing the bare Coulomb potential v by the dynamically screened potential W, e.g. Vex = iGv is replaced by icons/Journals/Common/Sigma" ALT="Sigma" ALIGN="TOP"/>GW = iGW. Here G is the one-electron Green's function. The GWA like the HFA is self-consistent, which allows for solutions beyond perturbation theory, like say spin-density waves. In a first approximation, iGW is a sum of a statically screened exchange potential plus a Coulomb hole (equal to the electrostatic energy associated with the charge pushed away around a given electron). The Coulomb hole part is larger in magnitude, but the two parts give comparable contributions to the dispersion of the quasi-particle energy. The GWA can be said to describe an electronic polaron (an electron surrounded by an electronic polarization cloud), which has great similarities to the ordinary polaron (an electron surrounded by a cloud of phonons). The dynamical screening adds new crucial features beyond the HFA. With the GWA not only bandstructures but also spectral functions can be calculated, as well as charge densities, momentum distributions, and total energies. We will discuss the ideas behind the GWA, and generalizations which are necessary to improve on the rather poor GWA satellite structures in the spectral functions. We will further extend the GWA approach to fully describe spectroscopies like photoemission, x-ray absorption, and electron scattering. Finally we will comment on the relation between the GWA and theories for strongly correlated electronic systems. In collecting the material for this review, a number of new results and perspectives became apparent, which have not been published elsewhere.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Karsten, Sven; Bokarev, Sergey I.; Aziz, Saadullah G.; Ivanov, Sergei D.; Kühn, Oliver

2017-06-01

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy.

PubMed

Karsten, Sven; Bokarev, Sergey I; Aziz, Saadullah G; Ivanov, Sergei D; Kühn, Oliver

2017-06-14

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

Particle-hole symmetry in many-body theories of electron correlation

NASA Astrophysics Data System (ADS)

Kats, Daniel; Usvyat, Denis; Manby, Frederick R.

2018-06-01

Second-quantised creation and annihilation operators for fermionic particles anticommute, but the same is true for the creation and annihilation operators for holes. This introduces a symmetry into the quantum theory of fermions that is absent for bosons. In ab initio electronic structure theory, it is common to classify methods by the number of electrons for which the method returns exact results: for example Hartree-Fock theory is exact for one-electron systems, whereas coupled-cluster theory with single and double excitations is exact for two-electron systems. Here, we discuss the generalisation: methods based on approximate wavefunctions that are exact for n-particle systems are also exact for n-hole systems. Novel electron correlation methods that attempt to improve on the coupled-cluster framework sometimes retain this property, and sometimes lose it. Here, we argue for retaining particle-hole symmetry as a desirable design criterion of approximate electron correlation methods. Dispensing with it might lead to loss of n-representability of density matrices, and this in turn can lead to spurious long-range behaviour in the correlation energy.

Electron-mediated relaxation following ultrafast pumping of strongly correlated materials: model evidence of a correlation-tuned crossover between thermal and nonthermal states.

PubMed

Moritz, B; Kemper, A F; Sentef, M; Devereaux, T P; Freericks, J K

2013-08-16

We examine electron-electron mediated relaxation following ultrafast electric field pump excitation of the fermionic degrees of freedom in the Falicov-Kimball model for correlated electrons. The results reveal a dichotomy in the temporal evolution of the system as one tunes through the Mott metal-to-insulator transition: in the metallic regime relaxation can be characterized by evolution toward a steady state well described by Fermi-Dirac statistics with an increased effective temperature; however, in the insulating regime this quasithermal paradigm breaks down with relaxation toward a nonthermal state with a complicated electronic distribution as a function of momentum. We characterize the behavior by studying changes in the energy, photoemission response, and electronic distribution as functions of time. This relaxation may be observable qualitatively on short enough time scales that the electrons behave like an isolated system not in contact with additional degrees of freedom which would act as a thermal bath, especially when using strong driving fields and studying materials whose physics may manifest the effects of correlations.

Using field-particle correlations to study auroral electron acceleration in the LAPD

NASA Astrophysics Data System (ADS)

Schroeder, J. W. R.; Howes, G. G.; Skiff, F.; Kletzing, C. A.; Carter, T. A.; Vincena, S.; Dorfman, S.

2017-10-01

Resonant nonlinear Alfvén wave-particle interactions are believed to contribute to the acceleration of auroral electrons. Experiments in the Large Plasma Device (LAPD) at UCLA have been performed with the goal of providing the first direct measurement of this nonlinear process. Recent progress includes a measurement of linear fluctuations of the electron distribution function associated with the production of inertial Alfvén waves in the LAPD. These linear measurements have been analyzed using the field-particle correlation technique to study the nonlinear transfer of energy between the Alfvén wave electric fields and the electron distribution function. Results of this analysis indicate collisions alter the resonant signature of the field-particle correlation, and implications for resonant Alfvénic electron acceleration in the LAPD are considered. This work was supported by NSF, DOE, and NASA.

Linked-cluster formulation of electron-hole interaction kernel in real-space representation without using unoccupied states.

PubMed

Bayne, Michael G; Scher, Jeremy A; Ellis, Benjamin H; Chakraborty, Arindam

2018-05-21

Electron-hole or quasiparticle representation plays a central role in describing electronic excitations in many-electron systems. For charge-neutral excitation, the electron-hole interaction kernel is the quantity of interest for calculating important excitation properties such as optical gap, optical spectra, electron-hole recombination and electron-hole binding energies. The electron-hole interaction kernel can be formally derived from the density-density correlation function using both Green's function and TDDFT formalism. The accurate determination of the electron-hole interaction kernel remains a significant challenge for precise calculations of optical properties in the GW+BSE formalism. From the TDDFT perspective, the electron-hole interaction kernel has been viewed as a path to systematic development of frequency-dependent exchange-correlation functionals. Traditional approaches, such as MBPT formalism, use unoccupied states (which are defined with respect to Fermi vacuum) to construct the electron-hole interaction kernel. However, the inclusion of unoccupied states has long been recognized as the leading computational bottleneck that limits the application of this approach for larger finite systems. In this work, an alternative derivation that avoids using unoccupied states to construct the electron-hole interaction kernel is presented. The central idea of this approach is to use explicitly correlated geminal functions for treating electron-electron correlation for both ground and excited state wave functions. Using this ansatz, it is derived using both diagrammatic and algebraic techniques that the electron-hole interaction kernel can be expressed only in terms of linked closed-loop diagrams. It is proved that the cancellation of unlinked diagrams is a consequence of linked-cluster theorem in real-space representation. The electron-hole interaction kernel derived in this work was used to calculate excitation energies in many-electron systems and results were found to be in good agreement with the EOM-CCSD and GW+BSE methods. The numerical results highlight the effectiveness of the developed method for overcoming the computational barrier of accurately determining the electron-hole interaction kernel to applications of large finite systems such as quantum dots and nanorods.

Correlation energy functional within the GW -RPA: Exact forms, approximate forms, and challenges

NASA Astrophysics Data System (ADS)

Ismail-Beigi, Sohrab

2010-05-01

In principle, the Luttinger-Ward Green’s-function formalism allows one to compute simultaneously the total energy and the quasiparticle band structure of a many-body electronic system from first principles. We present approximate and exact expressions for the correlation energy within the GW -random-phase approximation that are more amenable to computation and allow for developing efficient approximations to the self-energy operator and correlation energy. The exact form is a sum over differences between plasmon and interband energies. The approximate forms are based on summing over screened interband transitions. We also demonstrate that blind extremization of such functionals leads to unphysical results: imposing physical constraints on the allowed solutions (Green’s functions) is necessary. Finally, we present some relevant numerical results for atomic systems.

Uniform electron gases. III. Low-density gases on three-dimensional spheres

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

Agboola, Davids; Knol, Anneke L.; Gill, Peter M. W., E-mail: peter.gill@anu.edu.au

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGFmore » centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids — the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) — and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.« less

Why does MP2 work?

PubMed

Fink, Reinhold F

2016-11-14

We show analytically and numerically that the performance of second order Møller-Plesset (MP) perturbation theory (PT), coupled-cluster (CC) theory, and other perturbation theory approaches can be rationalized by analyzing the wavefunctions of these methods. While rather large deviations for the individual contributions of configurations to the electron correlation energy are found for MP wavefunctions, they profit from an advantageous and robust error cancellation: The absolute contribution to the correlation energy is generally underestimated for the critical excitations with small energy denominators and all other doubly excited configurations where the two excited electrons are coupled to a singlet. This is balanced by an overestimation of the contribution of triplet-coupled double excitations to the correlation energy. The even better performance of spin-component-scaled-MP2 theory is explained by a similar error compensation effect. The wavefunction analysis for the lowest singlet states of H 2 O, CH 2 , CO, and Cu + shows the predicted trends for MP methods, rapid but biased convergence of CC theory as well as the substantial potential of linearized CC, or retaining the excitation-degree (RE)-PT.

Electron binding energy of uranium-ligand and uranyl-ligand anions

NASA Astrophysics Data System (ADS)

Wang, Lei; Horowitz, Steven; Marston, Brad

2012-02-01

Electron binding energies of the early actinide element uranium in gas-phase anion complexes are calculated by relativistic density functional theory (DFT) with two different exchange-correlation functions (RPBE and B3LYP) and also in the Hartree-Fock (HF) approximationootnotetextADF2010.02, SCM.com. Scalar and spin-orbit calculations are performed, and the calculated energies are compared to available experimental measurements and shown to disagree by energies of order 1 eV. Strong correlations that are poorly treated in DFT and HF can be included by a hybrid approach in which a generalized Anderson impurity model is numerically diagonalized. Reduction-oxidation (redox) potentials of aqueous actinide ions show improved agreement with measured values in the hybrid approachootnotetextS. E. Horowitz and J. B. Marston, J. Chem. Phys 134 064510 (2011).. We test whether or not similar improvements are found in the gas-phase.

Electron-nuclear corellations for photoinduced dynamics in molecular dimers

NASA Astrophysics Data System (ADS)

Kilin, Dmitri S.; Pereversev, Yuryi V.; Prezhdo, Oleg V.

2003-03-01

Ultrafast photoinduced dynamics of electronic excitation in molecular dimers is drastically affected by dynamic reorganization of of inter- and intra- molecular nuclear configuration modelled by quantized nuclear degree of freedom [1]. The dynamics of the electronic population and nuclear coherence is analyzed with help of both numerical solution of the chain of coupled differential equations for mean coordinate, population inversion, electronic-vibrational correlation etc.[2] and by propagating the Gaussian wavepackets in relevant adiabatic potentials. Intriguing results were obtained in the approximation of small energy difference and small change of nuclear equilibrium configuration for excited electronic states. In the limiting case of resonance between electronic states energy difference and frequency of the nuclear mode these results have been justified by comparison to exactly solvable Jaynes-Cummings model. It has been found that the photoinduced processes in dimer are arranged according to their time scales:(i) fast scale of nuclear motion,(ii) intermediate scale of dynamical redistribution of electronic population between excited states as well as growth and dynamics of electronic -nuclear correlation,(iii) slow scale of electronic population approaching to the quasiequilibrium distribution, decay of electronic-nuclear correlation, and diminishing the amplitude of mean coordinate oscillations, accompanied by essential growth of the nuclear coordinate dispersion associated with the overall nuclear wavepacket width. Demonstrated quantum-relaxational features of photoinduced vibronic dinamical processess in molecular dimers are obtained by simple method, applicable to large biological systems with many degrees of freedom. [1] J. A. Cina, D. S. Kilin, T. S. Humble, J. Chem. Phys. (2003) in press. [2] O. V. Prezhdo, J. Chem. Phys. 117, 2995 (2002).

Radiation belt seed population and its association with the relativistic electron dynamics: A statistical study: Radiation Belt Seed Population

DOE PAGES

Tang, C. L.; Wang, Y. X.; Ni, B.; ...

2017-05-19

Using the Van Allen Probes data, we study the radiation belt seed population and it associated with the relativistic electron dynamics during 74 geomagnetic storm events. Based on the flux changes of 1 MeV electrons before and after the storm peak, these storm events are divided into two groups of “non-preconditioned” and “preconditioned”. The statistical study shows that the storm intensity is of significant importance for the distribution of the seed population (336 keV electrons) in the outer radiation belt. However, substorm intensity can also be important to the evolution of the seed population for some geomagnetic storm events. Formore » non-preconditioned storm events, the correlation between the peak fluxes and their L-shell locations of the seed population and relativistic electrons (592 keV, 1.0 MeV, 1.8 MeV, and 2.1 MeV) is consistent with the energy-dependent dynamic processes in the outer radiation belt. For preconditioned storm events, the correlation between the features of the seed population and relativistic electrons is not fully consistent with the energy-dependent processes. It is suggested that the good correlation between the radiation belt seed population and ≤1.0 MeV electrons contributes to the prediction of the evolution of ≤1.0 MeV electrons in the Earth’s outer radiation belt during periods of geomagnetic storms.« less

Radiation belt seed population and its association with the relativistic electron dynamics: A statistical study: Radiation Belt Seed Population

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

Tang, C. L.; Wang, Y. X.; Ni, B.

Using the Van Allen Probes data, we study the radiation belt seed population and it associated with the relativistic electron dynamics during 74 geomagnetic storm events. Based on the flux changes of 1 MeV electrons before and after the storm peak, these storm events are divided into two groups of “non-preconditioned” and “preconditioned”. The statistical study shows that the storm intensity is of significant importance for the distribution of the seed population (336 keV electrons) in the outer radiation belt. However, substorm intensity can also be important to the evolution of the seed population for some geomagnetic storm events. Formore » non-preconditioned storm events, the correlation between the peak fluxes and their L-shell locations of the seed population and relativistic electrons (592 keV, 1.0 MeV, 1.8 MeV, and 2.1 MeV) is consistent with the energy-dependent dynamic processes in the outer radiation belt. For preconditioned storm events, the correlation between the features of the seed population and relativistic electrons is not fully consistent with the energy-dependent processes. It is suggested that the good correlation between the radiation belt seed population and ≤1.0 MeV electrons contributes to the prediction of the evolution of ≤1.0 MeV electrons in the Earth’s outer radiation belt during periods of geomagnetic storms.« less

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

Tokár, K.; Derian, R.; Mitas, L.

Using explicitly correlated fixed-node quantum Monte Carlo and density functional theory (DFT) methods, we study electronic properties, ground-state multiplets, ionization potentials, electron affinities, and low-energy fragmentation channels of charged half-sandwich and multidecker vanadium-benzene systems with up to 3 vanadium atoms, including both anions and cations. It is shown that, particularly in anions, electronic correlations play a crucial role; these effects are not systematically captured with any commonly used DFT functionals such as gradient corrected, hybrids, and range-separated hybrids. On the other hand, tightly bound cations can be described qualitatively by DFT. A comparison of DFT and quantum Monte Carlo providesmore » an in-depth understanding of the electronic structure and properties of these correlated systems. The calculations also serve as a benchmark study of 3d molecular anions that require a balanced many-body description of correlations at both short- and long-range distances.« less

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

NASA Astrophysics Data System (ADS)

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

2012-08-01

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

Donor impurity-related photoionization cross section in GaAs cone-like quantum dots under applied electric field

NASA Astrophysics Data System (ADS)

Iqraoun, E.; Sali, A.; Rezzouk, A.; Feddi, E.; Dujardin, F.; Mora-Ramos, M. E.; Duque, C. A.

2017-06-01

The donor impurity-related electron states in GaAs cone-like quantum dots under the influence of an externally applied static electric field are theoretically investigated. Calculations are performed within the effective mass and parabolic band approximations, using the variational procedure to include the electron-impurity correlation effects. The uncorrelated Schrödinger-like electron states are obtained in quasi-analytical form and the entire electron-impurity correlated states are used to calculate the photoionisation cross section. Results for the electron state energies and the photoionisation cross section are reported as functions of the main geometrical parameters of the cone-like structures as well as of the electric field strength.

Accurate calculation and modeling of the adiabatic connection in density functional theory

NASA Astrophysics Data System (ADS)

Teale, A. M.; Coriani, S.; Helgaker, T.

2010-04-01

Using a recently implemented technique for the calculation of the adiabatic connection (AC) of density functional theory (DFT) based on Lieb maximization with respect to the external potential, the AC is studied for atoms and molecules containing up to ten electrons: the helium isoelectronic series, the hydrogen molecule, the beryllium isoelectronic series, the neon atom, and the water molecule. The calculation of AC curves by Lieb maximization at various levels of electronic-structure theory is discussed. For each system, the AC curve is calculated using Hartree-Fock (HF) theory, second-order Møller-Plesset (MP2) theory, coupled-cluster singles-and-doubles (CCSD) theory, and coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] theory, expanding the molecular orbitals and the effective external potential in large Gaussian basis sets. The HF AC curve includes a small correlation-energy contribution in the context of DFT, arising from orbital relaxation as the electron-electron interaction is switched on under the constraint that the wave function is always a single determinant. The MP2 and CCSD AC curves recover the bulk of the dynamical correlation energy and their shapes can be understood in terms of a simple energy model constructed from a consideration of the doubles-energy expression at different interaction strengths. Differentiation of this energy expression with respect to the interaction strength leads to a simple two-parameter doubles model (AC-D) for the AC integrand (and hence the correlation energy of DFT) as a function of the interaction strength. The structure of the triples-energy contribution is considered in a similar fashion, leading to a quadratic model for the triples correction to the AC curve (AC-T). From a consideration of the structure of a two-level configuration-interaction (CI) energy expression of the hydrogen molecule, a simple two-parameter CI model (AC-CI) is proposed to account for the effects of static correlation on the AC. When parametrized in terms of the same input data, the AC-CI model offers improved performance over the corresponding AC-D model, which is shown to be the lowest-order contribution to the AC-CI model. The utility of the accurately calculated AC curves for the analysis of standard density functionals is demonstrated for the BLYP exchange-correlation functional and the interaction-strength-interpolation (ISI) model AC integrand. From the results of this analysis, we investigate the performance of our proposed two-parameter AC-D and AC-CI models when a simple density functional for the AC at infinite interaction strength is employed in place of information at the fully interacting point. The resulting two-parameter correlation functionals offer a qualitatively correct behavior of the AC integrand with much improved accuracy over previous attempts. The AC integrands in the present work are recommended as a basis for further work, generating functionals that avoid spurious error cancellations between exchange and correlation energies and give good accuracy for the range of densities and types of correlation contained in the systems studied here.

Acceleration of electron bunches by intense laser pulse in vacuum

NASA Astrophysics Data System (ADS)

Hua, J. F.; Ho, Y. K.; Lin, Y. Z.; Cao, N.

2003-08-01

This paper addresses the output characteristics of real electron bunches accelerated with ultra-intense laser pulse in vacuum by the capture & acceleration scenario (CAS) scheme (see, e.g., Phys. Rev. E66 (2002) 066501). Normally, the size of an electron bunch is much larger than that of a tightly focused and compressed laser pulse. We examine in detail the features of the intersection region, the distribution of electrons which can experience an intense laser field and be accelerated to high energy. Furthermore, the output properties of the accelerated CAS electrons, such as the energy spectra, the angular distributions, the energy-angle correlations, the acceleration gradient, the energy which can be reached with this scheme, the emittances of the outgoing electron bunches, and the dependence of the output properties on the incident electron beam qualities such as the emittance, focusing status, etc. were studied and explained. We found that with intense laser systems and electron beam technology currently available nowadays, the number of CAS electrons can reach 10 4-10 5, when the total number of incident electrons in the practical bunch reaches ˜10 8. These results demonstrate that CAS is promising to become a novel mechanism of vacuum laser accelerators.

Efficient construction of exchange and correlation potentials by inverting the Kohn-Sham equations.

PubMed

Kananenka, Alexei A; Kohut, Sviataslau V; Gaiduk, Alex P; Ryabinkin, Ilya G; Staroverov, Viktor N

2013-08-21

Given a set of canonical Kohn-Sham orbitals, orbital energies, and an external potential for a many-electron system, one can invert the Kohn-Sham equations in a single step to obtain the corresponding exchange-correlation potential, vXC(r). For orbitals and orbital energies that are solutions of the Kohn-Sham equations with a multiplicative vXC(r) this procedure recovers vXC(r) (in the basis set limit), but for eigenfunctions of a non-multiplicative one-electron operator it produces an orbital-averaged potential. In particular, substitution of Hartree-Fock orbitals and eigenvalues into the Kohn-Sham inversion formula is a fast way to compute the Slater potential. In the same way, we efficiently construct orbital-averaged exchange and correlation potentials for hybrid and kinetic-energy-density-dependent functionals. We also show how the Kohn-Sham inversion approach can be used to compute functional derivatives of explicit density functionals and to approximate functional derivatives of orbital-dependent functionals.

Importance of Electronic Correlations and Unusual Excitonic Effects in Formamidinium Lead Halide Perovskites

NASA Astrophysics Data System (ADS)

Whitcher, T. J.; Zhu, J.-X.; Chi, X.; Hu, H.; Zhao, Daming; Asmara, T. C.; Yu, X.; Breese, M. B. H.; Castro Neto, A. H.; Lam, Y. M.; Wee, A. T. S.; Chia, Elbert E. M.; Rusydi, A.

2018-04-01

Hybrid inorganic-organic perovskites have recently attracted much interest because of both rich fundamental sciences and potential applications such as the primary energy-harvesting material in solar cells. However, an understanding of electronic and optical properties, particularly the complex dielectric function, of these materials is still lacking. Here, we report on the electronic and optical properties of selective perovskites using temperature-dependent spectroscopic ellipsometry, x-ray absorption spectroscopy supported by first-principles calculations. Surprisingly, the perovskite FA0.85Cs0.15PbI2.9Br0.1 has a very high density of low-energy excitons that increases with increasing temperature even at room temperature, which is not seen in any other material. This is found to be due to the strong, unscreened electron-electron and partially screened electron-hole interactions, which then tightly connect low- and high-energy bands caused by doping.

Density functional theory calculations of the water interactions with ZrO2 nanoparticles Y2O3 doped

NASA Astrophysics Data System (ADS)

Subhoni, Mekhrdod; Kholmurodov, Kholmirzo; Doroshkevich, Aleksandr; Asgerov, Elmar; Yamamoto, Tomoyuki; Lyubchyk, Andrei; Almasan, Valer; Madadzada, Afag

2018-03-01

Development of a new electricity generation techniques is one of the most relevant tasks, especially nowadays under conditions of extreme growth in energy consumption. The exothermic heterogeneous electrochemical energy conversion to the electric energy through interaction of the ZrO2 based nanopowder system with atmospheric moisture is one of the ways of electric energy obtaining. The questions of conversion into the electric form of the energy of water molecules adsorption in 3 mol% Y2O3 doped ZrO2 nanopowder systems were investigated using the density functional theory calculations. The density functional theory calculations has been realized as in the Kohn-Sham formulation, where the exchange-correlation potential is approximated by a functional of the electronic density. The electronic density, total energy and band structure calculations are carried out using the all-electron, full potential, linear augmented plane wave method of the electronic density and related approximations, i.e. the local density, the generalized gradient and their hybrid approximations.

Effects of target plasma electron-electron collisions on correlated motion of fragmented protons.

PubMed

Barriga-Carrasco, Manuel D

2006-02-01

The objective of the present work is to examined the effects of plasma target electron-electron collisions on H2 + protons traversing it. Specifically, the target is deuterium in a plasma state with temperature Te=10 eV and density n=10(23) cm(-3), and proton velocities are vp=vth, vp=2vth, and vp=3vth, where vth is the electron thermal velocity of the target plasma. Proton interactions with plasma electrons are treated by means of the dielectric formalism. The interactions among close protons through plasma electronic medium are called vicinage forces. It is checked that these forces always screen the Coulomb explosions of the two fragmented protons from the same H2 + ion decreasing their relative distance. They also align the interproton vector along the motion direction, and increase the energy loss of the two protons at early dwell times while for longer times the energy loss tends to the value of two isolated protons. Nevertheless, vicinage forces and effects are modified by the target electron collisions. These collisions enhance the calculated self-stopping and vicinage forces over the collisionless results. Regarding proton correlated motion, when these collisions are included, the interproton vector along the motion direction overaligns at slower proton velocities (vp=vth) and misaligns for faster ones (vp=2vth, vp=3vth). They also contribute to a great extend to increase the energy loss of the fragmented H2 + ion. This later effect is more significant in reducing projectile velocity.

Using High Energy Precipitation for Magnetic Mapping in the Nightside Transition Region During Dynamic Events

NASA Astrophysics Data System (ADS)

Spanswick, E.

2017-12-01

Identifying the magnetic footprint of a satellite can be done using the in situ observations together with some ionospheric or low-altitude satellite observation to argue that the two measurements were made on the same field line. Nishimura et al. [2011], e.g., correlated a time series of chorus wave power near the magnetic equator with the time series of intensities of every pixel of a is roughly magnetically conjugate ASI. Often, the pattern of correlation shows a well-defined peak at the location of the satellite's magnetic footprint. Their results cannot be replicated during dynamic events (e.g., substorms), because the required auroral forms do not occur at such times. It would be important if we could make mappings with such confidence during active times. The Transition Region Explorer (TREx), which is presently being implemented, is a new ground-based facility that will remote sense electron precipitation across 3 hours of MLT and 12 degrees of magnetic latitude spanning the auroral zone in western Canada. TREx includes the world's first imaging riometers array with a contiguous field of view large enough to seamlessly track the spatio-temporal evolution of high energy electron precipitation at mesoscales. Two studies motivated the TREx riometers array. First, Baker et al. [1981] demonstrated riometer absorption is an excellent proxy for the electron energy flux integrated from 30 keV to 200keV keV at the magnetic equator on the flux tube corresponding to the location of that riometers. Second, Spanswick et al. [2007] showed the correlation between the riometers absorption and the integrated electron energy flux near the magnetic equator peaked when the satellite was nearest to conjugate to the riometers. Here we present observations using CANOPUS single beam riometers and CRRES MEB to illustrate how the relative closeness of the footpoint of an equatorial spacecraft can be assessed using high energy precipitation. As well, we present the capabilities of the new TREx riometers facility for spatio-temporal observation of the high energy electron precipitation over the TREx field of view, and our plan to use that high energy electron precipitation to provide accurate tracking of satellite footpoints during dynamic geospace events including substorm expansion phase.

Double Photoionization of helium atom using Screening Potential Approach

NASA Astrophysics Data System (ADS)

Saha, Haripada

2014-05-01

The triple differential cross section for double Photoionization of helium atom will be investigated using our recently extended MCHF method. It is well known that electron correlation effects in both the initial and the final states are very important. To incorporate these effects we will use the multi-configuration Hartree-Fock method to account for electron correlation in the initial state. The electron correlation in the final state will be taken into account using the angle-dependent screening potential approximation. The triple differential cross section (TDCS) will be calculated for 20 eV photon energy, which has experimental results. Our results will be compared with available experimental and the theoretical observations.

Benchmark of Dynamic Electron Correlation Models for Seniority-Zero Wave Functions and Their Application to Thermochemistry.

PubMed

Boguslawski, Katharina; Tecmer, Paweł

2017-12-12

Wave functions restricted to electron-pair states are promising models to describe static/nondynamic electron correlation effects encountered, for instance, in bond-dissociation processes and transition-metal and actinide chemistry. To reach spectroscopic accuracy, however, the missing dynamic electron correlation effects that cannot be described by electron-pair states need to be included a posteriori. In this Article, we extend the previously presented perturbation theory models with an Antisymmetric Product of 1-reference orbital Geminal (AP1roG) reference function that allows us to describe both static/nondynamic and dynamic electron correlation effects. Specifically, our perturbation theory models combine a diagonal and off-diagonal zero-order Hamiltonian, a single-reference and multireference dual state, and different excitation operators used to construct the projection manifold. We benchmark all proposed models as well as an a posteriori Linearized Coupled Cluster correction on top of AP1roG against CR-CC(2,3) reference data for reaction energies of several closed-shell molecules that are extrapolated to the basis set limit. Moreover, we test the performance of our new methods for multiple bond breaking processes in the homonuclear N 2 , C 2 , and F 2 dimers as well as the heteronuclear BN, CO, and CN + dimers against MRCI-SD, MRCI-SD+Q, and CR-CC(2,3) reference data. Our numerical results indicate that the best performance is obtained from a Linearized Coupled Cluster correction as well as second-order perturbation theory corrections employing a diagonal and off-diagonal zero-order Hamiltonian and a single-determinant dual state. These dynamic corrections on top of AP1roG provide substantial improvements for binding energies and spectroscopic properties obtained with the AP1roG approach, while allowing us to approach chemical accuracy for reaction energies involving closed-shell species.

Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2016-07-21

Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.

Quantum coherence selective 2D Raman–2D electronic spectroscopy

PubMed Central

Spencer, Austin P.; Hutson, William O.; Harel, Elad

2017-01-01

Electronic and vibrational correlations report on the dynamics and structure of molecular species, yet revealing these correlations experimentally has proved extremely challenging. Here, we demonstrate a method that probes correlations between states within the vibrational and electronic manifold with quantum coherence selectivity. Specifically, we measure a fully coherent four-dimensional spectrum which simultaneously encodes vibrational–vibrational, electronic–vibrational and electronic–electronic interactions. By combining near-impulsive resonant and non-resonant excitation, the desired fifth-order signal of a complex organic molecule in solution is measured free of unwanted lower-order contamination. A critical feature of this method is electronic and vibrational frequency resolution, enabling isolation and assignment of individual quantum coherence pathways. The vibronic structure of the system is then revealed within an otherwise broad and featureless 2D electronic spectrum. This method is suited for studying elusive quantum effects in which electronic transitions strongly couple to phonons and vibrations, such as energy transfer in photosynthetic pigment–protein complexes. PMID:28281541

Sum-rule corrections: a route to error cancellations in correlation matrix renormalisation theory

NASA Astrophysics Data System (ADS)

Liu, C.; Liu, J.; Yao, Y. X.; Wang, C. Z.; Ho, K. M.

2017-03-01

We recently proposed the correlation matrix renormalisation (CMR) theory to efficiently and accurately calculate ground state total energy of molecular systems, based on the Gutzwiller variational wavefunction (GWF) to treat the electronic correlation effects. To help reduce numerical complications and better adapt the CMR to infinite lattice systems, we need to further refine the way to minimise the error originated from the approximations in the theory. This conference proceeding reports our recent progress on this key issue, namely, we obtained a simple analytical functional form for the one-electron renormalisation factors, and introduced a novel sum-rule correction for a more accurate description of the intersite electron correlations. Benchmark calculations are performed on a set of molecules to show the reasonable accuracy of the method.

Valence electronic properties of porphyrin derivatives.

PubMed

Stenuit, G; Castellarin-Cudia, C; Plekan, O; Feyer, V; Prince, K C; Goldoni, A; Umari, P

2010-09-28

We present a combined experimental and theoretical investigation of the valence electronic structure of porphyrin-derived molecules. The valence photoemission spectra of the free-base tetraphenylporphyrin and of the octaethylporphyrin molecule were measured using synchrotron radiation and compared with theoretical spectra calculated using the GW method and the density-functional method within the generalized gradient approximation. Only the GW results could reproduce the experimental data. We found that the contribution to the orbital energies due to electronic correlations has the same linear behavior in both molecules, with larger deviations in the vicinity of the HOMO level. This shows the importance of adequate treatment of electronic correlations in these organic systems.

Electron Correlation in Oxygen Vacancy in SrTiO3

NASA Astrophysics Data System (ADS)

Lin, Chungwei; Demkov, Alexander A.

2014-03-01

Oxygen vacancies are an important type of defect in transition metal oxides. In SrTiO3 they are believed to be the main donors in an otherwise intrinsic crystal. At the same time, a relatively deep gap state associated with the vacancy is widely reported. To explain this inconsistency we investigate the effect of electron correlation in an oxygen vacancy (OV) in SrTiO3. When taking correlation into account, we find that the OV-induced localized level can at most trap one electron, while the second electron occupies the conduction band. Our results offer a natural explanation of how the OV in SrTiO3 can produce a deep in-gap level (about 1 eV below the conduction band bottom) in photoemission, and at the same time be an electron donor. Our analysis implies an OV in SrTiO3 should be fundamentally regarded as a magnetic impurity, whose deep level is always partially occupied due to the strong Coulomb repulsion. An OV-based Anderson impurity model is derived, and its implications are discussed. This work was supported by Scientific Discovery through Advanced Computing (SciDAC) program funded by U.S. Department of Energy, Office of Science, Advanced Scientific Computing Research and Basic Energy Sciences under award number DESC0008877.

Theoretical study on the dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides

NASA Astrophysics Data System (ADS)

Cheng, Li; Shen, Zuochun; Lu, Jianye; Gao, Huide; Lü, Zhiwei

2005-11-01

Dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides, CF 3I, C 2F 5I, and i-C 3F 7I are calculated accurately with B3LYP, MP n ( n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) methods. Calculations are performed by using large-core correlation-consistent pseudopotential basis set (SDB-aug-cc-pVTZ) for iodine atom. In all energy calculations, the zero point vibration energy is corrected. And the basis set superposition error is corrected by counterpoise method in the calculation of dissociation energy. Theoretical results are compared with the experimental values.

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.

Energetics of impulsive solar flares: Correlating BATSE hard x-ray bursts and the solar atmosphere's soft x-ray response

NASA Technical Reports Server (NTRS)

Newton, Elizabeth

1996-01-01

This investigation has involved the correlation of BATSE-observed solar hard X-ray emission with the characteristics of soft X-ray emitting plasma observed by the Yohkoh Bragg Crystal Spectrometers. The goal was to test the hypothesis that localized electron beam heating is the dominant energy transport mechanism in impulsive flares, as formulated in the thick-target electron-heated model of Brown.

High-temperature fusion of a multielectron leviton

NASA Astrophysics Data System (ADS)

Moskalets, Michael

2018-04-01

The state of electrons injected onto the surface of the Fermi sea depends on temperature. The state is pure at zero temperature and is mixed at finite temperature. In the case of a single-electron injection, such a transformation can be detected as a decrease in shot noise with increasing temperature. In the case of a multielectron injection, the situation is subtler. The mixedness helps the development of quantum-mechanical exchange correlations between injected electrons, even if such correlations are absent at zero temperature. These correlations enhance the shot noise, which in part counteracts the reduction of noise with temperature. Moreover, at sufficiently high temperatures, the correlation contribution to noise predominates over the contribution of individual particles. As a result, in the system of N electrons, the apparent charge (which is revealed via the shot noise) is changed from e at zero temperature to N e at high temperatures. It looks like the exchange correlations glue electrons into one particle of total charge and energy. This point of view is supported by both charge noise and heat noise. Interestingly, in the macroscopic limit, N →∞ , the correlation contribution completely suppresses the effect of temperature on noise.

Interplay between strong correlation and adsorption distances: Co on Cu(001)

NASA Astrophysics Data System (ADS)

Bahlke, Marc Philipp; Karolak, Michael; Herrmann, Carmen

2018-01-01

Adsorbed transition metal atoms can have partially filled d or f shells due to strong on-site Coulomb interaction. Capturing all effects originating from electron correlation in such strongly correlated systems is a challenge for electronic structure methods. It requires a sufficiently accurate description of the atomistic structure (in particular bond distances and angles), which is usually obtained from first-principles Kohn-Sham density functional theory (DFT), which due to the approximate nature of the exchange-correlation functional may provide an unreliable description of strongly correlated systems. To elucidate the consequences of this popular procedure, we apply a combination of DFT with the Anderson impurity model (AIM), as well as DFT + U for a calculation of the potential energy surface along the Co/Cu(001) adsorption coordinate, and compare the results with those obtained from DFT. The adsorption minimum is shifted towards larger distances by applying DFT+AIM, or the much cheaper DFT +U method, compared to the corresponding spin-polarized DFT results, by a magnitude comparable to variations between different approximate exchange-correlation functionals (0.08 to 0.12 Å). This shift originates from an increasing correlation energy at larger adsorption distances, which can be traced back to the Co 3 dx y and 3 dz2 orbitals being more correlated as the adsorption distance is increased. We can show that such considerations are important, as they may strongly affect electronic properties such as the Kondo temperature.

Observation of the fractional quantum Hall effect in graphene.

PubMed

Bolotin, Kirill I; Ghahari, Fereshte; Shulman, Michael D; Stormer, Horst L; Kim, Philip

2009-11-12

When electrons are confined in two dimensions and subject to strong magnetic fields, the Coulomb interactions between them can become very strong, leading to the formation of correlated states of matter, such as the fractional quantum Hall liquid. In this strong quantum regime, electrons and magnetic flux quanta bind to form complex composite quasiparticles with fractional electronic charge; these are manifest in transport measurements of the Hall conductivity as rational fractions of the elementary conductance quantum. The experimental discovery of an anomalous integer quantum Hall effect in graphene has enabled the study of a correlated two-dimensional electronic system, in which the interacting electrons behave like massless chiral fermions. However, owing to the prevailing disorder, graphene has so far exhibited only weak signatures of correlated electron phenomena, despite intense experimental and theoretical efforts. Here we report the observation of the fractional quantum Hall effect in ultraclean, suspended graphene. In addition, we show that at low carrier density graphene becomes an insulator with a magnetic-field-tunable energy gap. These newly discovered quantum states offer the opportunity to study correlated Dirac fermions in graphene in the presence of large magnetic fields.

Electron correlations in L-subshell photoionization of intermediate-Z elements (47<=Z<=51)

NASA Astrophysics Data System (ADS)

Jitschin, W.; Stötzel, R.

1998-08-01

The x-ray mass attenuation of 48Cd, 49In, 50Sn, and 51Sb in the energy regime of the L-subshell edges has been measured. For a comparison of the data of neighboring elements, these were scaled to 47Ag. The scaled data were compared with theoretical calculations of photoionization cross sections by Scofield, which use the common single electron approach. The comparison reveals minor but significant deviations between measurement and calculation: The measured cross sections are smaller than the prediction in the regime between the L3 and L2 edges, they have a flatter slope in the regime between the L2 and L1 edges, and they exhibit a decrease just above the L3 and L2 edges. All observed deviations can be explained as electron correlation effects originating from a polarization of the whole electron cloud by the ionizing radiation, since they are qualitatively reproduced by comparative calculations of the ionization process either omitting (independent particle approach) or including (in the linear response approximation) the electron correlations. However, the comparative calculations quantitatively overestimate the electron correlation effects.

Theoretical Modeling of Various Spectroscopies for Cuprates and Topological Insulators

NASA Astrophysics Data System (ADS)

Basak, Susmita

Spectroscopies resolved highly in momentum, energy and/or spatial dimensions are playing an important role in unraveling key properties of wide classes of novel materials. However, spectroscopies do not usually provide a direct map of the underlying electronic spectrum, but act as a complex 'filter' to produce a 'mapping' of the underlying energy levels, Fermi surfaces (FSs) and excitation spectra. The connection between the electronic spectrum and the measured spectra is described as a generalized 'matrix element effect'. The nature of the matrix element involved differs greatly between different spectroscopies. For example, in angle-resolved photoemission (ARPES) an incoming photon knocks out an electron from the sample and the energy and momentum of the photoemitted electron is measured. This is quite different from what happens in K-edge resonant inelastic X-ray scattering (RIXS), where an X-ray photon is scattered after inducing electronic transitions near the Fermi energy through an indirect second order process, or in Compton scattering where the incident X-ray photon is scattered inelastically from an electron transferring energy and momentum to the scattering electron. For any given spectroscopy, the matrix element is, in general, a complex function of the phase space of the experiment, e.g. energy/polarization of the incoming photon and the energy/momentum/spin of the photoemitted electron in the case of ARPES. The matrix element can enhance or suppress signals from specific states, or merge signals of groups of states, making a good understanding of the matrix element effects important for not only a robust interpretation of the spectra, but also for ascertaining optimal regions of the experimental phase space for zooming in on states of the greatest interest. In this thesis I discuss a comprehensive scheme for modeling various highly resolved spectroscopies of the cuprates and topological insulators (TIs) where effects of matrix element, crystal structure, strong electron correlations (for cuprates) and spin-orbit coupling (for TIs) are included realistically in material-specific detail. Turning to the cuprates, in order to obtain a realistic description of various spectroscopies, one must include not only the effects of the matrix elements and the complexity of the crystal structure, but also of strong electronic correlations beyond the local density approximation (LDA)-based conventional picture, so that the physics of kinks, pseudogaps and superconductivity can be taken into account properly. In this connection, a self-consistent, intermediate coupling scheme informed by material-specific, first-principles band structures has been developed, where electron correlation effects beyond the LDA are incorporated via appropriate self-energy corrections to the electron and hole one-particle Green's functions. Here the antiferromagnetic (AFM) order is used as the simplest model of a competing order. A number of salient features of the resulting electronic spectrum and its energy, momentum and doping dependencies are in accord with experimental observations in electron as well as hole doped cuprates. This scheme thus provides a reasonable basis for undertaking a comprehensive, beyond-LDA level of modeling of various spectroscopies. The specific topics considered here are: (i) Origin of high-energy kink or the waterfall effect found in ARPES; (ii) Identification of the three energy scales observed in RIXS spectra as the pseudogap, charge transfer gap, and Mott gap; (iii) Evolution of the electron momentum densities with holedoping as seen in Compton scattering experiments. For three dimensional topological insulators, the ARPES and scanning tunneling microscopy (STM) spectra has been analyzed using a tight-binding model as well as a k · p model. The spin-orbit coupling, which is essential to produce the characteristic features of the surface states of a TI, is included realistically in the above models. In our generalized k · p model Dresselhaus spin-orbit coupling term extends up to fifth order to reproduce the correct spin-polarization of the surface electrons. These model calculations explain a number of important features associated with the energy and spins of the surface electrons of the first and second generations of TIs. The specific issues addressed in this article are: (i) Non-orthogonality between spin and momentum of the surface electrons; (ii) Electron dynamics at the TI-metal interface; (iii) Origin of the broken time-reversal symmetry observed in the Fourier transform scanning tunneling spectroscopy.

Extremely correlated Fermi liquid theory of the t-J model in 2 dimensions: low energy properties

NASA Astrophysics Data System (ADS)

Shastry, B. Sriram; Mai, Peizhi

2018-01-01

Low energy properties of the metallic state of the two-dimensional t-J model are presented for second neighbor hopping with hole-doping (t\\prime ≤slant 0) and electron-doping (t\\prime > 0), with various superexchange energy J. We use a closed set of equations for the Greens functions obtained from the extremely correlated Fermi liquid theory. These equations reproduce the known low energies features of the large U Hubbard model in infinite dimensions. The density and temperature dependent quasiparticle weight, decay rate and the peak spectral heights over the Brillouin zone are calculated. We also calculate the resistivity, Hall conductivity, Hall number and cotangent Hall angle. The spectral features display high thermal sensitivity at modest T for density n≳ 0.8, implying a suppression of the effective Fermi-liquid temperature by two orders of magnitude relative to the bare bandwidth. The cotangent Hall angle exhibits a T 2 behavior at low T, followed by an interesting kink at higher T. The Hall number exhibits strong renormalization due to correlations. Flipping the sign of t\\prime changes the curvature of the resistivity versus T curves between convex and concave. Our results provide a natural route for understanding the observed difference in the temperature dependent resistivity of strongly correlated electron-doped and hole-doped matter.

The uniform quantized electron gas revisited

NASA Astrophysics Data System (ADS)

Lomba, Enrique; Høye, Johan S.

2017-11-01

In this article we continue and extend our recent work on the correlation energy of the quantized electron gas of uniform density at temperature T=0 . As before, we utilize the methods, properties, and results obtained by means of classical statistical mechanics. These were extended to quantized systems via the Feynman path integral formalism. The latter translates the quantum problem into a classical polymer problem in four dimensions. Again, the well known RPA (random phase approximation) is recovered as a basic result which we then modify and improve upon. Here we analyze the condition of thermodynamic self-consistency. Our numerical calculations exhibit a remarkable agreement with well known results of a standard parameterization of Monte Carlo correlation energies.

Electron Identification and Energy Measurement with Emulsion Cloud Chamber

NASA Astrophysics Data System (ADS)

Kitagawa, Nobuko; Komatsu, Masahiro

Charged particles undergo the Multiple Coulomb Scattering (MCS) when passing through a material. Their momentum can be estimated from the distribution of the scattering angle directly. Angle of electrons (or positrons) largely changes because of the energy loss in bremsstrahlung, and they are distinguished from other charged particles by making use of its feature. Electron energy is generally measured by counting of electromagnetic shower (e.m. shower) tracks in Emulsion Cloud Chamber (ECC), so enough absorber material is needed to develop the shower. In the range from sub-GeV to a few GeV, electrons don't develop noticeable showers. In order to estimate the energy of electrons in this range with a limited material, we established the new method which is based on the scattering angle considering the energy loss in bremsstrahlung. From the Monte Carlo simulation (MC) data, which is generated by electron beam (0.5 GeV, 1 GeV, 2 GeV) exposure to ECC, we derived the correlation between energy and scattering angle in each emulsion layer. We fixed the function and some parameters which 1 GeV MC sample would return 1 GeV as the center value, and then applied to 0.5 GeV and 2 GeV sample and confirmed the energy resolution about 50% within two radiation length.

Improved correlation corrections to the local-spin-density approximation

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

Painter, G.S.

1981-10-15

The accurate correlation energies for the para- and ferromagnetic states of the electron liquid calculated by Ceperley and Alder were recently used by Vosko, Wilk, and Nusair to produce a new correlation-energy density of increased accuracy and proper limiting behavior in the metallic density regime (r/sub s/< or =6). In the present work, the correlation potential in the local-spin-density approximation (LSDA) is derived from the correlation-energy-density representation of Vosko et al. Characteristics of the new exchange-correlation model are compared with those of the LSDA model of Gunnarsson and Lundqvist. Specific comparison is made between these models and exact results inmore » the treatment of atomic and molecular hydrogen. Since the new treatment of correlation primarily affects the region of small r/sub s/, which is exchange dominated, correlation corrections are small compared with errors in the exchange energy. Thus, in light atoms the improved correlation model leads to a reduced cancellation of error between exchange and correlation energies, emphasizing the necessity for improved exchange treatment. For more homogeneous systems, the model should offer real improvement. The present results obtained with precise treatment of correlation within the prescription of Vosko et al. serve to define the present limitations of the LSDA and indicate the importance of nonlocal corrections, particularly for atoms.« less

High-level ab initio potential energy surface and dynamics of the F- + CH3I SN2 and proton-transfer reactions.

PubMed

Olasz, Balázs; Szabó, István; Czakó, Gábor

2017-04-01

Bimolecular nucleophilic substitution (S N 2) and proton transfer are fundamental processes in chemistry and F - + CH 3 I is an important prototype of these reactions. Here we develop the first full-dimensional ab initio analytical potential energy surface (PES) for the F - + CH 3 I system using a permutationally invariant fit of high-level composite energies obtained with the combination of the explicitly-correlated CCSD(T)-F12b method, the aug-cc-pVTZ basis, core electron correlation effects, and a relativistic effective core potential for iodine. The PES accurately describes the S N 2 channel producing I - + CH 3 F via Walden-inversion, front-side attack, and double-inversion pathways as well as the proton-transfer channel leading to HF + CH 2 I - . The relative energies of the stationary points on the PES agree well with the new explicitly-correlated all-electron CCSD(T)-F12b/QZ-quality benchmark values. Quasiclassical trajectory computations on the PES show that the proton transfer becomes significant at high collision energies and double-inversion as well as front-side attack trajectories can occur. The computed broad angular distributions and hot internal energy distributions indicate the dominance of indirect mechanisms at lower collision energies, which is confirmed by analyzing the integration time and leaving group velocity distributions. Comparison with available crossed-beam experiments shows usually good agreement.

Low-Energy Elastic Electron Scattering by Atomic Oxygen

NASA Technical Reports Server (NTRS)

Zatsarinny O.; Bartschat, K.; Tayal, S. S.

2006-01-01

The B-spline R-matrix method is employed to investigate the low-energy elastic electron scattering by atomic oxygen. Flexible non-orthogonal sets of radial functions are used to construct the target description and to represent the scattering functions. A detailed investigation regarding the dependence of the predicted partial and total cross sections on the scattering model and the accuracy of the target description is presented. The predicted angle-integrated elastic cross sections are in good agreement with experiment, whereas significant discrepancies are found in the angle-differential elastic cross sections near the forward direction. .The near-threshold results are found to strongly depend on the treatment of inner-core short-range correlation effects in the target description, as well as on a proper account of the target polarizability. A sharp increase in the elastic cross sections below 1 eV found in some earlier calculations is judged to be an artifact of an unbalanced description of correlation in the N-electron target structure and the (N+l)-electron-collision problems.

Multiconfiguration Pair-Density Functional Theory: A New Way To Treat Strongly Correlated Systems.

PubMed

Gagliardi, Laura; Truhlar, Donald G; Li Manni, Giovanni; Carlson, Rebecca K; Hoyer, Chad E; Bao, Junwei Lucas

2017-01-17

The electronic energy of a system provides the Born-Oppenheimer potential energy for internuclear motion and thus determines molecular structure and spectra, bond energies, conformational energies, reaction barrier heights, and vibrational frequencies. The development of more efficient and more accurate ways to calculate the electronic energy of systems with inherently multiconfigurational electronic structure is essential for many applications, including transition metal and actinide chemistry, systems with partially broken bonds, many transition states, and most electronically excited states. Inherently multiconfigurational systems are called strongly correlated systems or multireference systems, where the latter name refers to the need for using more than one ("multiple") configuration state function to provide a good zero-order reference wave function. This Account describes multiconfiguration pair-density functional theory (MC-PDFT), which was developed as a way to combine the advantages of wave function theory (WFT) and density functional theory (DFT) to provide a better treatment of strongly correlated systems. First we review background material: the widely used Kohn-Sham DFT (which uses only a single Slater determinant as reference wave function), multiconfiguration WFT methods that treat inherently multiconfigurational systems based on an active space, and previous attempts to combine multiconfiguration WFT with DFT. Then we review the formulation of MC-PDFT. It is a generalization of Kohn-Sham DFT in that the electron kinetic energy and classical electrostatic energy are calculated from a reference wave function, while the rest of the energy is obtained from a density functional. However, there are two main differences with respent to Kohn-Sham DFT: (i) The reference wave function is multiconfigurational rather than being a single Slater determinant. (ii) The density functional is a function of the total density and the on-top pair density rather than being a function of the spin-up and spin-down densities. In work carried out so far, the multiconfigurational wave function is a multiconfiguration self-consistent-field wave function. The new formulation has the advantage that the reference wave function has the correct spatial and spin symmetry and can describe bond dissociation (of both single and multiple bonds) and electronic excitations in a formally and physically correct way. We then review the formulation of density functionals in terms of the on-top pair density. Finally we review successful applications of the theory to bond energies and bond dissociation potential energy curves of main-group and transition metal bonds, to barrier heights (including pericyclic reactions), to proton affinities, to the hydrogen bond energy of water dimer, to ground- and excited-state charge transfer, to valence and Rydberg excitations of molecules, and to singlet-triplet splittings of radicals. We find that that MC-PDFT can give accurate results not only with complete-active-space multiconfiguration wave functions but also with generalized-active-space multiconfiguration wave functions, which are practical for larger numbers of active electrons and active orbitals than are complete-active-space wave functions. The separated-pair approximation, which is a special case of generalized active space self-consistent-field theory, is especially promising. MC-PDFT, because it requires much less computer time and storage than pure WFT methods, has the potential to open larger and more complex strongly correlated systems to accurate simulation.

Final Scientific/Technical Report (DE-FG02-05ER46201)

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

Car, Roberto

The research supported by this grant focused on the quantum mechanical theory of the electrons in materials and molecules. Progress was made in dealing with electronic correlation effects in the ground state energy of molecular systems, and with topological concepts to classify the electronic state of molecules and materials, including excitation and transport properties. The physical and chemical properties of molecules and materials derive from their electronic structure, but the latter cannot be calculated exactly even with the most powerful computers because the computational cost of solving the exact equations of quantum mechanics increases exponentially with the number of electrons.more » The exponential cost originates from the correlations among the electrons that repel each other via Coulombic forces. In this project we have developed a new functional approximation for the ground state electronic energy that includes explicitly, and in a controllable way, the effects of the interelectronic correlations. In addition we have further developed topological concepts for classifying the electronic states of periodic ring molecules and solids. Topological concepts are very powerful because they allow us to predict subtle properties of materials and molecules using very general geometrical properties of the electron wavefunctions that do not depend on the quantitative details of the electronic interactions, which are very difficult to calculate with high accuracy. The development of a new class of controlled functional approximations for the ground state energy of molecules and materials was the main goal of the project. It has been fulfilled with the formulation of the occupation-probabilities natural orbital functional theory (OP-NOFT). This approach introduces new theoretical concepts but practical application has proved to be harder than anticipated. So far it has been utilized only at its lowest level of approximation in the context of relatively small molecules (with up to 16 atoms). The study of topological properties of the electron wavefunctions in materials was not proposed in the original proposal but was prompted during the funding period by our interaction with leading experimental groups in materials chemistry and physics at Princeton University.« less

Electronic structure, magnetic properties, and mechanism of the insulator-metal transition in LaCoO3 taking into account strong electron correlations

NASA Astrophysics Data System (ADS)

Ovchinnikov, S. G.; Orlov, Yu. S.; Nekrasov, I. A.; Pchelkina, Z. V.

2011-01-01

The electronic structure of LaCoO3 at finite temperatures is calculated using the LDA+GTB method taking into account strong electron correlations and possible spin crossover upon an increase in temperature. Gap states revealed in the energy spectrum of LaCoO3 reduce the dielectric gap width upon heating; this allowed us to describe the insulator-metal transition observed in this compound at T = 500-600 K. The temperature dependence of the magnetic susceptibility with a peak at T ≈ 100 K is explained by the Curie contribution from thermally excited energy levels of the Co3+ ion. At high temperatures, the Pauli contribution from a band electron is added and the total magnetization of LaCoO3 is considered as the sum M tot = M loc + M band. The second term describes the band contribution appearing as a result of the insulator-metal transition and facilitating the emergence of a high-temperature anomaly in the magnetic susceptibility of LaCoO3.

Formation, stability and dissociation dynamics of {{\\rm{N}}}_{2}{}^{{\\rm{n}}+} cations (n = 1 - 2) in 3.5 keV e - -N2 collisions studied using the energy resolved electron-ion coincidence technique

NASA Astrophysics Data System (ADS)

Kumar, S.; Prajapati, S.; Singh, B.; Singh, B. K.; Shanker, R.

2018-04-01

Coincidences between energy selected electrons and ions produced in the decay of a core hole ionized (excited) state in a free nitrogen molecule have been measured at three specified energies of emitted electrons to reveal the individual pathways produced in 3.5 keV electron-induced fragmentation processes. From these measurements, it has been possible to show, for the first time, that in addition to the normal Auger decay, the resonant Auger excitation channels also share their appreciable contributions in producing singly charged parent ions in an electron-induced collision system. The correlations between ion fragmentation products and electronic structures with a hole configuration in singly-, doubly- and possibly in triply charged molecular electronic states populated in the electronic decay of the initial core hole have been studied and discussed. KER values obtained from our experiments are found to be consistent with the previous results of photo absorption experiments for fragmentation channel {{{{N}}}2}2+ → N+ + N+ however, N2+ fragment ions are found to arise mainly from the fragmentation channel {{{{N}}}2}2+ → N2+ + N and to possess relatively low kinetic energies in the considered region of binding energies.

Kinetic theory molecular dynamics and hot dense matter: theoretical foundations.

PubMed

Graziani, F R; Bauer, J D; Murillo, M S

2014-09-01

Electrons are weakly coupled in hot, dense matter that is created in high-energy-density experiments. They are also mildly quantum mechanical and the ions associated with them are classical and may be strongly coupled. In addition, the dynamical evolution of plasmas under these hot, dense matter conditions involve a variety of transport and energy exchange processes. Quantum kinetic theory is an ideal tool for treating the electrons but it is not adequate for treating the ions. Molecular dynamics is perfectly suited to describe the classical, strongly coupled ions but not the electrons. We develop a method that combines a Wigner kinetic treatment of the electrons with classical molecular dynamics for the ions. We refer to this hybrid method as "kinetic theory molecular dynamics," or KTMD. The purpose of this paper is to derive KTMD from first principles and place it on a firm theoretical foundation. The framework that KTMD provides for simulating plasmas in the hot, dense regime is particularly useful since current computational methods are generally limited by their inability to treat the dynamical quantum evolution of the electronic component. Using the N-body von Neumann equation for the electron-proton plasma, three variations of KTMD are obtained. Each variant is determined by the physical state of the plasma (e.g., collisional versus collisionless). The first variant of KTMD yields a closed set of equations consisting of a mean-field quantum kinetic equation for the electron one-particle distribution function coupled to a classical Liouville equation for the protons. The latter equation includes both proton-proton Coulombic interactions and an effective electron-proton interaction that involves the convolution of the electron density with the electron-proton Coulomb potential. The mean-field approach is then extended to incorporate equilibrium electron-proton correlations through the Singwi-Tosi-Land-Sjolander (STLS) ansatz. This is the second variant of KTMD. The STLS contribution produces an effective electron-proton interaction that involves the electron-proton structure factor, thereby extending the usual mean-field theory to correlated but near equilibrium systems. Finally, a third variant of KTMD is derived. It includes dynamical electrons and their correlations coupled to a MD description for the ions. A set of coupled equations for the one-particle electron Wigner function and the electron-electron and electron-proton correlation functions are coupled to a classical Liouville equation for the protons. This latter variation has both time and momentum dependent correlations.

A comparative study of inelastic scattering models at energy levels ranging from 0.5 keV to 10 keV

NASA Astrophysics Data System (ADS)

Hu, Chia-Yu; Lin, Chun-Hung

2017-03-01

Six models, including a single-scattering model, four hybrid models, and one dielectric function model, were evaluated using Monte Carlo simulations for aluminum and copper at incident beam energies ranging from 0.5 keV to 10 keV. The inelastic mean free path, mean energy loss per unit path length, and backscattering coefficients obtained by these models are compared and discussed to understand the merits of the various models. ANOVA (analysis of variance) statistical models were used to quantify the effects of inelastic cross section and energy loss models on the basis of the simulated results deviation from the experimental data for the inelastic mean free path, the mean energy loss per unit path length, and the backscattering coefficient, as well as their correlations. This work in this study is believed to be the first application of ANOVA models towards evaluating inelastic electron beam scattering models. This approach is an improvement over the traditional approach which involves only visual estimation of the difference between the experimental data and simulated results. The data suggests that the optimization of the effective electron number per atom, binding energy, and cut-off energy of an inelastic model for different materials at different beam energies is more important than the selection of inelastic models for Monte Carlo electron scattering simulation. During the simulations, parameters in the equations should be tuned according to different materials for different beam energies rather than merely employing default parameters for an arbitrary material. Energy loss models and cross-section formulas are not the main factors influencing energy loss. Comparison of the deviation of the simulated results from the experimental data shows a significant correlation (p < 0.05) between the backscattering coefficient and energy loss per unit path length. The inclusion of backscattering electrons generated by both primary and secondary electrons for backscattering coefficient simulation is recommended for elements with high atomic numbers. In hybrid models, introducing the inner shell ionization model improves the accuracy of simulated results.

Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO2 glasses.

PubMed

Sato, K; Hatta, T

2015-03-07

Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO2 glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

Combining Density Functional Theory and Green's Function Theory: Range-Separated, Nonlocal, Dynamic, and Orbital-Dependent Hybrid Functional.

PubMed

Kananenka, Alexei A; Zgid, Dominika

2017-11-14

We present a rigorous framework which combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short- and long-range components. Short-range contribution to the total energy and exchange-correlation potential is provided by a density functional approximation, while the long-range contribution is calculated using an explicit many-body Green's function method. Such a hybrid results in a nonlocal, dynamic, and orbital-dependent exchange-correlation functional of a single-particle Green's function. In particular, we present a range-separated hybrid functional called srSVWN5-lrGF2 which combines the local-density approximation and the second-order Green's function theory. We illustrate that similarly to density functional approximations, the new functional is weakly basis-set dependent. Furthermore, it offers an improved description of the short-range dynamic correlation. The many-body contribution to the functional mitigates the many-electron self-interaction error present in many density functional approximations and provides a better description of molecular properties. Additionally, we illustrate that the new functional can be used to scale down the self-energy and, therefore, introduce an additional sparsity to the self-energy matrix that in the future can be exploited in calculations for large molecules or periodic systems.

Electronic and optical properties of hexathiapentacene in the gas and crystal phases

NASA Astrophysics Data System (ADS)

Cardia, R.; Malloci, G.; Rignanese, G.-M.; Blase, X.; Molteni, E.; Cappellini, G.

2016-06-01

Using density functional theory (DFT) and its time-dependent (TD) extension, the electronic and optical properties of the hexathiapentacene (HTP) molecule, a derivative of pentacene (PNT) obtained by symmetric substitution of the six central H atoms with S atoms, are investigated for its gas and solid phases. For the molecular structure, all-electron calculations are performed using a Gaussian localized orbital basis set in conjunction with the Becke three-parameter Lee-Yang-Parr (B3LYP) hybrid exchange-correlation functional. Electron affinities, ionization energies, quasiparticle energy gaps, optical absorption spectra, and exciton binding energies are calculated and compared with the corresponding results for PNT, as well as with the available experimental data. The DFT and TDDFT results are also validated by performing many-body perturbation theory calculations within the G W and Bethe-Salpeter equation formalisms. The functionalization with S atoms induces an increase of both ionization energies and electron affinities, a sizable reduction of the fundamental electronic gap, and a redshift of the optical absorption onset. Notably, the intensity of the first absorption peak of HTP falling in the visible region is found to be nearly tripled with respect to the pure PNT molecule. For the crystal structures, pseudopotential calculations are adopted using a plane-wave basis set together with the Perdew-Burke-Ernzerhof exchange-correlation functional empirically corrected in order to take dispersive interactions into account. The electronic excitations are also obtained within a perturbative B3LYP scheme. A comparative analysis is carried out between the ground-state and excited-state properties of crystalline HTP and PNT linking to the findings obtained for the isolated molecules.

Enhanced photoelectrochemical activity in all-oxide heterojunction devices based on correlated "metallic" oxides.

PubMed

Apgar, Brent A; Lee, Sungki; Schroeder, Lauren E; Martin, Lane W

2013-11-20

n-n Schottky, n-n ohmic, and p-n Schottky heterojunctions based on TiO2 /correlated "metallic" oxide couples exhibit strong solar-light absorption driven by the unique electronic structure of the "metallic" oxides. Photovoltaic and photocatalytic responses are driven by hot electron injection from the "metallic" oxide into the TiO2 , enabling new modalities of operation for energy systems. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

orbital selective correlation reduce in collapse tetragonal phase of CaFe2(As0.935P0.065)2 and electronic structure reconstruction studied by angel resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Zeng, Lingkun

We performed an angle-resolved photoemission spectroscopy (ARPES) study of the CaFe2(As0.935P0.065)2 in the collapse tetragonal(CT) phase and uncollapse tetragonal(UCT) phase. We find in the CT phase the electronic correlation dramatically reduces respective to UCT phase. Meanwhile, the reduction of correlation in CT phase show an orbital selective effect: correlation in dxy reduces the most, and then dxz/yz, while the one in dz2-r2 almost keeps the same. In CT phase, almost all bands sink downwards to higher binding energy, leading to the hole like bands around Brillouin zone(BZ) center sink below EF compared with UCT phase. However, the electron pocket around Brillouin Zone(BZ) corner(M) in UCT phase, forms a hole pocket around BZ center(Z point) in CT phase. Moreover, the dxy exhibits larger movement down to higher binding energy, resulting in farther away from dyz/xz and closer to dxy.We propose the electron filling ,namely high spin state in UCT phase to low spin state in CT phase(due to competing between crystal structure field and Hund's coupling), other than the Fermi surface nesting might be responsible for the absent of magnetic ordering.

Single-Photon, Double Photodetachment of Nickel Phthalocyanine Tetrasulfonic Acid 4- Anions.

PubMed

Daly, Steven; Girod, Marion; Vojkovic, Marin; Giuliani, Alexandre; Antoine, Rodolphe; Nahon, Laurent; O'Hair, Richard A J; Dugourd, Philippe

2016-07-07

Single-photon, two-electron photodetachment from nickel phthalocyanine tetrasulfonic acid tetra anions, [NiPc](4-), was examined in the gas-phase using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. This system was chosen since it has a low detachment energy, known charge localization, and well-defined geometrical and electronic structures. A threshold for two-electron loss is observed at 10.2 eV, around 1 eV lower than previously observed double detachment thresholds on multiple charged protein anions. The photodetachment energy of [NiPc](4-) has been previously determined to be 3.5 eV and the photodetachment energy of [NiPc](3-•) is determined in this work to be 4.3 eV. The observed single photon double electron detachment threshold is hence 5.9 eV higher than the energy required for sequential single electron loss. Possible mechanisms are for double photodetachment are discussed. These observations pave the way toward new, exciting experiments for probing double photodetachment at relatively low energies, including correlation measurements on emitted photoelectrons.

Footprints of electron correlation in strong-field double ionization of Kr close to the sequential-ionization regime

NASA Astrophysics Data System (ADS)

Li, Xiaokai; Wang, Chuncheng; Yuan, Zongqiang; Ye, Difa; Ma, Pan; Hu, Wenhui; Luo, Sizuo; Fu, Libin; Ding, Dajun

2017-09-01

By combining kinematically complete measurements and a semiclassical Monte Carlo simulation we study the correlated-electron dynamics in the strong-field double ionization of Kr. Interestingly, we find that, as we step into the sequential-ionization regime, there are still signatures of correlation in the two-electron joint momentum spectrum and, more intriguingly, the scaling law of the high-energy tail is completely different from early predictions on the low-Z atom (He). These experimental observations are well reproduced by our generalized semiclassical model adapting a Green-Sellin-Zachor potential. It is revealed that the competition between the screening effect of inner-shell electrons and the Coulomb focusing of nuclei leads to a non-inverse-square central force, which twists the returned electron trajectory at the vicinity of the parent core and thus significantly increases the probability of hard recollisions between two electrons. Our results might have promising applications ranging from accurately retrieving atomic structures to simulating celestial phenomena in the laboratory.

Communication: Understanding molecular representations in machine learning: The role of uniqueness and target similarity

NASA Astrophysics Data System (ADS)

Huang, Bing; von Lilienfeld, O. Anatole

2016-10-01

The predictive accuracy of Machine Learning (ML) models of molecular properties depends on the choice of the molecular representation. Inspired by the postulates of quantum mechanics, we introduce a hierarchy of representations which meet uniqueness and target similarity criteria. To systematically control target similarity, we simply rely on interatomic many body expansions, as implemented in universal force-fields, including Bonding, Angular (BA), and higher order terms. Addition of higher order contributions systematically increases similarity to the true potential energy and predictive accuracy of the resulting ML models. We report numerical evidence for the performance of BAML models trained on molecular properties pre-calculated at electron-correlated and density functional theory level of theory for thousands of small organic molecules. Properties studied include enthalpies and free energies of atomization, heat capacity, zero-point vibrational energies, dipole-moment, polarizability, HOMO/LUMO energies and gap, ionization potential, electron affinity, and electronic excitations. After training, BAML predicts energies or electronic properties of out-of-sample molecules with unprecedented accuracy and speed.

Correlation effects in elastic e-N2 scattering

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Lima, Marco A. P.; Gibson, Thomas L.; Mckoy, Vincent

1987-01-01

The Schwinger multichannel formulation has been applied to study the role of electron correlation in low-energy e-N2 scattering. For the five nonresonant partial-wave channels studied here, angular correlation is found to be much more important than radial correlation. The calculated total and differential cross sections agree well with experiment except for the differential cross sections at 1.5 eV.

Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials

NASA Astrophysics Data System (ADS)

Jin, Ye; Yang, Yang; Zhang, Du; Peng, Degao; Yang, Weitao

2017-10-01

The optimized effective potential (OEP) that gives accurate Kohn-Sham (KS) orbitals and orbital energies can be obtained from a given reference electron density. These OEP-KS orbitals and orbital energies are used here for calculating electronic excited states with the particle-particle random phase approximation (pp-RPA). Our calculations allow the examination of pp-RPA excitation energies with the exact KS density functional theory (DFT). Various input densities are investigated. Specifically, the excitation energies using the OEP with the electron densities from the coupled-cluster singles and doubles method display the lowest mean absolute error from the reference data for the low-lying excited states. This study probes into the theoretical limit of the pp-RPA excitation energies with the exact KS-DFT orbitals and orbital energies. We believe that higher-order correlation contributions beyond the pp-RPA bare Coulomb kernel are needed in order to achieve even higher accuracy in excitation energy calculations.

Sum-rule corrections: A route to error cancellations in correlation matrix renormalisation theory

DOE PAGES

Liu, C.; Liu, J.; Yao, Y. X.; ...

2017-01-16

Here, we recently proposed the correlation matrix renormalisation (CMR) theory to efficiently and accurately calculate ground state total energy of molecular systems, based on the Gutzwiller variational wavefunction (GWF) to treat the electronic correlation effects. To help reduce numerical complications and better adapt the CMR to infinite lattice systems, we need to further refine the way to minimise the error originated from the approximations in the theory. This conference proceeding reports our recent progress on this key issue, namely, we obtained a simple analytical functional form for the one-electron renormalisation factors, and introduced a novel sum-rule correction for a moremore » accurate description of the intersite electron correlations. Benchmark calculations are performed on a set of molecules to show the reasonable accuracy of the method.« less

Sum-rule corrections: A route to error cancellations in correlation matrix renormalisation theory

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

Liu, C.; Liu, J.; Yao, Y. X.

Here, we recently proposed the correlation matrix renormalisation (CMR) theory to efficiently and accurately calculate ground state total energy of molecular systems, based on the Gutzwiller variational wavefunction (GWF) to treat the electronic correlation effects. To help reduce numerical complications and better adapt the CMR to infinite lattice systems, we need to further refine the way to minimise the error originated from the approximations in the theory. This conference proceeding reports our recent progress on this key issue, namely, we obtained a simple analytical functional form for the one-electron renormalisation factors, and introduced a novel sum-rule correction for a moremore » accurate description of the intersite electron correlations. Benchmark calculations are performed on a set of molecules to show the reasonable accuracy of the method.« less

Bursty Precipitation Driven by Chorus Waves

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Telnikhin, A. A.; Kronberg, T. K.

2011-01-01

The electron precipitation bursts have been shown to be a major sink for the radiation belt relativistic electrons. As underlying mechanism of such bursts, we propose particle scattering into the loss cone due to nonlinear resonance interaction between electrons and chorus. Stochastic heating due to the coupling leads to diffusion in pitch angle, and the rate of diffusion would be sufficient to account for the emptying of the Earth's radiation belt over the time of the main phase of geomagnetic storms. The results obtained in the present paper account for a strong energy dependence in the electron precipitation event and the correlation between the energization and loss processes on macroscopic timescales, which is primarily attributed to the cooperative effects of the coupling. This mechanism of chorus scattering should produce pitch angle distributions that are energy-dependent and butterfly-shaped. The calculated timescales and the total energy input to the atmosphere from precipitating relativistic electrons are in reasonable agreement with experimental data.

Electronic reconstruction of doped Mott insulator heterojunctions

NASA Astrophysics Data System (ADS)

Charlebois, M.; Hassan, S. R.; Karan, R.; Dion, M.; Senechal, D.; Tremblay, A.-M. S.

2012-02-01

Correlated electron heterostructures became a possible alternative when thin-film deposition techniques achieved structures with a sharp interface transition [1]. Soon thereafter, Okamoto & Millis introduced the concept of ``electronic reconstruction'' [2]. We study here the electronic reconstruction of doped Mott insulator heterostructures based on a Cluster Dynamical Mean Field Theory (CDMFT) calculations of the Hubbard model in the limit where electrostatic energy dominates over the kinetic energy associated with transport across layers. The grand potential of individual layers is first computed within CDMFT and then the electrostatic potential energy is taken into account in the Hartree approximation. The charge reconstruction in an ensemble of stacked planes of different nature can lead to a distribution of electron charge and to transport properties that are unique to doped-Mott insulators.[4pt] [1] J. Mannhart, D. G. Schlom, Science 327, 1607 (2010).[0pt] [2] S. Okamoto and A. J. Millis, Nature 428, 630 (2004).

Electronic properties of III-nitride semiconductors: A first-principles investigation using the Tran-Blaha modified Becke-Johnson potential

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

Araujo, Rafael B., E-mail: rafaelbna@gmail.com; Almeida, J. S. de, E-mail: jailton-almeida@hotmail.com; Ferreira da Silva, A.

In this work, we use density functional theory to investigate the influence of semilocal exchange and correlation effects on the electronic properties of III-nitride semiconductors considering zinc-blende and wurtzite crystal structures. We find that the inclusion of such effects through the use of the Tran-Blaha modified Becke-Johnson potential yields an excellent description of the electronic structures of these materials giving energy band gaps which are systematically larger than the ones obtained with standard functionals such as the generalized gradient approximation. The discrepancy between the experimental and theoretical band gaps is then significantly reduced with semilocal exchange and correlation effects. However,more » the effective masses are overestimated in the zinc-blende nitrides, but no systematic trend is found in the wurtzite compounds. New results for energy band gaps and effective masses of zinc-blende and wurtzite indium nitrides are presented.« less

Estimate of the Coulomb correlation energy in CeAg2Ge2 from inverse photoemission and high resolution photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Banik, Soma; Arya, A.; Bendounan, Azzedine; Maniraj, M.; Thamizhavel, A.; Vobornik, I.; Dhar, S. K.; Deb, S. K.

2014-08-01

The occupied and the unoccupied electronic structure of CeAg2Ge2 single crystal has been studied using high resolution photoemission and inverse photoemission spectroscopy, respectively. High resolution photoemission reveals the clear signature of Ce 4f states in the occupied electronic structure which was not observed clearly in our earlier studies. The Coulomb correlation energy in this system has been determined experimentally from the position of the 4f states above and below the Fermi level. Theoretically, the correlation energy has been determined by using the first principles density functional calculations within the generalized gradient approximations taking into account the strong intra-atomic (on-site) interaction Hubbard Ueff term. The calculated valence band shows minor changes in the spectral shape with increasing Ueff due to the fact that the density of Ce 4f state is narrow in the occupied part and is hybridized with the Ce 5d, Ag 4d and Ge 4p states. On the other hand, substantial changes are observed in the spectral shape of the calculated conduction band with increasing Ueff since the density of Ce 4f state is very large in the unoccupied part, compared to other states. The estimated value of correlation energy for CeAg2Ge2 from the experiment and the theory is ≈ 4.2 eV. The resonant photoemission data are analyzed in the framework of the single-impurity Anderson model which further confirms the presence of the Coulomb correlation energy and small hybridization in this system.

Bound and resonance states of positronic copper atoms

NASA Astrophysics Data System (ADS)

Yamashita, Takuma; Umair, Muhammad; Kino, Yasushi

2017-10-01

We report a theoretical calculation for the bound and S-wave resonance states of the positronic copper atom (e+Cu). A positron is a positively charged particle; therefore, a positronic atom has an attractive correlation between the positron and electron. A Gaussian expansion method is adopted to directly describe this correlation as well as the strong repulsive interaction with the nucleus. The correlation between the positron and electron is much more important than that between electrons in an analogous system of Cu-, although the formation of a positronium (Ps) in e+Cu is not expressed in the ground state structure explicitly. Resonance states are calculated with a complex scaling method and identified above the first excited state of the copper atom. Resonance states below Ps (n = 2) + Cu+ classified to a dipole series show agreement with a simple analytical law. Comparison of the resonance energies and widths of e+Cu with those of e+K, of which the potential energy of the host atom resembles that of e+Cu, reveals that the positions of the resonance for the e+Cu dipole series deviate equally from those of e+K.

Weak-coupling superconductivity in a strongly correlated iron pnictide

PubMed Central

Charnukha, A.; Post, K. W.; Thirupathaiah, S.; Pröpper, D.; Wurmehl, S.; Roslova, M.; Morozov, I.; Büchner, B.; Yaresko, A. N.; Boris, A. V.; Borisenko, S. V.; Basov, D. N.

2016-01-01

Iron-based superconductors have been found to exhibit an intimate interplay of orbital, spin, and lattice degrees of freedom, dramatically affecting their low-energy electronic properties, including superconductivity. Albeit the precise pairing mechanism remains unidentified, several candidate interactions have been suggested to mediate the superconducting pairing, both in the orbital and in the spin channel. Here, we employ optical spectroscopy (OS), angle-resolved photoemission spectroscopy (ARPES), ab initio band-structure, and Eliashberg calculations to show that nearly optimally doped NaFe0.978Co0.022As exhibits some of the strongest orbitally selective electronic correlations in the family of iron pnictides. Unexpectedly, we find that the mass enhancement of itinerant charge carriers in the strongly correlated band is dramatically reduced near the Γ point and attribute this effect to orbital mixing induced by pronounced spin-orbit coupling. Embracing the true band structure allows us to describe all low-energy electronic properties obtained in our experiments with remarkable consistency and demonstrate that superconductivity in this material is rather weak and mediated by spin fluctuations. PMID:26729630

Iridates and RuCl3 - from Heisenberg antiferromagnets to potential Kitaev spin-liquids

NASA Astrophysics Data System (ADS)

van den Brink, Jeroen

The observed richness of topological states on the single-electron level prompts the question what kind of topological phases can develop in more strongly correlated, many-body electron systems. Correlation effects, in particular intra- and inter-orbital electron-electron interactions, are very substantial in 3 d transition-metal compounds such as the copper oxides, but the spin-orbit coupling (SOC) is weak. In 5 d transition-metal compounds such as iridates, the interesting situation arises that the SOC and Coulomb interactions meet on the same energy scale. The electronic structure of iridates thus depends on a strong competition between the electronic hopping amplitudes, local energy-level splittings, electron-electron interaction strengths, and the SOC of the Ir 5d electrons. The interplay of these ingredients offers the potential to stabilise relatively well-understood states such as a 2D Heisenberg-like antiferromagnet in Sr2IrO4, but in principle also far more exotic ones, such a topological Kitaev quantum spin liquid, in (hyper)honeycomb iridates. I will discuss the microscopic electronic structures of these iridates, their proximity to idealized Heisenberg and Kitaev models and our contributions to establishing the physical factors that appear to have preempted the realization of quantum spin liquid phases so far and include a discussion on the 4d transition metal chloride RuCl3. Supported by SFB 1143 of the Deutsche Forschungsgemeinschaft.

Comparison Between Path Lengths Traveled by Solar Electrons and Ions in Ground-Level Enhancement Events

NASA Technical Reports Server (NTRS)

Tan, Lun C.; Malandraki, Olga E.; Reames, Donald; NG, Chee K.; Wang, Linghua; Patsou, Ioanna; Papaioannou, Athanasios

2013-01-01

We have examined the Wind/3DP/SST electron and Wind/EPACT/LEMT ion data to investigate the path length difference between solar electrons and ions in the ground-level enhancement (GLE) events in solar cycle 23. Assuming that the onset time of metric type II or decameter-hectometric (DH) type III radio bursts is the solar release time of non-relativistic electrons, we have found that within an error range of plus or minus 10% the deduced path length of low-energy (approximately 27 keV) electrons from their release site near the Sun to the 1 AU observer is consistent with the ion path length deduced by Reames from the onset time analysis. In addition, the solar longitude distribution and IMF topology of the GLE events examined are in favor of the coronal mass ejection-driven shock acceleration origin of observed non-relativistic electrons.We have also found an increase of electron path lengths with increasing electron energies. The increasing rate of path lengths is correlated with the pitch angle distribution (PAD) of peak electron intensities locally measured, with a higher rate corresponding to a broader PAD. The correlation indicates that the path length enhancement is due to the interplanetary scattering experienced by first arriving electrons. The observed path length consistency implies that the maximum stable time of magnetic flux tubes, along which particles transport, could reach 4.8 hr.

Dual roles of f electrons in mixing Al 3 p character into d -orbital conduction bands for lanthanide and actinide dialuminides

DOE PAGES

Altman, Alison B.; Pemmaraju, C. D.; Alayoglu, Selim; ...

2018-01-15

Correlated electron phenomena in lanthanide and actinide materials are driven by a complex interplay between the f and d orbitals. Here in this study, aluminum K-edge x-ray absorption spectroscopy and density functional theory calculations are used to evaluate the electronic structure of the dialuminides, MAl 2 (M = Ce, Sm, Eu, Yb, Lu, U, and Pu). The results show how the energy and occupancy of the 4f or 5f orbitals impacts mixing of Al 3p character into the 5d or 6d conduction bands, which has implications for understanding the magnetic and structural properties of correlated electron systems.

On the contribution of vibrational anharmonicity to the binding energies of water clusters.

PubMed

Diri, Kadir; Myshakin, Evgeniy M; Jordan, Kenneth D

2005-05-05

The second-order vibrational perturbation theory method has been used together with the B3LYP and MP2 electronic structure methods to investigate the effects of anharmonicity on the vibrational zero-point energy (ZPE) contributions to the binding energies of (H2O)n, n = 2-6, clusters. For the low-lying isomers of (H2O)6, the anharmonicity correction to the binding energy is calculated to range from -248 to -355 cm(-1). It is also demonstrated that although high-order electron correlation effects are important for the individual vibrational frequencies, they are relatively unimportant for the net ZPE contributions to the binding energies of water clusters.

Relativistic particles and gamma-ray in quasars and active galactic nuclei

NASA Technical Reports Server (NTRS)

Protheroe, R. J.; Kazanas, D.

1982-01-01

A model for a class of quasars and active galactic nuclei is described in which a shock around a massive black hole randomizes the infall kinetic energy of spherically accreting matter producing a nonthermal spectrum of high energy protons. These protons may be responsible for the secondary production (via tau + or - decay) of the radio emitting high energy electrons and also of high energy gamma rays (via pi decay and inverse Compton interactions of the electrons). The correlation between radio and gamma ray emission implied by the model is in good agreement with observations of 3C273. Observation of the flux of high energy neutrinos from quasars may provide a test for the model.

Relativistic particles and gamma-rays in quasars and active galactic nuclei

NASA Technical Reports Server (NTRS)

Protheroe, R. J.; Kazanas, D.

1983-01-01

A model for a class of quasars and active galactic nuclei is described in which a shock around a massive black hole randomizes the infall kinetic energy of spherically accreting matter producing a nonthermal spectrum of high energy protons. These protons may be responsible for the secondary production (via tau + or - decay) of the radio emitting high energy electrons and also of high energy gamma rays (via Pi decay and inverse Compton interactions of the electrons). The correlation between radio and gamma ray emission implied by the model is in good agreement with observations of 3C273. Observation of the flux of high energy neutrinos from quasars may provide a test for the model.

Influence of magnetism and correlation on the spectral properties of doped Mott insulators

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

Wang, Yao; Moritz, Brian; Chen, Cheng-Chien

Unraveling the nature of the doping-induced transition between a Mott insulator and a weakly correlated metal is crucial to understanding novel emergent phases in strongly correlated materials. Here, for this purpose, we study the evolution of spectral properties upon doping Mott insulating states by utilizing the cluster perturbation theory on the Hubbard and t – J -like models. Specifically, a quasifree dispersion crossing the Fermi level develops with small doping, and it eventually evolves into the most dominant feature at high doping levels. Although this dispersion is related to the free-electron hopping, our study shows that this spectral feature is,more » in fact, influenced inherently by both electron-electron correlation and spin-exchange interaction: the correlation destroys coherence, while the coupling between spin and mobile charge restores it in the photoemission spectrum. Due to the persistent impact of correlations and spin physics, the onset of gaps or the high-energy anomaly in the spectral functions can be expected in doped Mott insulators.« less

Influence of magnetism and correlation on the spectral properties of doped Mott insulators

DOE PAGES

Wang, Yao; Moritz, Brian; Chen, Cheng-Chien; ...

2018-03-01

Unraveling the nature of the doping-induced transition between a Mott insulator and a weakly correlated metal is crucial to understanding novel emergent phases in strongly correlated materials. Here, for this purpose, we study the evolution of spectral properties upon doping Mott insulating states by utilizing the cluster perturbation theory on the Hubbard and t – J -like models. Specifically, a quasifree dispersion crossing the Fermi level develops with small doping, and it eventually evolves into the most dominant feature at high doping levels. Although this dispersion is related to the free-electron hopping, our study shows that this spectral feature is,more » in fact, influenced inherently by both electron-electron correlation and spin-exchange interaction: the correlation destroys coherence, while the coupling between spin and mobile charge restores it in the photoemission spectrum. Due to the persistent impact of correlations and spin physics, the onset of gaps or the high-energy anomaly in the spectral functions can be expected in doped Mott insulators.« less

Electronic structures of of PuX (X=S, Se, Te)

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Sakai, Eijiro; Tatetsu, Yasutomi

2013-08-01

We have calculated the energy band structures and the Fermi surfaces of PuS, PuSe, and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in the local density approximation. In general, the energy bands near the Fermi level are mainly caused by the hybridization between the Pu 5 f and the monochalcogenide p electrons. The obtained main Fermi surfaces consisted of two hole sheets and one electron sheet, which were constructed from the band having both the Pu 5 f state and the monochalcogenide p state.

Analysis of Multilayer Devices for Superconducting Electronics by High-Resolution Scanning Transmission Electron Microscopy and Energy Dispersive Spectroscopy

DOE PAGES

Missert, Nancy; Kotula, Paul G.; Rye, Michael; ...

2017-02-15

We used a focused ion beam to obtain cross-sectional specimens from both magnetic multilayer and Nb/Al-AlOx/Nb Josephson junction devices for characterization by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX). An automated multivariate statistical analysis of the EDX spectral images produced chemically unique component images of individual layers within the multilayer structures. STEM imaging elucidated distinct variations in film morphology, interface quality, and/or etch artifacts that could be correlated to magnetic and/or electrical properties measured on the same devices.

Clar's sextet rule is a consequence of the sigma-electron framework.

PubMed

Maksić, Zvonimir B; Barić, Danijela; Müller, Thomas

2006-08-24

A number of condensed PAHs are examined to identify the underlying reasons governing empirical Clar's rule taking benzene as a limiting case. It is found that the so-called Clar's structures are the only minima on the MP2(fc) potential energy hypersurfaces, meaning that other conceivable valence isomers are nonexistent. The influence of the electron correlation energies to the stability of Clar's structures is substantial with predominating influence of the sigma-electrons. However, the contributions arising from the sigma- and pi-electron correlation energies are approximately the same, if Clar's structures are compared with some artificial pi-electron localized or graphite-like delocalized planar systems. Analysis of the Hartree-Fock (HF) energies provides a compelling evidence that the origin of stability of Clar's structures lies in a decrease of the positive T, V(ee) and V(nn) energy terms relative to some characteristic virtual "delocalized" or "localized" model geometries. Partitioning of the mixed and terms in the sigma- and pi-type contributions, by using the stockholder (SHR), equipartitioning (EQP) and standard pi (SPI) schemes, unequivocally shows that the driving force leading to Clar's structures are more favorable sigma-type interactions. All these conclusions hold for the archetypal benzene too, which could be considered as a limiting Clar system. Finally, the boundaries of Clar's hypothesis and some common misconceptions are briefly discussed. Perusal of the geometric parameters and pi-bond orders reveals that there are no benzene rings completely "vacant" or "fully occupied" by the pi-electrons, envisaged by Clar in his picture of condensed benzenoid compounds. Instead, there are six-membered rings with higher and lower total pi-electron density. The bond length anisotropy of the former rings is smaller. It is concluded that Clar's proposition is a useful rule of thumb providing qualitative information on the stability of the PAH systems, which in turn should not be overinterpreted.

Microscopic origin of magnetism and magnetic interactions in ferropnictides

NASA Astrophysics Data System (ADS)

Johannes, M. D.; Mazin, I. I.

2009-06-01

One year after their initial discovery, two schools of thought have crystallized regarding the electronic structure and magnetic properties of ferropnictide systems. One postulates that these are itinerant weakly correlated metallic systems that become magnetic by virtue of spin-Peierls-type transition due to near nesting between the hole and the electron Fermi-surface pockets. The other argues that these materials are strongly or at least moderately correlated and the electrons are considerably localized and close to a Mott-Hubbard transition, with the local magnetic moments interacting via short-range superexchange. In this Rapid Communication we argue that neither picture is fully correct. The systems are moderately correlated but with correlations driven by Hund’s rule coupling rather than by the on-site Hubbard repulsion. The iron moments are largely local, driven by Hund’s intra-atomic exchange. Superexchange is not operative, and the interactions between the Fe moments are considerably long range and driven mostly by one-electron energies of all occupied states.

Accurate Exchange-Correlation Energies for the Warm Dense Electron Gas.

PubMed

Malone, Fionn D; Blunt, N S; Brown, Ethan W; Lee, D K K; Spencer, J S; Foulkes, W M C; Shepherd, James J

2016-09-09

The density matrix quantum Monte Carlo (DMQMC) method is used to sample exact-on-average N-body density matrices for uniform electron gas systems of up to 10^{124} matrix elements via a stochastic solution of the Bloch equation. The results of these calculations resolve a current debate over the accuracy of the data used to parametrize finite-temperature density functionals. Exchange-correlation energies calculated using the real-space restricted path-integral formalism and the k-space configuration path-integral formalism disagree by up to ∼10% at certain reduced temperatures T/T_{F}≤0.5 and densities r_{s}≤1. Our calculations confirm the accuracy of the configuration path-integral Monte Carlo results available at high density and bridge the gap to lower densities, providing trustworthy data in the regime typical of planetary interiors and solids subject to laser irradiation. We demonstrate that the DMQMC method can calculate free energies directly and present exact free energies for T/T_{F}≥1 and r_{s}≤2.

Electron momentum density and Compton profile by a semi-empirical approach

NASA Astrophysics Data System (ADS)

Aguiar, Julio C.; Mitnik, Darío; Di Rocco, Héctor O.

2015-08-01

Here we propose a semi-empirical approach to describe with good accuracy the electron momentum densities and Compton profiles for a wide range of pure crystalline metals. In the present approach, we use an experimental Compton profile to fit an analytical expression for the momentum densities of the valence electrons. This expression is similar to a Fermi-Dirac distribution function with two parameters, one of which coincides with the ground state kinetic energy of the free-electron gas and the other resembles the electron-electron interaction energy. In the proposed scheme conduction electrons are neither completely free nor completely bound to the atomic nucleus. This procedure allows us to include correlation effects. We tested the approach for all metals with Z=3-50 and showed the results for three representative elements: Li, Be and Al from high-resolution experiments.

Wave-function-based approach to quasiparticle bands: Insight into the electronic structure of c-ZnS

NASA Astrophysics Data System (ADS)

Stoyanova, A.; Hozoi, L.; Fulde, P.; Stoll, H.

2011-05-01

Ab initio wave-function-based methods are employed for the study of quasiparticle energy bands of zinc-blende ZnS, with focus on the Zn 3d “semicore” states. The relative energies of these states with respect to the top of the S 3p valence bands appear to be poorly described as compared to experimental values not only within the local density approximation (LDA), but also when many-body corrections within the GW approximation are applied to the LDA or LDA + U mean-field solutions [T. Miyake, P. Zhang, M. L. Cohen, and S. G. Louie, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.74.245213 74, 245213 (2006)]. In the present study, we show that for the accurate description of the Zn 3d states a correlation treatment based on wave-function methods is needed. Our study rests on a local Hamiltonian approach which rigorously describes the short-range polarization and charge redistribution effects around an extra hole or electron placed into the valence respective conduction bands of semiconductors and insulators. The method also facilitates the computation of electron correlation effects beyond relaxation and polarization. The electron correlation treatment is performed on finite clusters cut off the infinite system. The formalism makes use of localized Wannier functions and embedding potentials derived explicitly from prior periodic Hartree-Fock calculations. The on-site and nearest-neighbor charge relaxation lead to corrections of several eV to the Hartree-Fock band energies and gap. Corrections due to long-range polarization are of the order of 1.0 eV. The dispersion of the Hartree-Fock bands is only slightly affected by electron correlations. We find the Zn 3d “semicore” states to lie ~9.0 eV below the top of the S 3p valence bands, in very good agreement with values from valence-band x-ray photoemission.

Quantum chemical study of relative reactivities of a series of amines and nitriles - Relevance to prebiotic chemistry

NASA Technical Reports Server (NTRS)

Loew, G. H.; Berkowitz, D.; Chang, S.

1975-01-01

Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.

Pitch angle scattering of relativistic electrons from stationary magnetic waves: Continuous Markov process and quasilinear theory

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

Lemons, Don S.

2012-01-15

We develop a Markov process theory of charged particle scattering from stationary, transverse, magnetic waves. We examine approximations that lead to quasilinear theory, in particular the resonant diffusion approximation. We find that, when appropriate, the resonant diffusion approximation simplifies the result of the weak turbulence approximation without significant further restricting the regime of applicability. We also explore a theory generated by expanding drift and diffusion rates in terms of a presumed small correlation time. This small correlation time expansion leads to results valid for relatively small pitch angle and large wave energy density - a regime that may govern pitchmore » angle scattering of high-energy electrons into the geomagnetic loss cone.« less

Detector Development for the abBA Experiment.

PubMed

Seo, P-N; Bowman, J D; Mitchell, G S; Penttila, S I; Wilburn, W S

2005-01-01

We have developed a new type of field-expansion spectrometer to measure the neutron beta decay correlations (a, b, B, and A). A precision measurement of these correlations places stringent requirements on charged particle detectors. The design employs large area segmented silicon detectors to detect both protons and electrons in coincidence. Other requirements include good energy resolution (< 5 keV), a thin dead layer to allow observation of 30-keV protons, fast timing resolution (~1 ns) to reconstruct electron-backscattering events, and nearly unity efficiency. We report results of testing commercially available surface-barrier silicon detectors for energy resolution and timing performance, and measurement of the dead-layer thickness of ion-implanted silicon detectors with a 3.2 MeV alpha source.

APES: Acute Precipitating Electron Spectrometer - A High Time Resolution Monodirectional Magnetic Deflection Electron Spectrometer

NASA Technical Reports Server (NTRS)

Michell, R. G.; Samara, M.; Grubbs, G., II; Ogasawara, K.; Miller, G.; Trevino, J. A.; Webster, J.; Stange, J.

2016-01-01

We present a description of the Acute Precipitating Electron Spectrometer (APES) that was designed and built for the Ground-to-Rocket Electron Electrodynamics Correlative Experiment (GREECE) auroral sounding rocket mission. The purpose was to measure the precipitating electron spectrum with high time resolution, on the order of milliseconds. The trade-off made in order to achieve high time resolution was to limit the aperture to only one look direction. The energy selection was done by using a permanent magnet to separate the incoming electrons, such that the different energies would fall onto different regions of the microchannel plate and therefore be detected by different anodes. A rectangular microchannel plate (MCP) was used (15 mm x 100 mm), and there was a total of 50 discrete anodes under the MCP, each one 15 mm x 1.5 mm, with a 0.5 mm spacing between anodes. The target energy range of APES was 200 eV to 30 keV.

Proton affinity and enthalpy of formation of formaldehyde

NASA Astrophysics Data System (ADS)

Czakó, Gábor; Nagy, Balázs; Tasi, Gyula; Somogyi, Árpád; Šimunek, Ján; Noga, Jozef; Braams, Bastiaan J.; Bowman, Joel M.; Császár; , Attila G.

The proton affinity and the enthalpy of formation of the prototypical carbonyl, formaldehyde, have been determined by the first-principles composite focal-point analysis (FPA) approach. The electronic structure computations employed the all-electron coupled-cluster method with up to single, double, triple, quadruple, and even pentuple excitations. In these computations the aug-cc-p(C)VXZ [X = 2(D), 3(T), 4(Q), 5, and 6] correlation-consistent Gaussian basis sets for C and O were used in conjunction with the corresponding aug-cc-pVXZ (X = 2-6) sets for H. The basis set limit values have been confirmed via explicitly correlated computations. Our FPA study supersedes previous computational work for the proton affinity and to some extent the enthalpy of formation of formaldehyde by accounting for (a) electron correlation beyond the "gold standard" CCSD(T) level; (b) the non-additivity of core electron correlation effects; (c) scalar relativity; (d) diagonal Born-Oppenheimer corrections computed at a correlated level; (e) anharmonicity of zero-point vibrational energies, based on global potential energy surfaces and variational vibrational computations; and (f) thermal corrections to enthalpies by direct summation over rovibrational energy levels. Our final proton affinities at 298.15 (0.0) K are ΔpaHo (H2CO) = 711.02 (704.98) ± 0.39 kJ mol-1. Our final enthalpies of formation at 298.15 (0.0) K are ΔfHo (H2CO) = -109.23 (-105.42) ± 0.33 kJ mol-1. The latter values are based on the enthalpy of the H2 + CO → H2CO reaction but supported by two further reaction schemes, H2O + C → H2CO and 2H + C + O → H2CO. These values, especially ΔpaHo (H2CO), have better accuracy and considerably lower uncertainty than the best previous recommendations and thus should be employed in future studies.

Relativistic coupled-cluster-theory analysis of energies, hyperfine-structure constants, and dipole polarizabilities of Cd+

NASA Astrophysics Data System (ADS)

Li, Cheng-Bin; Yu, Yan-Mei; Sahoo, B. K.

2018-02-01

Roles of electron correlation effects in the determination of attachment energies, magnetic-dipole hyperfine-structure constants, and electric-dipole (E 1 ) matrix elements of the low-lying states in the singly charged cadmium ion (Cd+) have been analyzed. We employ the singles and doubles approximated relativistic coupled-cluster (RCC) method to calculate these properties. Intermediate results from the Dirac-Hartree-Fock approximation,the second-order many-body perturbation theory, and considering only the linear terms of the RCC method are given to demonstrate propagation of electron correlation effects in this ion. Contributions from important RCC terms are also given to highlight the importance of various correlation effects in the evaluation of these properties. At the end, we also determine E 1 polarizabilities (αE 1) of the ground and 5 p 2P1 /2 ;3 /2 states of Cd+ in the ab initio approach. We estimate them again by replacing some of the E 1 matrix elements and energies from the measurements to reduce their uncertainties so that they can be used in the high-precision experiments of this ion.

A density functional theory study of the correlation between analyte basicity, ZnPc adsorption strength, and sensor response.

PubMed

Tran, N L; Bohrer, F I; Trogler, W C; Kummel, A C

2009-05-28

Density functional theory (DFT) simulations were used to determine the binding strength of 12 electron-donating analytes to the zinc metal center of a zinc phthalocyanine molecule (ZnPc monomer). The analyte binding strengths were compared to the analytes' enthalpies of complex formation with boron trifluoride (BF(3)), which is a direct measure of their electron donating ability or Lewis basicity. With the exception of the most basic analyte investigated, the ZnPc binding energies were found to correlate linearly with analyte basicities. Based on natural population analysis calculations, analyte complexation to the Zn metal of the ZnPc monomer resulted in limited charge transfer from the analyte to the ZnPc molecule, which increased with analyte-ZnPc binding energy. The experimental analyte sensitivities from chemiresistor ZnPc sensor data were proportional to an exponential of the binding energies from DFT calculations consistent with sensitivity being proportional to analyte coverage and binding strength. The good correlation observed suggests DFT is a reliable method for the prediction of chemiresistor metallophthalocyanine binding strengths and response sensitivities.

Use of near infrared correlation spectroscopy for quantitation of surface iron, absorbed water and stored electronic energy in a suite of Mars soil analog materials

NASA Technical Reports Server (NTRS)

Coyne, Lelia M.; Banin, Amos; Carle, Glenn; Orenberg, James; Scattergood, Thomas

1989-01-01

A number of questions concerning the surface mineralogy and the history of water on Mars remain unresolved using the Viking analyses and Earth-based telescopic data. Identification and quantitation of iron-bearing clays on Mars would elucidate these outstanding issues. Near infrared correlation analysis, a method typically applied to qualitative and quantitative analysis of individual constituents of multicomponent mixtures, is adapted here to selection of distinctive features of a small, highly homologous series of Fe/Ca-exchanged montmorillonites and several kalinites. Independently determined measures of surface iron, relative humidity and stored electronic energy were used as constituent data for linear regression of the constituent vs. reflectance data throughout the spectral region 0.68 to 2.5 micrometers. High correlations were found in appropriate regions for all three constituents, though that with stored energy is still considered tenuous. Quantitation was improved using 1st and 2nd derivative spectra. High resolution data over a broad spectral range would be required to quantitatively identify iron-bearing clays by remotely sensed reflectance.

Correlated natural transition orbital framework for low-scaling excitation energy calculations (CorNFLEx).

PubMed

Baudin, Pablo; Kristensen, Kasper

2017-06-07

We present a new framework for calculating coupled cluster (CC) excitation energies at a reduced computational cost. It relies on correlated natural transition orbitals (NTOs), denoted CIS(D')-NTOs, which are obtained by diagonalizing generalized hole and particle density matrices determined from configuration interaction singles (CIS) information and additional terms that represent correlation effects. A transition-specific reduced orbital space is determined based on the eigenvalues of the CIS(D')-NTOs, and a standard CC excitation energy calculation is then performed in that reduced orbital space. The new method is denoted CorNFLEx (Correlated Natural transition orbital Framework for Low-scaling Excitation energy calculations). We calculate second-order approximate CC singles and doubles (CC2) excitation energies for a test set of organic molecules and demonstrate that CorNFLEx yields excitation energies of CC2 quality at a significantly reduced computational cost, even for relatively small systems and delocalized electronic transitions. In order to illustrate the potential of the method for large molecules, we also apply CorNFLEx to calculate CC2 excitation energies for a series of solvated formamide clusters (up to 4836 basis functions).

Multiple mobility edges in a 1D Aubry chain with Hubbard interaction in presence of electric field: Controlled electron transport

NASA Astrophysics Data System (ADS)

Saha, Srilekha; Maiti, Santanu K.; Karmakar, S. N.

2016-09-01

Electronic behavior of a 1D Aubry chain with Hubbard interaction is critically analyzed in presence of electric field. Multiple energy bands are generated as a result of Hubbard correlation and Aubry potential, and, within these bands localized states are developed under the application of electric field. Within a tight-binding framework we compute electronic transmission probability and average density of states using Green's function approach where the interaction parameter is treated under Hartree-Fock mean field scheme. From our analysis we find that selective transmission can be obtained by tuning injecting electron energy, and thus, the present model can be utilized as a controlled switching device.

Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.

PubMed

Singh, Nakul; O'Malley, Patrick J; Popelier, Paul L A

2005-02-21

Density functional calculations using the B3LYP functional are used to provide insight into the hydrogen abstraction mechanism of phenolic antioxidants. The energy profiles for 13 ortho, meta, para and di-methyl substituted phenols with hydroperoxyl radical have been determined. An excellent correlation between the enthalpy (DeltaH) and activation energy (DeltaEa) was found, obeying the Evans-Polanyi rule. The effects of hydrogen bonding on DeltaEa are also discussed. Electron donating groups at the ortho and para positions are able to lower the activation energy for hydrogen abstraction. The highly electron withdrawing fluoro substituent increases the activation energies relative to phenol at the meta position but not at the para position. The electron density is studied using the atoms in molecules (AIM) approach. Atomic and bond properties are extracted to describe the hydrogen atom abstraction mechanism. It is found that on going from reactants to transition state, the hydrogen atom experiences a loss in volume, electronic population and dipole moment. These features suggest that the phenol hydroperoxyl reactions proceed according to a proton coupled electron transfer (PCET) as opposed to a hydrogen atom transfer (HAT) mechanism.

Use of household supermarket sales data to estimate nutrient intakes: a comparison with repeat 24-hour dietary recalls.

PubMed

Eyles, Helen; Jiang, Yannan; Ni Mhurchu, Cliona

2010-01-01

Electronic supermarket sales data provide a promising, novel way of estimating nutrient intakes. However, little is known about how these data reflect the nutrients consumed by an individual household member. A cross-sectional survey of 49 primary household shoppers (age [mean+/-standard deviation age]=48+/-14 years; 84% female) from Wellington, New Zealand, was undertaken. Three months of baseline electronic supermarket sales data were compared with individual dietary intakes estimated from four random 24-hour dietary recalls collected during the same 3-month period. Spearman rank correlations between household purchases and individual intakes ranged from 0.54 for percentage of energy from saturated fat (P<0.001) to 0.06 for sodium (P=0.68). Other correlation coefficients were: percentage of energy from carbohydrate, 0.48; and protein, 0.44; energy density of nonbeverages, 0.37 (kcal/oz); percentage of energy from total fat, 0.34; sugar, 0.33 (oz/kcal); and energy density of beverages, 0.09 (oz/kcal; all P values <0.05). This research suggests that household electronic supermarket sales data may be a useful surrogate measure of some nutrient intakes of individuals, particularly percentage of energy from saturated and total fat. In the case of a supermarket intervention, an effect on household sales of percentage energy from saturated and total fat is also likely to impact the saturated and total fat intake of individual household members. Copyright 2010 American Dietetic Association. Published by Elsevier Inc. All rights reserved.

Photoelectron spectroscopy and electronic structure of ScO{sub n}{sup {minus}}(n = 1--4) and YO{sub n}{sup {minus}}(n = 1--5): Strong electron correlation effects in ScO{sup {minus}} and YO{sup {minus}}

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

Wu, H.; Wang, L.S.

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

Real-Space Multiple-Scattering Theory and Its Applications at Exascale

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

Eisenbach, Markus; Wang, Yang

In recent decades, the ab initio methods based on density functional theory (DFT) (Hohenberg and Kohn 1964, Kohn and Sham 1965) have become a widely used tool in computational materials science, which allows theoretical prediction of physical properties of materials from the first principles and theoretical interpretation of new physical phenomena found in experiments. In the framework of DFT, the original problem that requires solving a quantum mechanical equation for a many-electron system is reduced to a one-electron problem that involves an electron moving in an effective field, while the effective field potential is made up of an electrostatic potential,more » also known as Hartree potential, arising from the electronic and ion charge distribution in space and an exchange–correlation potential, which is a function of the electron density and encapsulates the exchange and correlation effects of the many-electron system. Even though the exact functional form of the exchange-correlation potential is formally unknown, a local density approximation (LDA) or a generalized gradient approximation (GGA) is usually applied so that the calculation of the exchange–correlation potential, as well as the exchange–correlation energy, becomes tractable while a required accuracy is retained. Based on DFT, ab initio electronic structure calculations for a material generally involve a self-consistent process that iterates between two computational tasks: (1) solving an one-electron Schrödinger equation, also known as Kohn–Sham equation, to obtain the electron density and, if needed, the magnetic moment density, and (2) solving the Poisson equation to obtain the electrostatic potential corresponding to the electron density and constructing the effective potential by adding the exchange–correlation potential to the electrostatic potential. This self-consistent process proceeds until a convergence criteria is reached.« less

Formation of orbital-selective electron states in LaTiO3/SrTiO3 superlattices

NASA Astrophysics Data System (ADS)

Lechermann, Frank; Boehnke, Lewin; Grieger, Daniel

2013-06-01

The interface electronic structure of correlated LaTiO3/SrTiO3 superlattices is investigated by means of the charge self-consistent combination of the local density approximation (LDA) to density functional theory with dynamical mean-field theory. Utilizing a pseudopotential technique together with a continuous-time quantum Monte Carlo approach, the resulting complex multiorbital electronic states are addressed in a coherent fashion beyond static mean field. General structural relaxations are taken into account on the LDA level and cooperate with the driving forces from strong electronic correlations. This alliance leads to a Ti(3dxy) dominated low-energy quasiparticle peak and a lower Hubbard band in line with photoemission studies. Furthermore correlation effects close to the band-insulating bulk SrTiO3 limit as well as the Mott-insulating bulk LaTiO3 limit are studied via realistic single-layer embeddings.

Electron Correlation in the Ionization Continuum of Molecules: Photoionization of N2 in the Vicinity of the Hopfield Series of Autoionizing States.

PubMed

Klinker, Markus; Marante, Carlos; Argenti, Luca; González-Vázquez, Jesús; Martín, Fernando

2018-02-15

Direct measurement of autoionization lifetimes by using time-resolved experimental techniques is a promising approach when energy-resolved spectroscopic methods do not work. Attosecond time-resolved experiments have recently provided the first quantitative determination of autoionization lifetimes of the lowest members of the well-known Hopfield series of resonances in N 2 . In this work, we have used the recently developed XCHEM approach to study photoionization of the N 2 molecule in the vicinity of these resonances. The XCHEM approach allows us to describe electron correlation in the molecular electronic continuum at a level similar to that provided by multireference configuration interaction methods in bound state calculations, a necessary condition to accurately describe autoionization, shakeup, and interchannel couplings occurring in this range of photon energies. Our results show that electron correlation leading to interchannel mixing is the main factor that determines the magnitude and shape of the N 2 photoionization cross sections, as well as the lifetimes of the Hopfield resonances. At variance with recent speculations, nonadiabatic effects do not seem to play a significant role. These conclusions are supported by the very good agreement between the calculated cross sections and those determined in synchrotron radiation and attosecond experiments.

Orbit-orbit relativistic correction calculated with all-electron molecular explicitly correlated Gaussians.

PubMed

Stanke, Monika; Palikot, Ewa; Kȩdziera, Dariusz; Adamowicz, Ludwik

2016-12-14

An algorithm for calculating the first-order electronic orbit-orbit magnetic interaction correction for an electronic wave function expanded in terms of all-electron explicitly correlated molecular Gaussian (ECG) functions with shifted centers is derived and implemented. The algorithm is tested in calculations concerning the H 2 molecule. It is also applied in calculations for LiH and H 3 + molecular systems. The implementation completes our work on the leading relativistic correction for ECGs and paves the way for very accurate ECG calculations of ground and excited potential energy surfaces (PESs) of small molecules with two and more nuclei and two and more electrons, such as HeH - , H 3 + , HeH 2 + , and LiH 2 + . The PESs will be used to determine rovibrational spectra of the systems.

Ion-induced electron emission microscopy

DOEpatents

Doyle, Barney L.; Vizkelethy, Gyorgy; Weller, Robert A.

2001-01-01

An ion beam analysis system that creates multidimensional maps of the effects of high energy ions from an unfocussed source upon a sample by correlating the exact entry point of an ion into a sample by projection imaging of the secondary electrons emitted at that point with a signal from a detector that measures the interaction of that ion within the sample. The emitted secondary electrons are collected in a strong electric field perpendicular to the sample surface and (optionally) projected and refocused by the electron lenses found in a photon emission electron microscope, amplified by microchannel plates and then their exact position is sensed by a very sensitive X Y position detector. Position signals from this secondary electron detector are then correlated in time with nuclear, atomic or electrical effects, including the malfunction of digital circuits, detected within the sample that were caused by the individual ion that created these secondary electrons in the fit place.

Correlated phonons and the Tc-dependent dynamical phonon anomalies

NASA Astrophysics Data System (ADS)

Hakioğlu, T.; Türeci, H.

1997-11-01

Anomalously large low-temperature phonon anharmonicities can lead to static as well as dynamical changes in the low-temperature properties of the electron-phonon system. In this work, we focus our attention on the dynamically generated low-temperature correlations in an interacting electron-phonon system using a self-consistent dynamical approach in the intermediate coupling range. In the context of the model, the polaron correlations are produced by the charge-density fluctuations which are generated dynamically by the electron-phonon coupling. Conversely, the latter is influenced in the presence of the former. The purpose of this work is to examine the dynamics of this dual mechanism between the two using the illustrative Fröhlich model. In particular, the influence of the low-temperature phonon dynamics on the superconducting properties in the intermediate coupling range is investigated. The influence on the Holstein reduction factor as well as the enhancement in the zero-point fluctuations and in the electron-phonon coupling are calculated numerically. We also examine these effects in the presence of superconductivity. Within this model, the contribution of the electron-phonon interaction as one of the important elements in the mechanisms of superconductivity can reach values as high as 15-20% of the characteristic scale of the lattice vibrational energy. The second motivation of this work is to understand the nature of the Tc-dependent temperature anomalies observed in the Debye-Waller factor, dynamical pair correlations, and average atomic vibrational energies for a number of high-temperature superconductors. In our approach we do not claim nor believe that the electron-phonon interaction is the primary mechanism leading to high-temperature superconductivity. Nevertheless, our calculations suggest that the dynamically induced low-temperature phonon correlation model can account for these anomalies and illustrates their possible common origin. Finally, the relevance of incorporating these low-temperature effects into more realistic models of high-temperature superconductivity including both the charge and spin degrees and other similar ideas existing in the literature are discussed.

Nitric Oxide Produced by Energetic Electron Precipitation During a Geomagnetic Storm in April 2010

NASA Astrophysics Data System (ADS)

Smith-Johnsen, C.; Nesse, T. H.; Glesnes Ødegaard, L. K.; Orsolini, Y.; Stordal, F.; Hendrickx, K.; Megner, L. S.

2015-12-01

In April 2010 a relativistic electron precipitation (REP) event occurred. A coronal mass ejection (CME) caused the Dst-index to reach -80nT, followed by solar wind speeds of over 600 km/s lasting for three days. Electron fluxes measured by the NOAA POES satellites were increased by an order of magnitude and stayed elevated for three days. We investigate the atmospheric nitric oxide (NO) response to these incoming energetic electrons. By combining the low and medium energy electron fluxes from the Total Energy Detector (TED) and Medium Energy Proton and Electron Detector (MEPED) on the NOAA POES satellites we get a continuous energy spectrum ranging from 1-1100 keV, which corresponds to atmospheric altitudes of 50-150km. The multiple NOAA satellites enables us to construct global maps of the precipitating electrons. The energy spectra of the incoming electron fluxes are compared to NO measurements from The Solar Occultation for Ice Experiment (SOFIE) on board the Aeronomy of Ice in the Mesosphere (AIM) satellite and NO from Sub-Millimeter Radiometer (SMR) on the Odin satellite. The correlation between the incoming electrons and the increase of NO is strongly affected by NO's long lifetime when not exposed to sunlight. Winds from Whole Atmosphere Community Climate Model (WACCM) and the empirical wind model HWM07 are used to take into account the transport of NO in order to understand the total impact of the incoming electrons.

Ab-initio study of electronic structure and elastic properties of ZrC

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

Mund, H. S., E-mail: hmoond@gmail.com; Ahuja, B. L.

2016-05-23

The electronic and elastic properties of ZrC have been investigated using the linear combination of atomic orbitals method within the framework of density functional theory. Different exchange-correlation functionals are taken into account within generalized gradient approximation. We have computed energy bands, density of states, elastic constants, bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, lattice parameters and pressure derivative of the bulk modulus by calculating ground state energy of the rock salt structure type ZrC.

Computational Prediction of Kinetic Rate Constants

DTIC Science & Technology

2009-02-01

best experimental estimates are in kcal/mol. RMcdoo l> Uil. . 1 -.In 1 1 II. lei ,. »rrsnn • emu rtvm . « snfi. !>ii K.IIHlMi’ \\i . St"WTi H...straightforward extensions the HF energy and gradient expressions. For example, the energy and the gradient HF-DFT ’ dE designated as E r-IIF DF1 and...8217’ Coulomb Electron Electron «P Hartr » . pBecke-LYP I ^Hartree-Fock \\7 n ’ Exchange correlation \\H ’ r llarlree-Fock Contract

Three-Jet Production in Electron-Positron Collisions at Next-to-Next-to-Leading Order Accuracy

NASA Astrophysics Data System (ADS)

Del Duca, Vittorio; Duhr, Claude; Kardos, Adam; Somogyi, Gábor; Trócsányi, Zoltán

2016-10-01

We introduce a completely local subtraction method for fully differential predictions at next-to-next-to-leading order (NNLO) accuracy for jet cross sections and use it to compute event shapes in three-jet production in electron-positron collisions. We validate our method on two event shapes, thrust and C parameter, which are already known in the literature at NNLO accuracy and compute for the first time oblateness and the energy-energy correlation at the same accuracy.

Three-Jet Production in Electron-Positron Collisions at Next-to-Next-to-Leading Order Accuracy.

PubMed

Del Duca, Vittorio; Duhr, Claude; Kardos, Adam; Somogyi, Gábor; Trócsányi, Zoltán

2016-10-07

We introduce a completely local subtraction method for fully differential predictions at next-to-next-to-leading order (NNLO) accuracy for jet cross sections and use it to compute event shapes in three-jet production in electron-positron collisions. We validate our method on two event shapes, thrust and C parameter, which are already known in the literature at NNLO accuracy and compute for the first time oblateness and the energy-energy correlation at the same accuracy.

Strong correlation in incremental full configuration interaction

NASA Astrophysics Data System (ADS)

Zimmerman, Paul M.

2017-06-01

Incremental Full Configuration Interaction (iFCI) reaches high accuracy electronic energies via a many-body expansion of the correlation energy. In this work, the Perfect Pairing (PP) ansatz replaces the Hartree-Fock reference of the original iFCI method. This substitution captures a large amount of correlation at zero-order, which allows iFCI to recover the remaining correlation energy with low-order increments. The resulting approach, PP-iFCI, is size consistent, size extensive, and systematically improvable with increasing order of incremental expansion. Tests on multiple single bond, multiple double bond, and triple bond dissociations of main group polyatomics using double and triple zeta basis sets demonstrate the power of the method for handling strong correlation. The smooth dissociation profiles that result from PP-iFCI show that FCI-quality ground state computations are now within reach for systems with up to about 10 heavy atoms.

A theory of local and global processes which affect solar wind electrons. 2: Experimental support

NASA Technical Reports Server (NTRS)

Scudder, J. D.; Olbert, S.

1979-01-01

The microscopic characteristics of the Coulomb cross section show that there are three natural subpopulations for plasma electrons: the subthermals with local kinetic energy E kT sub c; the transthermals with kT sub c E 7 kT sub c and the extrathermals E 7 kT sub c. Data from three experimental groups on three different spacecraft in the interplanetary medium over a radial range are presented to support the five interrelations projected between solar wind electron properties and changes in the interplanetary medium: (1) subthermals respond primarily to local changes (compression and rarefactions) in stream dynamics; (2) the extrathermal fraction of the ambient electron density should be anti-correlated with the asymptotic bulk speed; (3) the extrathermal "temperature" should be anti-correlated with the local wind speed at 1 AU; (4) the heat flux carried by electrons should be anti-correlated with the local bulk speed; and (5) the extrathermal differential 'temperature' should be nearly independent of radius within 1 AU.

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

NASA Technical Reports Server (NTRS)

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

1986-01-01

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

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

PubMed

Xu, Peng; Gordon, Mark S

2014-09-04

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

Density functional with full exact exchange, balanced nonlocality of correlations, and constraint satisfaction

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

Tao, Jianmin; Perdew, John P; Staroverov, Viktor N

2008-01-01

We construct a nonlocal density functional approximation with full exact exchange, while preserving the constraint-satisfaction approach and justified error cancellations of simpler semilocal functionals. This is achieved by interpolating between different approximations suitable for two extreme regions of the electron density. In a 'normal' region, the exact exchange-correlation hole density around an electron is semilocal because its spatial range is reduced by correlation and because it integrates over a narrow range to -1. These regions are well described by popular semilocal approximations (many of which have been constructed nonempirically), because of proper accuracy for a slowly-varying density or because ofmore » error cancellation between exchange and correlation. 'Abnormal' regions, where non locality is unveiled, include those in which exchange can dominate correlation (one-electron, nonuniform high-density, and rapidly-varying limits), and those open subsystems of fluctuating electron number over which the exact exchange-correlation hole integrates to a value greater than -1. Regions between these extremes are described by a hybrid functional mixing exact and semi local exchange energy densities locally (i.e., with a mixing fraction that is a function of position r and a functional of the density). Because our mixing fraction tends to 1 in the high-density limit, we employ full exact exchange according to the rigorous definition of the exchange component of any exchange-correlation energy functional. Use of full exact exchange permits the satisfaction of many exact constraints, but the nonlocality of exchange also requires balanced nonlocality of correlation. We find that this nonlocality can demand at least five empirical parameters (corresponding roughly to the four kinds of abnormal regions). Our local hybrid functional is perhaps the first accurate size-consistent density functional with full exact exchange. It satisfies other known exact constraints, including exactness for all one-electron densities, and provides an excellent, fit 1.0 the 223 molecular enthalpies of formation of the G3/99 set and the 42 reaction barrier heights of the BH42/03 set, improving both (but especially the latter) over most semilocal functionals and global hybrids. Exact constraints, physical insights, and paradigm examples hopefully suppress 'overfitting'.« less

How accurate are the parametrized correlation energies of the uniform electron gas?

NASA Astrophysics Data System (ADS)

Bhattarai, Puskar; Patra, Abhirup; Shahi, Chandra; Perdew, John P.

2018-05-01

Density functional approximations to the exchange-correlation energy are designed to be exact for an electron gas of uniform density parameter rs and relative spin polarization ζ , requiring a parametrization of the correlation energy per electron ɛc(rs,ζ ) . We consider three widely used parametrizations [J. P. Perdew and A. Zunger, Phys. Rev. B 23, 5048 (1981), 10.1103/PhysRevB.23.5048 or PZ81, S. H. Vosko, L. Wilk, and M. Nusair, Can. J. Phys. 58, 1200 (1980), 10.1139/p80-159 or VWN80, and J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13244 (1992), 10.1103/PhysRevB.45.13244 or PW92] that interpolate the quantum Monte Carlo (QMC) correlation energies of Ceperley-Alder [Phys. Rev. Lett. 45, 566 (1980), 10.1103/PhysRevLett.45.566], while extrapolating them to known high-(rs→0 ) and low- (rs→∞ ) density limits. For the physically important range 0.5 ≤rs≤20 , they agree closely with one another, with differences of 0.01 eV (0.5%) or less between the latter two. The density parameter interpolation (DPI), designed to predict these energies by interpolation between the known high- and low-density limits, with almost no other input (and none for ζ =0 ), is also reasonably close, both in its original version and with corrections for ζ ≠0 . Moreover, the DPI and PW92 at rs=0.5 are very close to the high-density expansion. The larger discrepancies with the QMC of Spink et al. [Phys. Rev. B 88, 085121 (2013), 10.1103/PhysRevB.88.085121], of order 0.1 eV (5%) at rs=0.5 , are thus surprising, suggesting that the constraint-based PW92 and VWN80 parametrizations are more accurate than the QMC for rs<2 . For rs>2 , however, the QMC of Spink et al. confirms the dependence upon relative spin polarization predicted by the parametrizations.

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

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

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

2013-01-01

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

GW electronic Correlations in Quantum Transport : Renormalization and finite lifetime effects on real systems

NASA Astrophysics Data System (ADS)

Darancet, Pierre; Ferretti, Andrea; Mayou, Didier; Olevano, Valerio

2007-03-01

We present an ab initio approach to electronic transport in nanoscale systems which includes electronic correlations through the GW approximation. With respect to Landauer approaches based on density-functional theory (DFT), we introduce a physical quasiparticle electronic-structure into a non-equilibrium Green's function theory framework. We use an equilibrium non-selfconsistent G^0W^0 self-energy considering both full non-hermiticity and dynamical effects. The method is applied to a real system, a gold mono-atomic chain. With respect to DFT results, the conductance profile is modified and reduced by to the introduction of diffusion and loss-of-coherence effects. The linear response conductance characteristic appear to be in agreement with experimental results.

Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy.

PubMed

Zhang, Zhengyang; Lambrev, Petar H; Wells, Kym L; Garab, Győző; Tan, Howe-Siang

2015-07-31

During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

A theory of solar type 3 radio bursts

NASA Technical Reports Server (NTRS)

Goldstein, M. L.; Papadopoulos, K.; Smith, R. A.

1979-01-01

Energetic electrons propagating through the interplanetary medium are shown to excite the one dimensional oscillating two stream instability (OTSI). The OTSI is in turn stabilized by anomalous resistivity which completes the transfer of long wavelength Langmuir waves to short wavelengths, out of resonance with the electrons. The theory explains the small energy losses suffered by the electrons in propagating to 1 AU, the predominance of second harmonic radiation, and the observed correlation between radio and electron fluxes.

Energy spectrum and electrical conductivity of graphene with a nitrogen impurity

NASA Astrophysics Data System (ADS)

Repetskii, S. P.; Vyshivanaya, I. G.; Skotnikov, V. A.; Yatsenyuk, A. A.

2015-04-01

The electronic structure of graphene with a nitrogen impurity has been studied based on the model of tight binding using exchange-correlation potentials in the density-functional theory. Wave functions of 2 s and 2 p states of neutral noninteracting carbon atoms have been chosen as the basis. When studying the matrix elements of the Hamiltonian, the first three coordination shells have been taken into account. It has been established that the hybridization of electron-energy bands leads to the splitting of the electron energy spectrum near the Fermi level. Due to the overlap of the energy bands, the arising gap behaves as a quasi-gap, in which the density of the electron levels is much lower than in the rest of the spectrum. It has been established that the conductivity of graphene decreases with increasing nitrogen concentration. Since the increase in the nitrogen concentration leads to an increase in the density of states at the Fermi level, the decrease in the conductivity is due to a sharper decrease in the time of relaxation of the electron sates.

Electron correlation at the MgF2(110) surface: a comparison of incremental and local correlation methods.

PubMed

Hammerschmidt, Lukas; Maschio, Lorenzo; Müller, Carsten; Paulus, Beate

2015-01-13

We have applied the Method of Increments and the periodic Local-MP2 approach to the study of the (110) surface of magnesium fluoride, a system of significant interest in heterogeneous catalysis. After careful assessment of the approximations inherent in both methods, the two schemes, though conceptually different, are shown to yield nearly identical results. This remains true even when analyzed in fine detail through partition of the individual contribution to the total energy. This kind of partitioning also provides thorough insight into the electron correlation effects underlying the surface formation process, which are discussed in detail.

Probing Ligand Effects on the Redox Energies of [4Fe-4S] Clusters Using Broken-Symmetry Density Functional Theory

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

Niu, Shuqiang; Ichiye, Toshiko

A central issue in understanding redox properties of iron-sulfur proteins is determining the factors that tune the reduction potentials of the Fe-S clusters. Recently, Solomon and coworkers have shown that the Fe-S bond covalency of protein analogs measured by %L, the percent ligand character of the Fe 3d orbitals, from ligand K-edge X-ray absorption spectroscopy (XAS) correlates with the electrochemical redox potentials. Also, Wang and coworkers have measured electron detachment energies for iron-sulfur clusters without environmental perturbations by gas-phase photoelectron spectroscopy (PES). Here the correlations of the ligand character with redox energy and %L character are examined in [Fe₄S₄L₄]2⁻ clustersmore » with different ligands by broken symmetry density functional theory (BS-DFT) calculations using the B3LYP functional together with PES and XAS experimental results. These gas-phase studies assess ligand effects independently of environmental perturbations and thus provide essential information for computational studies of iron-sulfur proteins. The B3LYP oxidation energies agree well with PES data, and the %L character obtained from natural bond orbital analysis correlates with XAS values, although it systematically underestimates them because of basis set effects. The results show that stronger electron-donating terminal ligands increase %Lt, the percent ligand character from terminal ligands, but decrease %Sb, the percent ligand character from the bridging sulfurs. Because the oxidized orbital has significant Fe-Lt antibonding character, the oxidation energy correlates well with %Lt. However, because the reduced orbital has varying contributions of both Fe-Lt and Fe-Sb antibonding character, the reduction energy does not correlate with either %Lt or %Sb. Overall, BSDFT calculations together with XAS and PES experiments can unravel the complex underlying factors in the redox energy and chemical bonding of the [4Fe-4S] clusters in iron-sulfur proteins.« less

Influence of scattering processes on electron quantum states in nanowires

PubMed Central

Galenchik, Vadim; Borzdov, Andrei; Borzdov, Vladimir; Komarov, Fadei

2007-01-01

In the framework of quantum perturbation theory the self-consistent method of calculation of electron scattering rates in nanowires with the one-dimensional electron gas in the quantum limit is worked out. The developed method allows both the collisional broadening and the quantum correlations between scattering events to be taken into account. It is an alternativeper seto the Fock approximation for the self-energy approach based on Green’s function formalism. However this approach is free of mathematical difficulties typical to the Fock approximation. Moreover, the developed method is simpler than the Fock approximation from the computational point of view. Using the approximation of stable one-particle quantum states it is proved that the electron scattering processes determine the dependence of electron energy versus its wave vector.

The order of three lowest-energy states of the six-electron harmonium at small force constant

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

Strasburger, Krzysztof

2016-06-21

The order of low-energy states of six-electron harmonium is uncertain in the case of strong correlation, which is not a desired situation for the model system being considered for future testing of approximate methods of quantum chemistry. The computational study of these states has been carried out at the frequency parameter ω = 0.01, using the variational method with the basis of symmetry-projected, explicitly correlated Gaussian (ECG) lobe functions. It has revealed that the six-electron harmonium at this confinement strength is an octahedral Wigner molecule, whose order of states is different than in the strong confinement regime and does notmore » agree with the earlier predictions. The results obtained for ω = 0.5 and 10 are consistent with the findings based on the Hund’s rules for the s{sup 2}p{sup 4} electron configuration. Substantial part of the computations has been carried out on the graphical processing units and the efficiency of these devices in calculation of the integrals over ECG functions has been compared with traditional processors.« less

Evolution and Control of 2219 Aluminum Microstructural Features Through Electron Beam Freeform Fabrication

NASA Technical Reports Server (NTRS)

Taminger, Karen M.; Hafley, Robert A.; Domack, Marcia S.

2006-01-01

The layer-additive nature of the electron beam freeform fabrication (EBF3) process results in a tortuous thermal path producing complex microstructures including: small homogeneous equiaxed grains; dendritic growth contained within larger grains; and/or pervasive dendritic formation in the interpass regions of the deposits. Several process control variables contribute to the formation of these different microstructures, including translation speed, wire feed rate, beam current and accelerating voltage. In electron beam processing, higher accelerating voltages embed the energy deeper below the surface of the substrate. Two EBF3 systems have been established at NASA Langley, one with a low-voltage (10-30kV) and the other a high-voltage (30-60 kV) electron beam gun. Aluminum alloy 2219 was processed over a range of different variables to explore the design space and correlate the resultant microstructures with the processing parameters. This report is specifically exploring the impact of accelerating voltage. Of particular interest is correlating energy to the resultant material characteristics to determine the potential of achieving microstructural control through precise management of the heat flux and cooling rates during deposition.

Suppression of spin and optical gaps in phosphorene quantum dots

NASA Astrophysics Data System (ADS)

Zhang, Yingjie; Sheng, Weidong

2018-05-01

Electronic structure and optical properties of triangular phosphorene quantum dots have been investigated theoretically. Based on systematic configuration interaction calculations, the ground and excited states of the interacting many-electron system together with its optical absorption spectrum are obtained. For the nanodot with 60 phosphorus atoms in various dielectric environments, it is found that the spin gap of the correlated system surprisingly overlaps its optical gap over a large range of the effective dielectric constant. The overlapping of the spin and optical gaps can be attributed to the fact that the extra correlation energy in the spin singlet almost compensates the exchange energy in the spin triplet in the presence of strong long-range electron-electron interactions. Moreover, both the spin and optical gaps are shown to be greatly suppressed as the screening effect becomes strong. When the dielectric constant decreases below 2.65, it is seen that the spin gap becomes negative and the quantum dot undergoes a phase transition from nonmagnetic to ferromagnetic. Our results are compared with the previous experimental and theoretical works.

Measurements of hot electrons in the Extrap T1 reversed-field pinch

NASA Astrophysics Data System (ADS)

Welander, A.; Bergsåker, H.

1998-02-01

The presence of an anisotropic energetic electron population in the edge region is a characteristic feature of reversed-field pinch (RFP) plasmas. In the Extrap T1 RFP, the anisotropic, parallel heat flux in the edge region measured by calorimetry was typically several hundred 0741-3335/40/2/011/img1. To gain more insight into the origin of the hot electron component and to achieve time resolution of the hot electron flow during the discharge, a target probe with a soft x-ray monitor was designed, calibrated and implemented. The x-ray emission from the target was measured with a surface barrier detector covered with a set of different x-ray filters to achieve energy resolution. A calibration in the range 0.5-2 keV electron energy was performed on the same target and detector assembly using a 0741-3335/40/2/011/img2 cathode electron gun. The calibration data are interpolated and extrapolated numerically. A directional asymmetry of more than a factor of 100 for the higher energy electrons is observed. The hot electrons are estimated to constitute 10% of the total electron density at the edge and their energy distribution is approximated by a half-Maxwellian with a temperature slightly higher than the central electron temperature. Scalings with plasma current, as well as correlations with local 0741-3335/40/2/011/img3 measurements and radial dependences, are presented.

Insights on the Cuprate High Energy Anomaly Observed in ARPES

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

Moritz, Brian

2011-08-16

Recently, angle-resolved photoemission spectroscopy has been used to highlight an anomalously large band renormalization at high binding energies in cuprate superconductors: the high energy 'waterfall' or high energy anomaly (HEA). The anomaly is present for both hole- and electron-doped cuprates as well as the half-filled parent insulators with different energy scales arising on either side of the phase diagram. While photoemission matrix elements clearly play a role in changing the aesthetic appearance of the band dispersion, i.e. creating a 'waterfall'-like appearance, they provide an inadequate description for the physics that underlies the strong band renormalization giving rise to the HEA.more » Model calculations of the single-band Hubbard Hamiltonian showcase the role played by correlations in the formation of the HEA and uncover significant differences in the HEA energy scale for hole- and electron-doped cuprates. In addition, this approach properly captures the transfer of spectral weight accompanying doping in a correlated material and provides a unifying description of the HEA across both sides of the cuprate phase diagram. We find that the anomaly demarcates a transition, or cross-over, from a quasiparticle band at low binding energies near the Fermi level to valence bands at higher binding energy, assumed to be of strong oxygen character.« less

Quantum Monte Carlo analysis of a charge ordered insulating antiferromagnet: The Ti 4O 7 Magneli phase

DOE PAGES

Benali, Anouar; Shulenburger, Luke; Krogel, Jaron T.; ...

2016-06-07

The Magneli phase Ti 4O 7 is an important transition metal oxide with a wide range of applications because of its interplay between charge, spin, and lattice degrees of freedom. At low temperatures, it has non-trivial magnetic states very close in energy, driven by electronic exchange and correlation interactions. We have examined three low- lying states, one ferromagnetic and two antiferromagnetic, and calculated their energies as well as Ti spin moment distributions using highly accurate Quantum Monte Carlo methods. We compare our results to those obtained from density functional theory- based methods that include approximate corrections for exchange and correlation.more » Our results confirm the nature of the states and their ordering in energy, as compared with density-functional theory methods. However, the energy differences and spin distributions differ. Here, a detailed analysis suggests that non-local exchange-correlation functionals, in addition to other approximations such as LDA+U to account for correlations, are needed to simultaneously obtain better estimates for spin moments, distributions, energy differences and energy gaps.« less

Role of cooperative structural distortions in the metal--insulator transitions of perovskite ferrates

NASA Astrophysics Data System (ADS)

Cammarata, Antonio; Rondinelli, James

2012-02-01

Transition-metal oxides within the perovskite crystal family exhibit strong electron--electron correlation effects that coexist with complex structural distortions, leading to metal-insulator (MI) transitions. Using first-principles density functional calculations, we investigate the effects of cooperative octahedral rotations and dilations/contractions on the charge-ordering MI-transition in CaFeO3. By calculating the evolution in the lattice phonons, which describe the different octahedral distortions present in the low-symmetry monoclinic phase of CaFeO3 with increasing electron correlation, we show that the MI-transition results from a complex interplay between these modes and correlation effects. We combine this study with group theoretical tools to disentangle the electron--lattice interactions by computing the evolution in the low-energy electronic band structure with the lattice phonons, demonstrating the MI-transition in CaFeO3 proceeds through a symmetry-lowering transition driven by a cooperative three-dimensional octahedral dilation/contraction pattern. Finally, we suggest a possible route by which to control the charge ordering by fine-tuning the electron--lattice coupling.

Bandgap profiling in CIGS solar cells via valence electron energy-loss spectroscopy

NASA Astrophysics Data System (ADS)

Deitz, Julia I.; Karki, Shankar; Marsillac, Sylvain X.; Grassman, Tyler J.; McComb, David W.

2018-03-01

A robust, reproducible method for the extraction of relative bandgap trends from scanning transmission electron microscopy (STEM) based electron energy-loss spectroscopy (EELS) is described. The effectiveness of the approach is demonstrated by profiling the bandgap through a CuIn1-xGaxSe2 solar cell that possesses intentional Ga/(In + Ga) composition variation. The EELS-determined bandgap profile is compared to the nominal profile calculated from compositional data collected via STEM-based energy dispersive X-ray spectroscopy. The EELS based profile is found to closely track the calculated bandgap trends, with only a small, fixed offset difference. This method, which is particularly advantageous for relatively narrow bandgap materials and/or STEM systems with modest resolution capabilities (i.e., >100 meV), compromises absolute accuracy to provide a straightforward route for the correlation of local electronic structure trends with nanoscale chemical and physical structure/microstructure within semiconductor materials and devices.

Electronic structures of Plutonium compounds with the NaCl-type monochalcogenides structure

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Tatetsu, Yasutomi

2012-12-01

We calculate the energy band structure and the Fermi surface of PuS, PuSe and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in a local density approximation. It is found in common that the energy bands in the vicinity of the Fermi level are mainly due to the hybridization between Pu 5/ and monochalcogenide p electrons. The obtained main Fermi surfaces are composed of two hole sheets and one electron sheet, all of which are constructed from the band having the Pu 5/ state and the monochalcogenide p state.

Strong electron correlation in UO{sub 2}{sup −}: A photoelectron spectroscopy and relativistic quantum chemistry study

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

Li, Wei-Li; Jian, Tian; Lopez, Gary V.

2014-03-07

The electronic structures of actinide systems are extremely complicated and pose considerable challenges both experimentally and theoretically because of significant electron correlation and relativistic effects. Here we report an investigation of the electronic structure and chemical bonding of uranium dioxides, UO{sub 2}{sup −} and UO{sub 2}, using photoelectron spectroscopy and relativistic quantum chemistry. The electron affinity of UO{sub 2} is measured to be 1.159(20) eV. Intense detachment bands are observed from the UO{sub 2}{sup −} low-lying (7sσ{sub g}){sup 2}(5fϕ{sub u}){sup 1} orbitals and the more deeply bound O2p-based molecular orbitals which are separated by a large energy gap from themore » U-based orbitals. Surprisingly, numerous weak photodetachment transitions are observed in the gap region due to extensive two-electron transitions, suggesting strong electron correlations among the (7sσ{sub g}){sup 2}(5fϕ{sub u}){sup 1} electrons in UO{sub 2}{sup −} and the (7sσ{sub g}){sup 1}(5fϕ{sub u}){sup 1} electrons in UO{sub 2}. These observations are interpreted using multi-reference ab initio calculations with inclusion of spin-orbit coupling. The strong electron correlations and spin-orbit couplings generate orders-of-magnitude more detachment transitions from UO{sub 2}{sup −} than expected on the basis of the Koopmans’ theorem. The current experimental data on UO{sub 2}{sup −} provide a long-sought opportunity to arbitrating various relativistic quantum chemistry methods aimed at handling systems with strong electron correlations.« less

A Method to Improve Electron Density Measurement of Cone-Beam CT Using Dual Energy Technique

PubMed Central

Men, Kuo; Dai, Jian-Rong; Li, Ming-Hui; Chen, Xin-Yuan; Zhang, Ke; Tian, Yuan; Huang, Peng; Xu, Ying-Jie

2015-01-01

Purpose. To develop a dual energy imaging method to improve the accuracy of electron density measurement with a cone-beam CT (CBCT) device. Materials and Methods. The imaging system is the XVI CBCT system on Elekta Synergy linac. Projection data were acquired with the high and low energy X-ray, respectively, to set up a basis material decomposition model. Virtual phantom simulation and phantoms experiments were carried out for quantitative evaluation of the method. Phantoms were also scanned twice with the high and low energy X-ray, respectively. The data were decomposed into projections of the two basis material coefficients according to the model set up earlier. The two sets of decomposed projections were used to reconstruct CBCT images of the basis material coefficients. Then, the images of electron densities were calculated with these CBCT images. Results. The difference between the calculated and theoretical values was within 2% and the correlation coefficient of them was about 1.0. The dual energy imaging method obtained more accurate electron density values and reduced the beam hardening artifacts obviously. Conclusion. A novel dual energy CBCT imaging method to calculate the electron densities was developed. It can acquire more accurate values and provide a platform potentially for dose calculation. PMID:26346510

Spiral magnetic order, non-uniform states and electron correlations in the conducting transition metal systems

NASA Astrophysics Data System (ADS)

Igoshev, P. A.; Timirgazin, M. A.; Arzhnikov, A. K.; Antipin, T. V.; Irkhin, V. Yu.

2017-10-01

The ground-state magnetic phase diagram is calculated within the Hubbard and s-d exchange (Kondo) models for square and simple cubic lattices vs. band filling and interaction parameter. The difference of the results owing to the presence of localized moments in the latter model is discussed. We employ a generalized Hartree-Fock approximation (HFA) to treat commensurate ferromagnetic (FM), antiferromagnetic (AFM), and incommensurate (spiral) magnetic phases. The electron correlations are taken into account within the Hubbard model by using the Kotliar-Ruckenstein slave boson approximation (SBA). The main advantage of this approach is a correct qualitative description of the paramagnetic phase: its energy becomes considerably lower as compared with HFA, and the gain in the energy of magnetic phases is substantially reduced.

Theory of the classical electron gas

NASA Technical Reports Server (NTRS)

Guernsey, R. L.

1978-01-01

In a previous paper Cohen and Murphy (1969) used the Meeron resummation (1958) of the Mayer diagrams (1950) to calculate the pair correlation for the classical electron gas in thermal equilibrium. They found that successive terms in the expression for the pair correlation were more and more singular for small interparticle spacing, actually dominating the Debye-Hueckel result for sufficiently small distances. This led to apparent divergence in the higher order contributions to the internal energy. The present paper shows that the apparent anomalies in the Cohen-Murphy results can be removed without further resummation by a more careful treatment of the region of small interparticle spacing. It is shown that there is really no anomalous behavior at short range in any order and all integrals in the expression for the internal energy converge.

Development and Application of Explicitly Correlated Wave Function Based Methods for the Investigation of Optical Properties of Semiconductor Nanomaterials

NASA Astrophysics Data System (ADS)

Elward, Jennifer Mary

Semiconductor nanoparticles, or quantum dots (QDs), are well known to have very unique optical and electronic properties. These properties can be controlled and tailored as a function of several influential factors, including but not limited to the particle size and shape, effect of composition and heterojunction as well as the effect of ligand on the particle surface. This customizable nature leads to extensive experimental and theoretical research on the capabilities of these quantum dots for many application purposes. However, in order to be able to understand and thus further the development of these materials, one must first understand the fundamental interaction within these nanoparticles. In this thesis, I have developed a theoretical method which is called electron-hole explicitly correlated Hartee-Fock (eh-XCHF). It is a variational method for solving the electron-hole Schrodinger equation and has been used in this work to study electron-hole interaction in semiconductor quantum dots. The method was benchmarked with respect to a parabolic quantum dot system, and ground state energy and electron-hole recombination probability were computed. Both of these properties were found to be in good agreement with expected results. Upon successful benchmarking, I have applied the eh-XCHF method to study optical properties of several quantum dot systems including the effect of dot size on exciton binding energy and recombination probability in a CdSe quantum dot, the effect of shape on a CdSe quantum dot, the effect of heterojunction on a CdSe/ZnS quantum dot and the effect of quantum dot-biomolecule interaction within a CdSe-firefly Luciferase protein conjugate system. As metrics for assessing the effect of these influencers on the electron-hole interaction, the exciton binding energy, electron-hole recombination probability and the average electron-hole separation distance have been computed. These excitonic properties have been found to be strongly infuenced by the changing composition of the particle. It has also been found through this work that the explicitly correlated method performs very well when computing these properties as it provides a feasible computational route to compare to both experimental and other theoretical results.

High resolution energy-angle correlation measurement of hard x rays from laser-Thomson backscattering.

PubMed

Jochmann, A; Irman, A; Bussmann, M; Couperus, J P; Cowan, T E; Debus, A D; Kuntzsch, M; Ledingham, K W D; Lehnert, U; Sauerbrey, R; Schlenvoigt, H P; Seipt, D; Stöhlker, Th; Thorn, D B; Trotsenko, S; Wagner, A; Schramm, U

2013-09-13

Thomson backscattering of intense laser pulses from relativistic electrons not only allows for the generation of bright x-ray pulses but also for the investigation of the complex particle dynamics at the interaction point. For this purpose a complete spectral characterization of a Thomson source powered by a compact linear electron accelerator is performed with unprecedented angular and energy resolution. A rigorous statistical analysis comparing experimental data to 3D simulations enables, e.g., the extraction of the angular distribution of electrons with 1.5% accuracy and, in total, provides predictive capability for the future high brightness hard x-ray source PHOENIX (photon electron collider for narrow bandwidth intense x rays) and potential gamma-ray sources.

The multifarious temporal variations of low energy, relativistic cosmic ray electrons

NASA Technical Reports Server (NTRS)

Mcdonald, F. B.; Cline, T. L.; Simnett, G. M.

1972-01-01

A detailed examination is made of the intensity variations of 3 - 12 MeV interplanetary electrons. The data used are from the cosmic ray experiment flown on the IMP solar minimum through to the onset of the present solar maximum (i.e., from December 1963 through August 1969). A morphology for the intensity changes is tentatively proposed which includes solar flare-associated events, solar co-rotating increases, Forbush decreases, and quiet-time increases, as well as the long term eleven-year variation. It is contended that the electron component observed both during quiescent times and during quiet-time increases are galactic in origin. The quiet-time increases represent a completely new phenomenon that appears to be unique to the low energy electron population. During a quiet-time increase the electron intensity is enhanced by a factor of 3 to 5 over a period of days, and, in general, these periods anti-correlate with low-energy solar particle events. Qualitatively, their amplitude diminishes with increasing solar activity.

Spatially inhomogeneous electron state deep in the extreme quantum limit of strontium titanate

DOE PAGES

Bhattacharya, Anand; Skinner, Brian; Khalsa, Guru; ...

2016-09-29

When an electronic system is subjected to a sufficiently strong magnetic field that the cyclotron energy is much larger than the Fermi energy, the system enters the extreme quantum limit (EQL) and becomes susceptible to a number of instabilities. Bringing a three-dimensional electronic system deeply into the EQL can be difficult however, since it requires a small Fermi energy, large magnetic field, and low disorder. Here we present an experimental study of the EQL in lightly-doped single crystals of strontium titanate. Our experiments probe deeply into the regime where theory has long predicted an interaction-driven charge density wave or Wignermore » crystal state. A number of interesting features arise in the transport in this regime, including a striking re-entrant nonlinearity in the current-voltage characteristics. As a result, we discuss these features in the context of possible correlated electron states, and present an alternative picture based on magnetic-field induced puddling of electrons.« less

The impact of electron correlations on the energetics and stability of silicon nanoclusters

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

Matsko, N. L.; Baturin, V. S.; Lepeshkin, S. V.

2016-08-21

The first-principles prediction of stable nanocluster structure is often hampered by the existence of many isomer configurations with energies close to the ground state. This fact attaches additional importance to many-electron effects beyond density functional theory (DFT), because their contributions can change a subtle energy order of competitive structures. To analyze this problem, we consider, as an example, the energetics of silicon nanoclusters passivated by hydrogen Si{sub 10}H{sub 2n} (0 ≤ n ≤ 11), where passivation changes the structure from compact to loosely packed and branched. Our calculations performed with DFT, hybrid functionals, and Hartree-Fock methods, as well as bymore » the GW approximation, confirm a considerable sensitivity of isomer energy ordering to many-electron effects.« less

Relationships for electron-vibrational coupling in conjugated π organic systems

NASA Astrophysics Data System (ADS)

O'Neill, L.; Lynch, P.; McNamara, M.; Byrne, H. J.

2005-06-01

A series of π conjugated systems were studied by absorption, photoluminescence and vibrational spectroscopy. As is common for these systems, a linear relationship between the positioning of the absorption and photoluminescence maxima plotted against inverse conjugation length is observed. The relationships are in good agreement with the simple particle in a box method, one of the earliest descriptions of the properties of one-dimensional organic molecules. In addition to the electronic transition energies, it was observed that the Stokes shift also exhibited a well-defined relationship with increasing conjugation length, implying a correlation between the electron-vibrational coupling and chain length. This correlation is further examined using Raman spectroscopy, whereby the integrated Raman scattering is seen to behave superlinearly with chain length. There is a clear indication that the vibrational activity and thus nonradiative decay processes are controllable through molecular structure. The correlations between the Stokes energies and the vibrational structure are also observed in a selection of PPV based polymers and a clear trend of increasing luminescence efficiency with decreasing vibrational activity and Stokes shift is observable. The implications of such structure property relationships in terms of materials design are discussed.

Calculation on spectrum of direct DNA damage induced by low-energy electrons including dissociative electron attachment.

PubMed

Liu, Wei; Tan, Zhenyu; Zhang, Liming; Champion, Christophe

2017-03-01

In this work, direct DNA damage induced by low-energy electrons (sub-keV) is simulated using a Monte Carlo method. The characteristics of the present simulation are to consider the new mechanism of DNA damage due to dissociative electron attachment (DEA) and to allow determining damage to specific bases (i.e., adenine, thymine, guanine, or cytosine). The electron track structure in liquid water is generated, based on the dielectric response model for describing electron inelastic scattering and on a free-parameter theoretical model and the NIST database for calculating electron elastic scattering. Ionization cross sections of DNA bases are used to generate base radicals, and available DEA cross sections of DNA components are applied for determining DNA-strand breaks and base damage induced by sub-ionization electrons. The electron elastic scattering from DNA components is simulated using cross sections from different theoretical calculations. The resulting yields of various strand breaks and base damage in cellular environment are given. Especially, the contributions of sub-ionization electrons to various strand breaks and base damage are quantitatively presented, and the correlation between complex clustered DNA damage and the corresponding damaged bases is explored. This work shows that the contribution of sub-ionization electrons to strand breaks is substantial, up to about 40-70%, and this contribution is mainly focused on single-strand break. In addition, the base damage induced by sub-ionization electrons contributes to about 20-40% of the total base damage, and there is an evident correlation between single-strand break and damaged base pair A-T.

A non-Hermitian analysis of strongly correlated quantum systems

NASA Astrophysics Data System (ADS)

Nakamura, Yuichi; Hatano, Naomichi

2006-03-01

We study a non-Hermitian generalization of strongly correlated quantum systems in which the transfer energy of electrons is asymmetric. Hatano and Nelson[1] applied this technique to non-interacting random electron systems. They related a non-Hermitian critical point to the inverse localization length of the Hermitian systems. We here conjecture that we can obtain in the same way the correlation length of Hermitian interacting non-random systems[2]. We show for the Hubbard model and the antiferromagnetic XXZ model in one dimension that the non-Hermitian critical point of the ground state, where the energy gap vanishes, is equal to the inverse correlation length. We also show that the conjecture is consistent with numerical results for S=1/2 frustrated quantum spin chains with the nearest- and next-nearest-neighbor interactions including the Majumdar-Ghosh model[3]. [1] N. Hatano and D. R. Nelson, PRL 77 (1996) 570; PRB 56 (1997) 8651. [2] Y. Nakamura and N. Hatano, Physica B, accepted. [3] C. K. Majumdar and D. K. Ghosh, J. Phys. C3 (1970) 911; J. Math. Phys. 10 (1969) 1388, 1399.

Many-body effects and excitonic features in 2D biphenylene carbon

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

Lüder, Johann, E-mail: johann.luder@physics.uu.se; Puglia, Carla; Eriksson, Olle

2016-01-14

The remarkable excitonic effects in low dimensional materials in connection to large binding energies of excitons are of great importance for research and technological applications such as in solar energy and quantum information processing as well as for fundamental investigations. In this study, the unique electronic and excitonic properties of the two dimensional carbon network biphenylene carbon were investigated with GW approach and the Bethe-Salpeter equation accounting for electron correlation effects and electron-hole interactions, respectively. Biphenylene carbon exhibits characteristic features including bright and dark excitons populating the optical gap of 0.52 eV and exciton binding energies of 530 meV asmore » well as a technologically relevant intrinsic band gap of 1.05 eV. Biphenylene carbon’s excitonic features, possibly tuned, suggest possible applications in the field of solar energy and quantum information technology in the future.« less

Measuring the dependence of the decay curve on the electron energy deposit in NaI(Tl)

NASA Astrophysics Data System (ADS)

Choong, W.-S.; Bizarri, G.; Cherepy, N. J.; Hull, G.; Moses, W. W.; Payne, S. A.

2011-08-01

We report on the first measurement of the decay times of NaI(Tl) as a function of the deposited electron energy. It has been suggested that the decay curve depends on the ionization density, which is correlated with the electron energy deposit in the scintillator. The ionization creates excitation states, which can decay radiatively and non-radiatively through a number of competing processes. As a result, the rate at which the excitation decays depends on the ionization density. A measurement of the decay curve as a function of the ionization density will allow us to probe the kinetic rates of the competing processes. The Scintillator Light Yield Non-proportionality Characterization Instrument (SLYNCI) measures the electron response of scintillators utilizing fast sampling ADCs to digitize the raw signals from the detectors, and so can provide a measurement of the light pulse shape from the scintillator. Using data collected with the SLYNCI instrument, the intrinsic scintillation profile is extracted on an event-by-event basis by deconvolving the raw signal with the impulse response of the system. Scintillation profiles with the same electron energy deposit are summed to obtain decay curves as a function of the deposited electron energy. The decay time constants are obtained by fitting the decay curves with a two-component exponential decay. While a slight dependence of the decay time constants on the electron energy deposit is observed, the results are not statistically significant.

The first-principles investigations on magnetic ground-state in Sm-doped phenanthrene

NASA Astrophysics Data System (ADS)

Han, Jia-Xing; Zhong, Guo-Hua; Wang, Xiao-Hui; Chen, Xiao-Jia; Lin, Hai-Qing

2017-05-01

Based on the density functional theory plus the effective Coulomb repulsion U, we have investigated the crystal structure, electronic properties and magnetic characteristics in Sm-doped phenanthrene, recently characterized as a superconductor with Tc˜5 -6 Kelvin. Calculated total energies of different magnetic states indicate that Sm-doped phenanthrene is stable at the ferromagnetic ground-state. Considered the strong electronic correlations effect due to the intercalation of Sm-4f electrons, we found that the Sm-4f contributes to the Fermi surface together with C-2p, which is different from K-doped phenanthrene. Compared with alkali-metal-doped phenanthrene, Sm atom has larger local magnetic moment, which suppresses the superconductivity in conventional superconductors. Our results indicate that the electron-electron correlations play an important role in superconductivity of Sm-doped phenanthrene.

Local-spin-density calculations for iron: Effect of spin interpolation on ground-state properties

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

MacLaren, J.M.; Clougherty, D.P.; Albers, R.C.

1990-08-15

Scalar-relativistic self-consistent linear muffin-tin orbital (LMTO) calculations for bcc and fcc Fe have been performed with several different local approximations to the exchange and correlation energy density and potential. Overall, in contrast to the conclusions of previous studies, we find that the local-spin-density approximation to exchange and correlation can provide an adequate description of bulk Fe {ital provided} that a proper parametrization of the correlation energy density and potential of the homogeneous electron gas over both spin and density is used. Lattice constants, found from the position of the minimum of the total energy as a function of Wigner-Seitz radius,more » agree to within 1% (for {ital s},{ital p},{ital d} LMTO's only) and within 1--2% (for {ital s},{ital p},{ital d},{ital f} LMTO's) of the experimental lattice constants for all forms used for the local correlation. The best agreement, however, was obtained using a local correlation potential derived from the Vosko-Wilk-Nusair form for the spin dependence of the correlation energy density. The calculation performed with this correlation potential was also the only calculation to correctly predict a bcc ferromagnetic ground state.« less

Semilocal density functional obeying a strongly tightened bound for exchange

PubMed Central

Sun, Jianwei; Perdew, John P.; Ruzsinszky, Adrienn

2015-01-01

Because of its useful accuracy and efficiency, density functional theory (DFT) is one of the most widely used electronic structure theories in physics, materials science, and chemistry. Only the exchange-correlation energy is unknown, and needs to be approximated in practice. Exact constraints provide useful information about this functional. The local spin-density approximation (LSDA) was the first constraint-based density functional. The Lieb–Oxford lower bound on the exchange-correlation energy for any density is another constraint that plays an important role in the development of generalized gradient approximations (GGAs) and meta-GGAs. Recently, a strongly and optimally tightened lower bound on the exchange energy was proved for one- and two-electron densities, and conjectured for all densities. In this article, we present a realistic “meta-GGA made very simple” (MGGA-MVS) for exchange that respects this optimal bound, which no previous beyond-LSDA approximation satisfies. This constraint might have been expected to worsen predicted thermochemical properties, but in fact they are improved over those of the Perdew–Burke–Ernzerhof GGA, which has nearly the same correlation part. MVS exchange is however radically different from that of other GGAs and meta-GGAs. Its exchange enhancement factor has a very strong dependence upon the orbital kinetic energy density, which permits accurate energies even with the drastically tightened bound. When this nonempirical MVS meta-GGA is hybridized with 25% of exact exchange, the resulting global hybrid gives excellent predictions for atomization energies, reaction barriers, and weak interactions of molecules. PMID:25561554

Semilocal density functional obeying a strongly tightened bound for exchange.

PubMed

Sun, Jianwei; Perdew, John P; Ruzsinszky, Adrienn

2015-01-20

Because of its useful accuracy and efficiency, density functional theory (DFT) is one of the most widely used electronic structure theories in physics, materials science, and chemistry. Only the exchange-correlation energy is unknown, and needs to be approximated in practice. Exact constraints provide useful information about this functional. The local spin-density approximation (LSDA) was the first constraint-based density functional. The Lieb-Oxford lower bound on the exchange-correlation energy for any density is another constraint that plays an important role in the development of generalized gradient approximations (GGAs) and meta-GGAs. Recently, a strongly and optimally tightened lower bound on the exchange energy was proved for one- and two-electron densities, and conjectured for all densities. In this article, we present a realistic "meta-GGA made very simple" (MGGA-MVS) for exchange that respects this optimal bound, which no previous beyond-LSDA approximation satisfies. This constraint might have been expected to worsen predicted thermochemical properties, but in fact they are improved over those of the Perdew-Burke-Ernzerhof GGA, which has nearly the same correlation part. MVS exchange is however radically different from that of other GGAs and meta-GGAs. Its exchange enhancement factor has a very strong dependence upon the orbital kinetic energy density, which permits accurate energies even with the drastically tightened bound. When this nonempirical MVS meta-GGA is hybridized with 25% of exact exchange, the resulting global hybrid gives excellent predictions for atomization energies, reaction barriers, and weak interactions of molecules.

Stability conditions for exact-exchange Kohn-Sham methods and their relation to correlation energies from the adiabatic-connection fluctuation-dissipation theorem.

PubMed

Bleiziffer, Patrick; Schmidtel, Daniel; Görling, Andreas

2014-11-28

The occurrence of instabilities, in particular singlet-triplet and singlet-singlet instabilities, in the exact-exchange (EXX) Kohn-Sham method is investigated. Hessian matrices of the EXX electronic energy with respect to the expansion coefficients of the EXX effective Kohn-Sham potential in an auxiliary basis set are derived. The eigenvalues of these Hessian matrices determine whether or not instabilities are present. Similar as in the corresponding Hartree-Fock case instabilities in the EXX method are related to symmetry breaking of the Hamiltonian operator for the EXX orbitals. In the EXX methods symmetry breaking can easily be visualized by displaying the local multiplicative exchange potential. Examples (N2, O2, and the polyyne C10H2) for instabilities and symmetry breaking are discussed. The relation of the stability conditions for EXX methods to approaches calculating the Kohn-Sham correlation energy via the adiabatic-connection fluctuation-dissipation (ACFD) theorem is discussed. The existence or nonexistence of singlet-singlet instabilities in an EXX calculation is shown to indicate whether or not the frequency-integration in the evaluation of the correlation energy is singular in the EXX-ACFD method. This method calculates the Kohn-Sham correlation energy through the ACFD theorem theorem employing besides the Coulomb kernel also the full frequency-dependent exchange kernel and yields highly accurate electronic energies. For the case of singular frequency-integrands in the EXX-ACFD method a regularization is suggested. Finally, we present examples of molecular systems for which the self-consistent field procedure of the EXX as well as the Hartree-Fock method can converge to more than one local minimum depending on the initial conditions.

Investigation on the correlation between energy deposition and clustered DNA damage induced by low-energy electrons.

PubMed

Liu, Wei; Tan, Zhenyu; Zhang, Liming; Champion, Christophe

2018-05-01

This study presents the correlation between energy deposition and clustered DNA damage, based on a Monte Carlo simulation of the spectrum of direct DNA damage induced by low-energy electrons including the dissociative electron attachment. Clustered DNA damage is classified as simple and complex in terms of the combination of single-strand breaks (SSBs) or double-strand breaks (DSBs) and adjacent base damage (BD). The results show that the energy depositions associated with about 90% of total clustered DNA damage are below 150 eV. The simple clustered DNA damage, which is constituted of the combination of SSBs and adjacent BD, is dominant, accounting for 90% of all clustered DNA damage, and the spectra of the energy depositions correlating with them are similar for different primary energies. One type of simple clustered DNA damage is the combination of a SSB and 1-5 BD, which is denoted as SSB + BD. The average contribution of SSB + BD to total simple clustered DNA damage reaches up to about 84% for the considered primary energies. In all forms of SSB + BD, the SSB + BD including only one base damage is dominant (above 80%). In addition, for the considered primary energies, there is no obvious difference between the average energy depositions for a fixed complexity of SSB + BD determined by the number of base damage, but average energy depositions increase with the complexity of SSB + BD. In the complex clustered DNA damage constituted by the combination of DSBs and BD around them, a relatively simple type is a DSB combining adjacent BD, marked as DSB + BD, and it is of substantial contribution (on average up to about 82%). The spectrum of DSB + BD is given mainly by the DSB in combination with different numbers of base damage, from 1 to 5. For the considered primary energies, the DSB combined with only one base damage contributes about 83% of total DSB + BD, and the average energy deposition is about 106 eV. However, the energy deposition increases with the complexity of clustered DNA damage, and therefore, the clustered DNA damage with high complexity still needs to be considered in the study of radiation biological effects, in spite of their small contributions to all clustered DNA damage.

Electron Correlation and Tranport Properties in Nuclear Fuel Materials

NASA Astrophysics Data System (ADS)

Yin, Quan; Haule, Kristjan; Kotliar, Gabriel; Savrasov, Sergey; Pickett, Warren

2011-03-01

Using first principle LDA+DMFT method, we conduct a systematic study on the correlated electronic structures and transport properties of select actinide carbides, nitrides, and oxides, many of which are nuclear fuel materials. Our results capture the metal--insulator Mott transition within the studied systems, and the appearance of the Zhang-Rice state in uranium dioxide. More importantly, by understanding the physics underlying their transport properties, we suggest ways to improve the efficiency of currently used fuels. This work is supported by the DOE Nuclear Energy University Program, contract No. 00088708.

Spectroscopic and electric properties of the LiCs molecule: a coupled cluster study including higher excitations

NASA Astrophysics Data System (ADS)

Sørensen, L. K.; Fleig, T.; Olsen, J.

2009-08-01

Aimed at obtaining complete and highly accurate potential energy surfaces for molecules containing heavy elements, we present a new general-order coupled cluster method which can be applied in the framework of the spin-free Dirac formalism. As an initial application we present a systematic study of electron correlation and relativistic effects on the spectroscopic and electric properties of the LiCs molecule in its electronic ground state. In particular, we closely investigate the importance of excitations higher than coupled cluster doubles, spin-free and spin-dependent relativistic effects and the correlation of outer-core electrons on the equilibrium bond length, the harmonic vibrational frequency, the dissociation energy, the dipole moment and the static electric dipole polarizability. We demonstrate that our new implementation allows for highly accurate calculations not only in the bonding region but also along the complete potential curve. The quality of our results is demonstrated by a vibrational analysis where an almost complete set of vibrational levels has been calculated accurately.

Electron-impact excitation of He: Dependence of electron-photon coherence parameters on the principal quantum number

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

Hammond, P.; Khakoo, M.A.; McConkey, J.W.

1987-12-01

Measurements are presented representing a complete set of electron-photon polarization correlation parameters for the excitation of n /sup 1/P states of He at an incident energy of 80 eV and an electron scattering angle of 20/sup 0/. The data support the predictions of a recent theoretical paper that these parameters should exhibit little variation with n. However, disagreement in absolute values between experiment and theory indicates the need for additional theoretical input into the problem.

Spectroscopic evidence for negative electronic compressibility in a quasi-three-dimensional spin–orbit correlated metal

DOE PAGES

He, Junfeng; Hogan, T.; Mion, Thomas R.; ...

2015-04-27

Negative compressibility is a sign of thermodynamic instability of open1,2,3 or non-equilibrium4,5 systems. In quantum materials consisting of multiple mutually coupled subsystems, the compressibility of one subsystem can be negative if it is countered by positive compressibility of the others. Manifestations of this effect have so far been limited to low-dimensional dilute electron systems6,7,8,9,10,11. Here, we present evidence from angle-resolved photoemission spectroscopy (ARPES) for negative electronic compressibility (NEC) in the quasi-three-dimensional (3D) spin–orbit correlated metal (Sr1-xLax)3Ir2O7. Increased electron filling accompanies an anomalous decrease of the chemical potential, as indicated by the overall movement of the deep valence bands. Such anomaly,more » suggestive of NEC, is shown to be primarily driven by the lowering in energy of the conduction band as the correlated bandgap reduces. Our finding points to a distinct pathway towards an uncharted territory of NEC featuring bulk correlated metals with unique potential for applications in low-power nanoelectronics and novel metamaterials.« less

Local self-energies for V and Pd emergent from a nonlocal LDA+FLEX implementation

NASA Astrophysics Data System (ADS)

Savrasov, Sergey Y.; Resta, Giacomo; Wan, Xiangang

2018-04-01

In the spirit of recently developed LDA+U and LDA+DMFT methods, we implement a combination of density functional theory in its local density approximation (LDA) with a k - and ω -dependent self-energy found from diagrammatic fluctuational exchange (FLEX) approximation. The active Hilbert space here is described by the correlated subset of electrons which allows one to tremendously reduce the sizes of the matrices needed to represent charge and spin susceptibilities. The method is perturbative in nature but accounts for both bubble and ladder diagrams and accumulates the physics of momentum-resolved spin fluctuations missing in such popular approach as GW. As an application, we study correlation effects on band structures in V and Pd. The d -electron self-energies emergent from this calculation are found to be remarkably k independent. However, when we compare our calculated electronic mass enhancements against LDA+DMFT, we find that for the longstanding problem of spin fluctuations in Pd, LDA+FLEX delivers a better agreement with experiment, although this conclusion depends on a particular value of the Hubbard U used in the simulation. We also discuss outcomes of a recently proposed combination of k -dependent FLEX with dynamical mean-field theory (DMFT).

TMDs and GPDs at a future Electron-Ion Collider

DOE PAGES

Ent, Rolf

2016-06-21

With two options studied at Brookhaven National Lab and Jefferson Laboratory the U.S., an Electron-Ion Collider (EIC) of energy √s=20-100 GeV was under design. Furthermore, the recent 2015 US Nuclear Science Long-Range Planning effort included a future EIC as a recommendation for future construction. The EIC will be unique in colliding polarised electrons off polarised protons and light nuclei, providing the spin degrees of freedom essential to pursue its physics program driven by spin structure, multi-dimensional tomographic images of protons and nuclei, and discovery of the role of collective effects of gluons in nuclei. The foreseen luminosity of the EIC,more » coupled with its energy variability and reach, will allow unprecedented three-dimensional imaging of the gluon and sea quark distributions, via both TMDs and GPDs, and to explore correlations amongst them. Its hermetic detection capability of correlated fragments promises to similar allow for precise tomographic images of the quark-gluon landscape in nuclei, transcending from light few-body nuclei to the heaviest nuclei, and could uncover how the TMD and GPD landscape changes when gluons display an anticipated collective behavior at the higher energies.« less

Ab initio model potential calculations on the electronic spectrum of Ni2 + -doped MgO including correlation, spin-orbit and embedding effects

NASA Astrophysics Data System (ADS)

Llusar, Rosa; Casarrubios, Marcos; Barandiarán, Zoila; Seijo, Luis

1996-10-01

An ab initio theoretical study of the optical absorption spectrum of Ni2+-doped MgO has been conducted by means of calculations in a MgO-embedded (NiO6)10-cluster. The calculations include long- and short-range embedding effects of electrostatic and quantum nature brought about by the MgO crystalline lattice, as well as electron correlation and spin-orbit effects within the (NiO6)10- cluster. The spin-orbit calculations have been performed using the spin-orbit-CI WB-AIMP method [Chem. Phys. Lett. 147, 597 (1988); J. Chem. Phys. 102, 8078 (1995)] which has been recently proposed and is applied here for the first time to the field of impurities in crystals. The WB-AIMP method is extended in order to handle correlation effects which, being necessary to produce accurate energy differences between spin-free states, are not needed for the proper calculation of spin-orbit couplings. The extension of the WB-AIMP method, which is also aimed at keeping the size of the spin-orbit-CI within reasonable limits, is based on the use of spin-free-state shifting operators. It is shown that the unreasonable spin-orbit splittings obtained for MgO:Ni2+ in spin-orbit-CI calculations correlating only 8 electrons become correct when the proposed extension is applied, so that the same CI space is used but energy corrections due to correlating up to 26 electrons are included. The results of the ligand field spectrum of MgO:Ni2+ show good overall agreement with the experimental measurements and a reassignment of the observed Eg(b3T1g) excited state is proposed and discussed.

Towards prediction of correlated material properties using quantum Monte Carlo methods

NASA Astrophysics Data System (ADS)

Wagner, Lucas

Correlated electron systems offer a richness of physics far beyond noninteracting systems. If we would like to pursue the dream of designer correlated materials, or, even to set a more modest goal, to explain in detail the properties and effective physics of known materials, then accurate simulation methods are required. Using modern computational resources, quantum Monte Carlo (QMC) techniques offer a way to directly simulate electron correlations. I will show some recent results on a few extremely challenging materials including the metal-insulator transition of VO2, the ground state of the doped cuprates, and the pressure dependence of magnetic properties in FeSe. By using a relatively simple implementation of QMC, at least some properties of these materials can be described truly from first principles, without any adjustable parameters. Using the QMC platform, we have developed a way of systematically deriving effective lattice models from the simulation. This procedure is particularly attractive for correlated electron systems because the QMC methods treat the one-body and many-body components of the wave function and Hamiltonian on completely equal footing. I will show some examples of using this downfolding technique and the high accuracy of QMC to connect our intuitive ideas about interacting electron systems with high fidelity simulations. The work in this presentation was supported in part by NSF DMR 1206242, the U.S. Department of Energy, Office of Science, Office of Advanced Scientific Computing Research, Scientific Discovery through Advanced Computing (SciDAC) program under Award Number FG02-12ER46875, and the Center for Emergent Superconductivity, Department of Energy Frontier Research Center under Grant No. DEAC0298CH1088. Computing resources were provided by a Blue Waters Illinois grant and INCITE PhotSuper and SuperMatSim allocations.

An (e, 2e+ ion) study of electron-impact ionization and fragmentation of tetrafluoromethane at low energies

NASA Astrophysics Data System (ADS)

Hossen, Khokon; Ren, Xueguang; Wang, Enliang; Kumar, S. V. K.; Dorn, Alexander

2018-03-01

We study ionization and fragmentation of tetrafluoromethane (CF4) molecule induced by electron impact at low energies ( E 0 = 38 and 67 eV). We use a reaction microscope combined with a pulsed photoemission electron beam for our experimental investigation. The momentum vectors of the two outgoing electrons (energies E 1, E 2) and one fragment ion are detected in triple coincidence (e, 2e+ ion). After dissociation, the fragment products observed are CF3 +, CF2 +, CF+, F+ and C+. For CF3 + and CF2 + channels, we measure the ionized orbitals binding energies, the kinetic energy (KE) of the charged fragments and the two-dimensional (2D) correlation map between binding energy (BE) and KE of the fragments. From the BE and KE spectra, we conclude which molecular orbitals contribute to particular fragmentation channels of CF4. We also measure the total ionization cross section for the formation of CF3 + and CF2 + ions as function of projectile energy. We compare our results with earlier experiments and calculations for electron-impact and photoionization. The major contribution to CF3 + formation originates from ionization of the 4t2 orbital while CF2 + is mainly formed after 3t2 orbital ionization. We also observe a weak contribution of the (4a1)-1 state for the channel CF3 +.

Suppression of the "Quasiclassical" proximity gap in correlated-metal--superconductor structures.

PubMed

Nikolić, Branislav K; Freericks, J K; Miller, P

2002-02-18

We study the energy and spatial dependence of the local density of states in a superconductor--correlated-metal--superconductor Josephson junction, where the correlated metal is a non-Fermi liquid (described by the Falicov-Kimball model). Many-body correlations are treated with dynamical mean-field theory, extended to inhomogeneous systems. While quasiclassical theories predict a minigap in the spectrum of a disordered Fermi liquid which is proximity-coupled within a mesoscopic junction, we find that increasing electron correlations destroy any minigap that might be opened in the absence of many-body correlations.

Magnetic ground state and electronic structure of CeRu(2)Al(10).

PubMed

Goraus, Jerzy; Ślebarski, Andrzej

2012-03-07

We present a combined theoretical and experimental study of the electronic structure for CeRu(2)Al(10) based on ab initio band structure calculations and x-ray photoemission spectroscopy (XPS) data. Our calculations were performed for the base unit cell and for the hypothetical unit cell which enables antiferromagnetic ordering. The stability of the magnetic phase was investigated within fixed spin moment calculations. When additional 4f correlations are not included in the LSDA C U approach, CeRu(2)Al(10) exhibits an unstable magnetic configuration with the difference in total energy per unit cell between the weakly magnetic state and the non-magnetic one of the order ~0.3 meV. We found that Coulomb correlations among 4f electrons, when they are included in the LSDA C U approach, stabilize the magnetic structure. In the weakly correlated system (small U) an antiferromagnetic (AFM) ground state with the lowest total energy is preferred. The situation is, however, the opposite when the 4f correlations are strong. In this case the ferromagnetic (FM) ground state is preferred. By comparing our calculations with the experimental data we conclude that the 4f correlations in CeRu(2)Al(10) are weak. We also carried out a structural relaxation of atomic positions within the Cmcm unit cell and we found that the Al atoms exhibit noticeable displacement from their positions known from x-ray diffraction (XRD) analysis.

Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder

NASA Astrophysics Data System (ADS)

Thouin, Félix; Neutzner, Stefanie; Cortecchia, Daniele; Dragomir, Vlad Alexandru; Soci, Cesare; Salim, Teddy; Lam, Yeng Ming; Leonelli, Richard; Petrozza, Annamaria; Kandada, Ajay Ram Srimath; Silva, Carlos

2018-03-01

With strongly bound and stable excitons at room temperature, single-layer, two-dimensional organic-inorganic hybrid perovskites are viable semiconductors for light-emitting quantum optoelectronics applications. In such a technological context, it is imperative to comprehensively explore all the factors—chemical, electronic, and structural—that govern strong multiexciton correlations. Here, by means of two-dimensional coherent spectroscopy, we examine excitonic many-body effects in pure, single-layer (PEA) 2PbI4 (PEA = phenylethylammonium). We determine the binding energy of biexcitons—correlated two-electron, two-hole quasiparticles—to be 44 ±5 meV at room temperature. The extraordinarily high values are similar to those reported in other strongly excitonic two-dimensional materials such as transition-metal dichalcogenides. Importantly, we show that this binding energy increases by ˜25 % upon cooling to 5 K. Our work highlights the importance of multiexciton correlations in this class of technologically promising, solution-processable materials, in spite of the strong effects of lattice fluctuations and dynamic disorder.

Correlation Among the Variant Group, Effective Grain Size, and Elastic Strain Energy During the Phase Transformation in 9Ni Steels

NASA Astrophysics Data System (ADS)

Terasaki, Hidenori; Moriguchi, Koji; Tomio, Yusaku; Yamagishi, Hideki; Morito, Shigekazu

2017-12-01

The effect of carbon content on the density of variant-pair boundaries was investigated in 9Ni steel using an electron backscatter diffraction patterns method. The changes in the density of variant-pair boundaries were correlated with the nondestructive measured values of shear modulus of the austenite phase at the phase transformation point. Furthermore, the effective grain size was correlated with the shear modulus and the density of variant-pair boundaries. These relations are discussed from the viewpoint of self-accommodation of elastic strain energy and the nucleation event in the bainite and martensitic transformations.

Electronic field emission models beyond the Fowler-Nordheim one

NASA Astrophysics Data System (ADS)

Lepetit, Bruno

2017-12-01

We propose several quantum mechanical models to describe electronic field emission from first principles. These models allow us to correlate quantitatively the electronic emission current with the electrode surface details at the atomic scale. They all rely on electronic potential energy surfaces obtained from three dimensional density functional theory calculations. They differ by the various quantum mechanical methods (exact or perturbative, time dependent or time independent), which are used to describe tunneling through the electronic potential energy barrier. Comparison of these models between them and with the standard Fowler-Nordheim one in the context of one dimensional tunneling allows us to assess the impact on the accuracy of the computed current of the approximations made in each model. Among these methods, the time dependent perturbative one provides a well-balanced trade-off between accuracy and computational cost.

On the influence of noise correlations in measurement data on basis image noise in dual-energylike x-ray imaging

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

Roessl, Ewald; Ziegler, Andy; Proksa, Roland

2007-03-15

In conventional dual-energy systems, two transmission measurements with distinct spectral characteristics are performed. These measurements are used to obtain the line integrals of two basis material densities. Usually, the measurement process is such that the two measured signals can be treated as independent and therefore uncorrelated. Recently, however, a readout system for x-ray detectors has been introduced for which this is no longer the case. The readout electronics is designed to obtain simultaneous measurements of the total number of photons N and the total energy E they deposit in the sensor material. Practically, this is realized by a signal replicationmore » and separate counting and integrating processing units. Since the quantities N and E are (electronically) derived from one and the same physical sensor signal, they are statistically correlated. Nevertheless, the pair N and E can be used to perform a dual-energy processing following the well-known approach by Alvarez and Macovski. Formally, this means that N is to be identified with the first dual-energy measurement M{sub 1} and E with the second measurement M{sub 2}. In the presence of input correlations between M{sub 1}=N and M{sub 2}=E, however, the corresponding analytic expressions for the basis image noise have to be modified. The main observation made in this paper is that for positively correlated data, as is the case for the simultaneous counting and integrating device mentioned above, the basis image noise is suppressed through the influence of the covariance between the two signals. We extend the previously published relations for the basis image noise to the case where the original measurements are not independent and illustrate the importance of the input correlations by comparing dual-energy basis image noise resulting from the device mentioned above and a device measuring the photon numbers and the deposited energies consecutively.« less

Hot-electron luminescence and polarization in GaAs/sub 1-x/P/sub x/ alloys

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

Charfi, F.F.; Zouaghi, M.; Planel, R.

1986-04-15

The weak direct-gap luminescence originating from the GAMMA valley of GaAs/sub 1-x/P/sub x/ indirect-gap alloys is observed. Incident energy dependence and polarization correlation of the luminescence with the exciting light are presented. The luminescence is interpreted as recombination of hot electrons, with strong momentum anisotropy, on acceptors. The dynamics of conduction electrons in the GAMMA valley can be discussed.

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

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Target surface area effects on hot electron dynamics from high intensity laser–plasma interactions

DOE PAGES

Zulick, C.; Raymond, A.; McKelvey, A.; ...

2016-06-15

Reduced surface area targets were studied using an ultra-high intensity femtosecond laser in order to determine the effect of electron sheath field confinement on electron dynamics. X-ray emission due to energetic electrons was imaged using a K α imaging crystal. Electrons were observed to travel along the surface of wire targets, and were slowed mainly by the induced fields. Targets with reduced surface areas were correlated with increased hot electron densities and proton energies. Furthermore, Hybrid Vlasov–Fokker–Planck simulations demonstrated increased electric sheath field strength in reduced surface area targets.

Electron correlation in the interacting quantum atoms partition via coupled-cluster lagrangian densities.

PubMed

Holguín-Gallego, Fernando José; Chávez-Calvillo, Rodrigo; García-Revilla, Marco; Francisco, Evelio; Pendás, Ángel Martín; Rocha-Rinza, Tomás

2016-07-15

The electronic energy partition established by the Interacting Quantum Atoms (IQA) approach is an important method of wavefunction analyses which has yielded valuable insights about different phenomena in physical chemistry. Most of the IQA applications have relied upon approximations, which do not include either dynamical correlation (DC) such as Hartree-Fock (HF) or external DC like CASSCF theory. Recently, DC was included in the IQA method by means of HF/Coupled-Cluster (CC) transition densities (Chávez-Calvillo et al., Comput. Theory Chem. 2015, 1053, 90). Despite the potential utility of this approach, it has a few drawbacks, for example, it is not consistent with the calculation of CC properties different from the total electronic energy. To improve this situation, we have implemented the IQA energy partition based on CC Lagrangian one- and two-electron orbital density matrices. The development presented in this article is tested and illustrated with the H2 , LiH, H2 O, H2 S, N2 , and CO molecules for which the IQA results obtained under the consideration of (i) the CC Lagrangian, (ii) HF/CC transition densities, and (iii) HF are critically analyzed and compared. Additionally, the effect of the DC in the different components of the electronic energy in the formation of the T-shaped (H2 )2 van der Waals cluster and the bimolecular nucleophilic substitution between F(-) and CH3 F is examined. We anticipate that the approach put forward in this article will provide new understandings on subjects in physical chemistry wherein DC plays a crucial role like molecular interactions along with chemical bonding and reactivity. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Bond breaking and bond formation: how electron correlation is captured in many-body perturbation theory and density-functional theory.

PubMed

Caruso, Fabio; Rohr, Daniel R; Hellgren, Maria; Ren, Xinguo; Rinke, Patrick; Rubio, Angel; Scheffler, Matthias

2013-04-05

For the paradigmatic case of H(2) dissociation, we compare state-of-the-art many-body perturbation theory in the GW approximation and density-functional theory in the exact-exchange plus random-phase approximation (RPA) for the correlation energy. For an unbiased comparison and to prevent spurious starting point effects, both approaches are iterated to full self-consistency (i.e., sc-RPA and sc-GW). The exchange-correlation diagrams in both approaches are topologically identical, but in sc-RPA they are evaluated with noninteracting and in sc-GW with interacting Green functions. This has a profound consequence for the dissociation region, where sc-RPA is superior to sc-GW. We argue that for a given diagrammatic expansion, sc-RPA outperforms sc-GW when it comes to bond breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

Kinetic Energy of Hydrocarbons as a Function of Electron Density and Convolutional Neural Networks.

PubMed

Yao, Kun; Parkhill, John

2016-03-08

We demonstrate a convolutional neural network trained to reproduce the Kohn-Sham kinetic energy of hydrocarbons from an input electron density. The output of the network is used as a nonlocal correction to conventional local and semilocal kinetic functionals. We show that this approximation qualitatively reproduces Kohn-Sham potential energy surfaces when used with conventional exchange correlation functionals. The density which minimizes the total energy given by the functional is examined in detail. We identify several avenues to improve on this exploratory work, by reducing numerical noise and changing the structure of our functional. Finally we examine the features in the density learned by the neural network to anticipate the prospects of generalizing these models.

Correlation of doping, structure, and carrier dynamics in a single GaN nanorod

NASA Astrophysics Data System (ADS)

Zhou, Xiang; Lu, Ming-Yen; Lu, Yu-Jung; Gwo, Shangjr; Gradečak, Silvija

2013-06-01

We report the nanoscale optical investigation of a single GaN p-n junction nanorod by cathodoluminescence (CL) in a scanning transmission electron microscope. CL emission characteristic of dopant-related transitions was correlated to doping and structural defect in the nanorod, and used to determine p-n junction position and minority carrier diffusion lengths of 650 nm and 165 nm for electrons and holes, respectively. Temperature-dependent CL study reveals an activation energy of 19 meV for non-radiative recombination in Mg-doped GaN nanorods. These results directly correlate doping, structure, carrier dynamics, and optical properties of GaN nanostructure, and provide insights for device design and fabrication.

Dynamics of correlation-frozen antinodal quasiparticles in superconducting cuprates

PubMed Central

Cilento, Federico; Manzoni, Giulia; Sterzi, Andrea; Peli, Simone; Ronchi, Andrea; Crepaldi, Alberto; Boschini, Fabio; Cacho, Cephise; Chapman, Richard; Springate, Emma; Eisaki, Hiroshi; Greven, Martin; Berciu, Mona; Kemper, Alexander F.; Damascelli, Andrea; Capone, Massimo; Giannetti, Claudio; Parmigiani, Fulvio

2018-01-01

Many puzzling properties of high–critical temperature (Tc) superconducting (HTSC) copper oxides have deep roots in the nature of the antinodal quasiparticles, the elementary excitations with wave vector parallel to the Cu–O bonds. These electronic states are most affected by the onset of antiferromagnetic correlations and charge instabilities, and they host the maximum of the anisotropic superconducting gap and pseudogap. We use time-resolved extreme-ultraviolet photoemission with proper photon energy (18 eV) and time resolution (50 fs) to disclose the ultrafast dynamics of the antinodal states in a prototypical HTSC cuprate. After photoinducing a nonthermal charge redistribution within the Cu and O orbitals, we reveal a dramatic momentum-space differentiation of the transient electron dynamics. Whereas the nodal quasiparticle distribution is heated up as in a conventional metal, new quasiparticle states transiently emerge at the antinodes, similarly to what is expected for a photoexcited Mott insulator, where the frozen charges can be released by an impulsive excitation. This transient antinodal metallicity is mapped into the dynamics of the O-2p bands, thus directly demonstrating the intertwining between the low- and high-energy scales that is typical of correlated materials. Our results suggest that the correlation-driven freezing of the electrons moving along the Cu–O bonds, analogous to the Mott localization mechanism, constitutes the starting point for any model of high-Tc superconductivity and other exotic phases of HTSC cuprates. PMID:29507885

Visualizing nanoscale phase morphology for understanding photovoltaic performance of PTB7: PC71BM solar cell

NASA Astrophysics Data System (ADS)

Supasai, Thidarat; Amornkitbamrung, Vittaya; Thanachayanont, Chanchana; Tang, I.-Ming; Sutthibutpong, Thana; Rujisamphan, Nopporn

2017-11-01

Visualizing and controlling the phase separation of the donor and acceptor domains in organic bulk-hetero-junction (BHJ) solar devices made with poly([4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethyl-hexyl)carbon-yl]thieno[3,4-bthiophenediyl]) (PTB7) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) are needed to achieve high power conversion efficiency (PCE). Traditional bright-field (BF) imaging, especially of polymeric materials, produces images of poor contrast when done at the nanoscale level. Clear nanoscale morphologies of the PTB7:PC71BM blends prepared with different 1,8-diiodooctane (DIO) concentrations were seen when using the energy-filtered transmission electron microscopy (EFTEM). The electron energy loss (EELS) spectra of the pure PTB7 and PC71BM samples are centered at 22.7 eV and 24.5 eV, respectively. Using the electrons whose energy losses are in the range of 16-30 eV, detail information of the phase morphology at the nanoscale was obtained. Correlations between the improvement in the photovoltaic performances and the increased electron mobility were seen. These correlations are discussed in terms of the changes (at the nanoscale level) in blending phase morphology when different DIO concentrations are added.

Measurement of the Positron Annihilation Induced Auger Electron Spectrum from Ag(100)

NASA Astrophysics Data System (ADS)

Joglekar, P.; Shastry, K.; Fazleev, N. G.; Weiss, A. H.

2013-06-01

Research has demonstrated that Positron Annihilation Induced Auger Spectroscopy (PAES) can be used to probe the top-most atomic layer of surfaces and to obtain Auger spectra that are completely free of beam-impact induced secondary background. The high degree of surface selectivity in PAES is a result of the fact that positrons implanted at low energies are trapped with high efficiency at an image-correlation potential well at the surface resulting in almost all of the positrons annihilating with atoms in the top-most layer. Secondary electrons associated with the impact of the incident positrons can be eliminated by a suitable choice of an incident beam energy. In this paper we present the results of measurements of the energy spectrum of electrons emitted as a result of positron annihilation induced Auger electron emission from a clean Ag(100) surface using a series of incident beam energies ranging from 20 eV down to 2 eV. A peak in the spectrum was observed at ~40 eV corresponding to the N2,3VV Auger transition in agreement with previous PAES studies. This peak was accompanied by an even larger low energy tail which persisted even at the lowest beam energies. Our results for Ag(100) are consistent with previous studies of Cu and Au and indicate that a significant fraction of electrons leaving the sample are emitted in the low energy tail and suggest a strong mechanism for energy sharing in the Auger process.

PAREMD: A parallel program for the evaluation of momentum space properties of atoms and molecules

NASA Astrophysics Data System (ADS)

Meena, Deep Raj; Gadre, Shridhar R.; Balanarayan, P.

2018-03-01

The present work describes a code for evaluating the electron momentum density (EMD), its moments and the associated Shannon information entropy for a multi-electron molecular system. The code works specifically for electronic wave functions obtained from traditional electronic structure packages such as GAMESS and GAUSSIAN. For the momentum space orbitals, the general expression for Gaussian basis sets in position space is analytically Fourier transformed to momentum space Gaussian basis functions. The molecular orbital coefficients of the wave function are taken as an input from the output file of the electronic structure calculation. The analytic expressions of EMD are evaluated over a fine grid and the accuracy of the code is verified by a normalization check and a numerical kinetic energy evaluation which is compared with the analytic kinetic energy given by the electronic structure package. Apart from electron momentum density, electron density in position space has also been integrated into this package. The program is written in C++ and is executed through a Shell script. It is also tuned for multicore machines with shared memory through OpenMP. The program has been tested for a variety of molecules and correlated methods such as CISD, Møller-Plesset second order (MP2) theory and density functional methods. For correlated methods, the PAREMD program uses natural spin orbitals as an input. The program has been benchmarked for a variety of Gaussian basis sets for different molecules showing a linear speedup on a parallel architecture.

Positive semidefinite tensor factorizations of the two-electron integral matrix for low-scaling ab initio electronic structure.

PubMed

Hoy, Erik P; Mazziotti, David A

2015-08-14

Tensor factorization of the 2-electron integral matrix is a well-known technique for reducing the computational scaling of ab initio electronic structure methods toward that of Hartree-Fock and density functional theories. The simplest factorization that maintains the positive semidefinite character of the 2-electron integral matrix is the Cholesky factorization. In this paper, we introduce a family of positive semidefinite factorizations that generalize the Cholesky factorization. Using an implementation of the factorization within the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)], we study several inorganic molecules, alkane chains, and potential energy curves and find that this generalized factorization retains the accuracy and size extensivity of the Cholesky factorization, even in the presence of multi-reference correlation. The generalized family of positive semidefinite factorizations has potential applications to low-scaling ab initio electronic structure methods that treat electron correlation with a computational cost approaching that of the Hartree-Fock method or density functional theory.

A correlative approach to segmenting phases and ferrite morphologies in transformation-induced plasticity steel using electron back-scattering diffraction and energy dispersive X-ray spectroscopy.

PubMed

Gazder, Azdiar A; Al-Harbi, Fayez; Spanke, Hendrik Th; Mitchell, David R G; Pereloma, Elena V

2014-12-01

Using a combination of electron back-scattering diffraction and energy dispersive X-ray spectroscopy data, a segmentation procedure was developed to comprehensively distinguish austenite, martensite, polygonal ferrite, ferrite in granular bainite and bainitic ferrite laths in a thermo-mechanically processed low-Si, high-Al transformation-induced plasticity steel. The efficacy of the ferrite morphologies segmentation procedure was verified by transmission electron microscopy. The variation in carbon content between the ferrite in granular bainite and bainitic ferrite laths was explained on the basis of carbon partitioning during their growth. Copyright © 2014 Elsevier B.V. All rights reserved.

Correlated electron-nuclear dynamics with conditional wave functions.

PubMed

Albareda, Guillermo; Appel, Heiko; Franco, Ignacio; Abedi, Ali; Rubio, Angel

2014-08-22

The molecular Schrödinger equation is rewritten in terms of nonunitary equations of motion for the nuclei (or electrons) that depend parametrically on the configuration of an ensemble of generally defined electronic (or nuclear) trajectories. This scheme is exact and does not rely on the tracing out of degrees of freedom. Hence, the use of trajectory-based statistical techniques can be exploited to circumvent the calculation of the computationally demanding Born-Oppenheimer potential-energy surfaces and nonadiabatic coupling elements. The concept of the potential-energy surface is restored by establishing a formal connection with the exact factorization of the full wave function. This connection is used to gain insight from a simplified form of the exact propagation scheme.

Epitaxial Ba2IrO4 thin-films grown on SrTiO3 substrates by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Nichols, J.; Korneta, O. B.; Terzic, J.; Cao, G.; Brill, J. W.; Seo, S. S. A.

2014-03-01

We have synthesized epitaxial Ba2IrO4 (BIO) thin-films on SrTiO3 (001) substrates by pulsed laser deposition and studied their electronic structure by dc-transport and optical spectroscopic experiments. We have observed that BIO thin-films are insulating but close to the metal-insulator transition boundary with significantly smaller transport and optical gap energies than its sister compound, Sr2IrO4. Moreover, BIO thin-films have both an enhanced electronic bandwidth and electronic-correlation energy. Our results suggest that BIO thin-films have great potential for realizing the interesting physical properties predicted in layered iridates.

Characterization of radiation belt electron energy spectra from CRRES observations

NASA Astrophysics Data System (ADS)

Johnston, W. R.; Lindstrom, C. D.; Ginet, G. P.

2010-12-01

Energetic electrons in the outer radiation belt and the slot region exhibit a wide variety of energy spectral forms, more so than radiation belt protons. We characterize the spatial and temporal dependence of these forms using observations from the CRRES satellite Medium Electron Sensor A (MEA) and High-Energy Electron Fluxmeter (HEEF) instruments, together covering an energy range 0.15-8 MeV. Spectra were classified with two independent methods, data clustering and curve-fitting analyses, in each case defining categories represented by power law, exponential, and bump-on-tail (BOT) or other complex shapes. Both methods yielded similar results, with BOT, exponential, and power law spectra respectively dominating in the slot region, outer belt, and regions just beyond the outer belt. The transition from exponential to power law spectra occurs at higher L for lower magnetic latitude. The location of the transition from exponential to BOT spectra is highly correlated with the location of the plasmapause. In the slot region during the days following storm events, electron spectra were observed to evolve from exponential to BOT yielding differential flux minima at 350-650 keV and maxima at 1.5-2 MeV; such evolution has been attributed to energy-dependent losses from scattering by whistler hiss.

Electronic properties of CdWO{sub 4}: Use of hybrid exchange and correlation functionals

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

Meena, B. S., E-mail: bsmphysics@gmail.com; Mund, H. S.; Ahuja, B. L.

Energy bands, density of states (DOS), Mulliken population (MP) and electron momentum densities (EMDs) of CdWO{sub 4} are presented using hybrid exchange and correlation functionals namely B3LYP, B3PW and PBE0. To validate the present hybrid potentials, theoretical EMDs have been compared with the experimental Compton profile. It is found that LCAO-B3LYP based Compton profile gives a better agreement with experiment than other theoretical profiles. The energy bands and DOS show a wide band gap semiconducting nature of CdWO{sub 4}. The theoretical band gap obtained using B3LYP scheme reconciles well with the available experimental data. In addition, we have also presentedmore » the anisotropies in EMDs along [100], [110] and [001] directions and the bonding effects using the MP data.« less

Quantum Femtosecond Magnetism: Phase Transition in Step with Light in a Strongly Correlated Manganese Oxide

NASA Astrophysics Data System (ADS)

Wang, Jigang

2014-03-01

Research of non-equilibrium phase transitions of strongly correlated electrons is built around addressing an outstanding challenge: how to achieve ultrafast manipulation of competing magnetic/electronic phases and reveal thermodynamically hidden orders at highly non-thermal, femtosecond timescales? Recently we reveal a new paradigm called quantum femtosecond magnetism-photoinduced femtosecond magnetic phase transitions driven by quantum spin flip fluctuations correlated with laser-excited inter-atomic coherent bonding. We demonstrate an antiferromagnetic (AFM) to ferromagnetic (FM) switching during about 100 fs laser pulses in a colossal magneto-resistive manganese oxide. Our results show a huge photoinduced femtosecond spin generation, measured by magnetic circular dichroism, with photo-excitation threshold behavior absent in the picosecond dynamics. This reveals an initial quantum coherent regime of magnetism, while the optical polarization/coherence still interacts with the spins to initiate local FM correlations that compete with the surrounding AFM matrix. Our results thus provide a framework that explores quantum non-equilibrium kinetics to drive phase transitions between exotic ground states in strongly correlated elecrons, and raise fundamental questions regarding some accepted rules, such as free energy and adiabatic potential surface. This work is in collaboration with Tianqi Li, Aaron Patz, Leonidas Mouchliadis, Jiaqiang Yan, Thomas A. Lograsso, Ilias E. Perakis. This work was supported by the National Science Foundation (contract no. DMR-1055352). Material synthesis at the Ames Laboratory was supported by the US Department of Energy-Basic Energy Sciences (contract no. DE-AC02-7CH11358).

Pair 2-electron reduced density matrix theory using localized orbitals

NASA Astrophysics Data System (ADS)

Head-Marsden, Kade; Mazziotti, David A.

2017-08-01

Full configuration interaction (FCI) restricted to a pairing space yields size-extensive correlation energies but its cost scales exponentially with molecular size. Restricting the variational two-electron reduced-density-matrix (2-RDM) method to represent the same pairing space yields an accurate lower bound to the pair FCI energy at a mean-field-like computational scaling of O (r3) where r is the number of orbitals. In this paper, we show that localized molecular orbitals can be employed to generate an efficient, approximately size-extensive pair 2-RDM method. The use of localized orbitals eliminates the substantial cost of optimizing iteratively the orbitals defining the pairing space without compromising accuracy. In contrast to the localized orbitals, the use of canonical Hartree-Fock molecular orbitals is shown to be both inaccurate and non-size-extensive. The pair 2-RDM has the flexibility to describe the spectra of one-electron RDM occupation numbers from all quantum states that are invariant to time-reversal symmetry. Applications are made to hydrogen chains and their dissociation, n-acene from naphthalene through octacene, and cadmium telluride 2-, 3-, and 4-unit polymers. For the hydrogen chains, the pair 2-RDM method recovers the majority of the energy obtained from similar calculations that iteratively optimize the orbitals. The localized-orbital pair 2-RDM method with its mean-field-like computational scaling and its ability to describe multi-reference correlation has important applications to a range of strongly correlated phenomena in chemistry and physics.

Nonthermal X-ray Spectral Flattening toward Low Energies in Early Impulsive Flares

NASA Technical Reports Server (NTRS)

Holman, Gordon D.

2007-01-01

The determination of the low-energy cutoff to nonthermal electron distributions is critical to the calculation of the nonthermal energy in solar flares. The most direct evidence for low-energy cutoffs is flattening of the power-law, nontherma1 X-ray spectra at low energies. However, because of the plasma preheating often seen in flares, the thermal emissions at low energies may hide such spectral flattening of the nonthermal component. We select a category of flares, which we call "early impulsive flares", in which the > 25 keV hard X-ray (HXR) flux increase is delayed by less than 30 s after the flux increase at lower energies. Thus, the plasma preheating in these flares is minimal, so the nonthermal spectrum can be determined to lower energies than in flares with significant preheating. Out of a sample of 33 early impulsive flares observed by the Ramaty High Energy Solar Spectroscopy Imager (RHESSI), 9 showed spectral flattening toward low energies. In these events, the break energy of the double power-law fit to the HXR spectra lies in the range of 10-50 keV, significantly lower than the value we have seen for other flares that do not show such early impulsive emissions. In particular, it correlates with the HXR flux. After correcting the spatially-integrated spectra for albedo from isotropically emitted X-rays and using RHESSI imaging spectroscopy to exclude the extended albedo halo, we find that albedo associated with isotropic or nearly isotropic electrons can only account for the spectral flattening in 3 flares near Sun center. The spectral flattening in the remaining 6 flares is found to be consistent with the existence of a low-energy cutoff in the electron spectrum, falling in the range of 15-50 keV, which also correlates with the HXR flux.

Two-electron states of a group-V donor in silicon from atomistic full configuration interactions

NASA Astrophysics Data System (ADS)

Tankasala, Archana; Salfi, Joseph; Bocquel, Juanita; Voisin, Benoit; Usman, Muhammad; Klimeck, Gerhard; Simmons, Michelle Y.; Hollenberg, Lloyd C. L.; Rogge, Sven; Rahman, Rajib

2018-05-01

Two-electron states bound to donors in silicon are important for both two-qubit gates and spin readout. We present a full configuration interaction technique in the atomistic tight-binding basis to capture multielectron exchange and correlation effects taking into account the full band structure of silicon and the atomic-scale granularity of a nanoscale device. Excited s -like states of A1 symmetry are found to strongly influence the charging energy of a negative donor center. We apply the technique on subsurface dopants subjected to gate electric fields and show that bound triplet states appear in the spectrum as a result of decreased charging energy. The exchange energy, obtained for the two-electron states in various confinement regimes, may enable engineering electrical control of spins in donor-dot hybrid qubits.

Potential energy curves of the Na2+ molecular ion from all-electron ab initio relativistic calculations

NASA Astrophysics Data System (ADS)

Bewicz, Anna; Musiał, Monika; Kucharski, Stanisław A.

2017-11-01

The equation-of-motion coupled-cluster method for electron affinity calculations has been used to study potential energy curves (PECs) for the Na+2 molecular ion. Although the studied molecule represents the open shell system the applied approach employs the closed shell Na+ 22 ion as the reference. In addition the Na+ 22 system dissociates into the closed shell fragments; hence, the restricted Hartree-Fock scheme can be used within the whole range of interatomic distances, from 2 to 45 Å. We used large basis set engaging 268 basis functions with all 21 electrons correlated. The relativistic effects are included via second-order Douglas-Kroll method. The computed PECs, spectroscopic molecular constants and vibrational energy levels agree well with experimental values if the latter are available or with other theoretical data.

Ensemble Monte Carlo particle investigation of hot electron induced source-drain burnout characteristics of GaAs field-effect transistors

NASA Astrophysics Data System (ADS)

Moglestue, C.; Buot, F. A.; Anderson, W. T.

1995-08-01

The lattice heating rate has been calculated for GaAs field-effect transistors of different source-drain channel design by means of the ensemble Monte Carlo particle model. Transport of carriers in the substrate and the presence of free surface charges are also included in our simulation. The actual heat generation was obtained by accounting for the energy exchanged with the lattice of the semiconductor during phonon scattering. It was found that the maximum heating rate takes place below the surface near the drain end of the gate. The results correlate well with a previous hydrodynamic energy transport estimate of the electronic energy density, but shifted slightly more towards the drain. These results further emphasize the adverse effects of hot electrons on the Ohmic contacts.

First Direct Observation of Runaway-Electron-Driven Whistler Waves in Tokamaks

NASA Astrophysics Data System (ADS)

Spong, D. A.; Heidbrink, W. W.; Paz-Soldan, C.; Du, X. D.; Thome, K. E.; Van Zeeland, M. A.; Collins, C.; Lvovskiy, A.; Moyer, R. A.; Austin, M. E.; Brennan, D. P.; Liu, C.; Jaeger, E. F.; Lau, C.

2018-04-01

DIII-D experiments at low density (ne˜1019 m-3 ) have directly measured whistler waves in the 100-200 MHz range excited by multi-MeV runaway electrons. Whistler activity is correlated with runaway intensity (hard x-ray emission level), occurs in novel discrete frequency bands, and exhibits nonlinear limit-cycle-like behavior. The measured frequencies scale with the magnetic field strength and electron density as expected from the whistler dispersion relation. The modes are stabilized with increasing magnetic field, which is consistent with wave-particle resonance mechanisms. The mode amplitudes show intermittent time variations correlated with changes in the electron cyclotron emission that follow predator-prey cycles. These can be interpreted as wave-induced pitch angle scattering of moderate energy runaways. The tokamak runaway-whistler mechanisms have parallels to whistler phenomena in ionospheric plasmas. The observations also open new directions for the modeling and active control of runaway electrons in tokamaks.

Low-energy measurements of electron-photon angular correlation in electron-impact excitation of the 2/sup 1/P state of helium

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

Steph, N.C.; Golden, D.E.

1983-03-01

Electron-photon angular correlations between electrons which have excited the 2/sup 1/P state of He and photons from the 2/sup 1/P..-->..1/sup 1/S transition have been studied for 27-, 30-, 35-, and 40-eV incident electrons. Values of lambda and Vertical BarchiVertical Bar obtained from these measurements are compared to values obtained in distorted-wave and R-matrix calculations. The values of lambda and Vertical BarchiVertical Bar have been combined to examine the behavior of Vertical BarO/sub 1//sub -//sup colvertical-bar/ (lambda(1-lambda)sinVertical BarchiVertical Bar), the nonvanishing component of orientation. At 27 eV, a substantial decrease was observed in the values of lambda and Vertical BarO/sub 1//submore » -//sup colvertical-bar/, compared with their values for E> or =30 eV.« less

SU-E-T-781: Using An Electronic Portal Imaging Device (EPID) for Correlating Linac Photon Beam Energies

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

Yaddanapudi, S; Cai, B; Sun, B

2015-06-15

Purpose: Electronic portal imaging devices (EPIDs) have proven to be useful for measuring several parameters of interest in linear accelerator (linac) quality assurance (QA). The purpose of this project was to evaluate the feasibility of using EPIDs for determining linac photon beam energies. Methods: Two non-clinical Varian TrueBeam linacs (Varian Medical Systems, Palo Alto, CA) with 6MV and 10MV photon beams were used to perform the measurements. The linacs were equipped with an amorphous silicon based EPIDs (aSi1000) that were used for the measurements. We compared the use of flatness versus percent depth dose (PDD) for predicting changes in linacmore » photon beam energy. PDD was measured in 1D water tank (Sun Nuclear Corporation, Melbourne FL) and the profiles were measured using 2D ion-chamber array (IC-Profiler, Sun Nuclear) and the EPID. Energy changes were accomplished by varying the bending magnet current (BMC). The evaluated energies conformed with the AAPM TG142 tolerance of ±1% change in PDD. Results: BMC changes correlating with a ±1% change in PDD corresponded with a change in flatness of ∼1% to 2% from baseline values on the EPID. IC Profiler flatness values had the same correlation. We observed a similar trend for the 10MV beam energy changes. Our measurements indicated a strong correlation between changes in linac photon beam energy and changes in flatness. For all machines and energies, beam energy changes produced change in the uniformity (AAPM TG-142), varying from ∼1% to 2.5%. Conclusions: EPID image analysis of beam profiles can be used to determine linac photon beam energy changes. Flatness-based metrics or uniformity as defined by AAPM TG-142 were found to be more sensitive to linac photon beam energy changes than PDD. Research funding provided by Varian Medical Systems. Dr. Sasa Mutic receives compensation for providing patient safety training services from Varian Medical Systems, the sponsor of this study.« less

Electronic structure of HxVO2 probed with in-situ spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Sandilands, Luke J.; Kang, Taedong; Son, Jaeseok; Sohn, C. H.; Yoon, Hyojin; Son, Junwoo; Moon, S. J.; Noh, T. W.

Vanadium dioxide (VO2) undergoes a metal-to-insulator transition (MIT) near 340K. Despite extensive studies on this material, the role of electron-electron correlation and electron-lattice interactions in driving this MIT is still under debate. Recently, it was demonstrated that hydrogen can be reversibly absorbed into VO2 thin film without destroying the lattice framework. This H-doping allows systematic control of the electron density and lattice structure which in turn leads to a insulator (VO2) - metal (HxVO2) - insulator (HVO2) phase modulation. To better understand the phase modulation of HxVO2, we used in-situ spectroscopic ellipsometry to monitor the electronic structure during the hydrogenization process, i.e. we measured the optical conductivity of HxVO2 while varying x. Starting in the high temperature rutile metallic phase of VO2, we observed a large change in the electronic structure upon annealing in H gas at 370K: the low energy conductivity is continuously suppressed, consistent with reported DC resistivity data, while the conductivity peaks at high energy show strong changes in energy and spectral weight. The implications of our results for the MIT in HxVO2 will be discussed.

High-level ab initio potential energy surface and dynamics of the F– + CH3I SN2 and proton-transfer reactions† †Electronic supplementary information (ESI) available: Benchmark classical and adiabatic relative energies (Table S1), vibrational frequencies of all the stationary points (Tables S2 and S3), direct/indirect trajectory separation function parameters (Table S4), entrance-channel potential (Fig. S1), structures of the minima and saddle points corresponding to the abstraction channel (Fig. S2), reaction probabilities (Fig. S3), trajectory integration time distributions (Fig. S4), trajectory integration time vs. I– velocity distributions (Fig. S5), and mechanism-specific reaction probabilities (Fig. S6). See DOI: 10.1039/c7sc00033b Click here for additional data file.

PubMed Central

Olasz, Balázs; Szabó, István

2017-01-01

Bimolecular nucleophilic substitution (SN2) and proton transfer are fundamental processes in chemistry and F– + CH3I is an important prototype of these reactions. Here we develop the first full-dimensional ab initio analytical potential energy surface (PES) for the F– + CH3I system using a permutationally invariant fit of high-level composite energies obtained with the combination of the explicitly-correlated CCSD(T)-F12b method, the aug-cc-pVTZ basis, core electron correlation effects, and a relativistic effective core potential for iodine. The PES accurately describes the SN2 channel producing I– + CH3F via Walden-inversion, front-side attack, and double-inversion pathways as well as the proton-transfer channel leading to HF + CH2I–. The relative energies of the stationary points on the PES agree well with the new explicitly-correlated all-electron CCSD(T)-F12b/QZ-quality benchmark values. Quasiclassical trajectory computations on the PES show that the proton transfer becomes significant at high collision energies and double-inversion as well as front-side attack trajectories can occur. The computed broad angular distributions and hot internal energy distributions indicate the dominance of indirect mechanisms at lower collision energies, which is confirmed by analyzing the integration time and leaving group velocity distributions. Comparison with available crossed-beam experiments shows usually good agreement. PMID:28507692

Methodological study of computational approaches to address the problem of strong correlations

NASA Astrophysics Data System (ADS)

Lee, Juho

The main focus of this thesis is the detailed investigation of computational methods to tackle strongly correlated materials in which a rich variety of exotic phenomena are found. A many-body problem with sizable electronic correlations can no longer be explained by independent-particle approximations such as density functional theory (DFT) or tight-binding approaches. The influence of an electron to the others is too strong for each electron to be treated as an independent quasiparticle and consequently those standard band-structure methods fail even at a qualitative level. One of the most powerful approaches for strong correlations is the dynamical mean-field theory (DMFT), which has enlightened the understanding of the Mott transition based on the Hubbard model. For realistic applications, the dynamical mean-field theory is combined with various independent-particles approaches. The most widely used one is the DMFT combined with the DFT in the local density approximation (LDA), so-called LDA+DMFT. In this approach, the electrons in the weakly correlated orbitals are calculated by LDA while others in the strongly correlated orbitals are treated by DMFT. Recently, the method combining DMFT with Hedin's GW approximation was also developed, in which the momentum-dependent self-energy is also added. In this thesis, we discuss the application of those methodologies based on DMFT. First, we apply the dynamical mean-field theory to solve the 3-dimensional Hubbard model in Chap. 3. In this application, we model the interface between the thermodynamically coexisting metal and Mott insulator. We show how to model the required slab geometry and extract the electronic spectra. We construct an effective Landau free energy and compute the variation of its parameters across the phase diagram. Finally, using a linear mixture of the density and double-occupancy, we identify a natural Ising order parameter which unifies the treatment of the bandwidth and filling controlled Mott transitions. Secondly, we study the double-counting problem, a subtle issue that arises in LDA+DMFT. We propose a highly precise double-counting functional, in which the intersection of LDA and DMFT is calculated exactly, and implement a parameter-free version of the LDA+DMFT that is tested on one of the simplest strongly correlated systems, the H2 molecule. We show that the exact double-counting treatment along with a good DMFT projector leads to very accurate and total energy and excitation spectrum of H2 molecule. Finally, we implement various versions of GW+DMFT, in its fully self-consistent way, one shot GW approximation, and quasiparticle self-consistent scheme, and studied how well these combined methods perform on H2 molecule as compared to more established methods such as LDA+DMFT. We found that most flavors of GW+DMFT break down in strongly correlated regime due to causality violation. Among GW+DMFT methods, only the self-consistent quasiparticle GW+DMFT with static double-counting, and a new method with causal double-counting, correctly recover the atomic limit at large H-atom separation. While some flavors of GW+DMFT improve the single-electron spectra of LDA+DMFT, the total energy is best predicted by LDA+DMFT, for which the exact double-counting is known, and is static.

Adler Award Lecture: Fermi-Liquid Instabilities in Strongly Correlated f-Electron Materials.^*

NASA Astrophysics Data System (ADS)

Maple, M. Brian

1996-03-01

Strongly correlated f-electron materials are replete with novel electronic states and phenomena ; e. g. , a metallic ``heavy electron'' state with a quasiparticle effective mass of several hundred times the free electron mass, anisotropic superconductivity with an energy gap that may vanish at points or along lines on the Fermi surface, the coexistence of superconductivity and antiferromagnetism over different parts of the Fermi surface, multiple superconducting phases in the hyperspace of chemical composition, temperature, pressure, and magnetic field, and an insulating phase, in so-called ``hybridization gap semiconductors'' or ``Kondo insulators'', with a small energy gap of only a few meV. During the last several years, a new low temperature non-Fermi-liquid (NFL) state has been observed in a new class of strongly correlated f-electron materials which currently consists of certain Ce and U intermetallics into which a nonmagnetic element has been substituted.(M. B. Maple et al./) , J. Low Temp. Phys. 99 , 223 (1995). The Ce and U ions have partially-filled f-electron shells and carry magnetic dipole or electric quadrupole moments which interact with the spins and charges of the conduction electrons and can participate in magnetic or quadrupolar ordering at low temperatures. The physical properties of these materials exhibit weak power law or logarithmic divergences in temperature and suggest the existence of a critical point at T=0 K. Possible origins of the 0 K critical point include an unconventional moment compensation process, such as a multichannel Kondo effect, and fluctuations of the order parameter in the vicinity of a 0 K second order phase transition. In some systems, such as Y_1-xU_xPd 3 and U_1-xTh_xPd _2Al 3 , the NFL characteristics appear to be single ion effects since they persist to low concentrations of f-moments, whereas in other systems, such as CeCu _5.9Au _0.1 , the NFL behavior seems to be associated with interactions between the f-moments. In this talk, we review recent experimental efforts to determine the characteristics, establish the systematics, and develop an understanding of NFL behavior in f-electron materials. \\vspace*3mm ^* Research supported by the U.S. National Science Foundation under Grant No. DMR-94-08835 and the U.S. Department of Energy under Grant No. DE-FG03-86ER45230.

HIGH ENERGY, HIGH BRIGHTNESS X-RAYS PRODUCED BY COMPTON BACKSCATTERING AT THE LIVERMORE PLEIADES FACILITY

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

Tremaine, A M; Anderson, S G; Betts, S

2005-05-19

PLEIADES (Picosecond Laser Electron Interaction for the Dynamic Evaluation of Structures) produces tunable 30-140 keV x-rays with 0.3-5 ps pulse lengths and up to 10{sup 7} photons/pulse by colliding a high brightness electron beam with a high power laser. The electron beam is created by an rf photo-injector system, accelerated by a 120 MeV linac, and focused to 20 {micro}m with novel permanent magnet quadrupoles. To produce Compton back scattered x-rays, the electron bunch is overlapped with a Ti:Sapphire laser that delivers 500 mJ, 100 fs, pulses to the interaction point. K-edge radiography at 115 keV on Uranium has verifiedmore » the angle correlated energy spectrum inherent in Compton scattering and high-energy tunability of the Livermore source. Current upgrades to the facility will allow laser pumping of targets synchronized to the x-ray source enabling dynamic diffraction and time-resolved studies of high Z materials. Near future plans include extending the radiation energies to >400 keV, allowing for nuclear fluorescence studies of materials.« less

Landscape of an exact energy functional

NASA Astrophysics Data System (ADS)

Cohen, Aron J.; Mori-Sánchez, Paula

2016-04-01

One of the great challenges of electronic structure theory is the quest for the exact functional of density functional theory. Its existence is proven, but it is a complicated multivariable functional that is almost impossible to conceptualize. In this paper the asymmetric two-site Hubbard model is studied, which has a two-dimensional universe of density matrices. The exact functional becomes a simple function of two variables whose three-dimensional energy landscape can be visualized and explored. A walk on this unique landscape, tilted to an angle defined by the one-electron Hamiltonian, gives a valley whose minimum is the exact total energy. This is contrasted with the landscape of some approximate functionals, explaining their failure for electron transfer in the strongly correlated limit. We show concrete examples of pure-state density matrices that are not v representable due to the underlying nonconvex nature of the energy landscape. The exact functional is calculated for all numbers of electrons, including fractional, allowing the derivative discontinuity to be visualized and understood. The fundamental gap for all possible systems is obtained solely from the derivatives of the exact functional.

Tuning Charge and Correlation Effects for a Single Molecule on a Graphene Device

NASA Astrophysics Data System (ADS)

Tsai, Hsin-Zon; Wickenburg, Sebastian; Lu, Jiong; Lischner, Johannes; Omrani, Arash A.; Riss, Alexander; Karrasch, Christoph; Jung, Han Sae; Khajeh, Ramin; Wong, Dillon; Watanabe, Kenji; Taniguchi, Takashi; Zettl, Alex; Louie, Steven G.; Crommie, Michael F.

Controlling electronic devices down to the single molecule level is a grand challenge of nanotechnology. Single-molecules have been integrated into devices capable of tuning electronic response, but a drawback for these systems is that their microscopic structure remains unknown due to inability to image molecules in the junction region. Here we present a combined STM and nc-AFM study demonstrating gate-tunable control of the charge state of individual F4TCNQ molecules at the surface of a graphene field effect transistor. This is different from previous studies in that the Fermi level of the substrate was continuously tuned across the molecular orbital energy level. Using STS we have determined the resulting energy level evolution of the LUMO, its associated vibronic modes, and the graphene Dirac point (ED). We show that the energy difference between ED and the LUMO increases as EF is moved away from ED due to electron-electron interactions that renormalize the molecular quasiparticle energy. This is attributed to gate-tunable image-charge screening in graphene and corroborated by ab initio calculations.

Gedanken densities and exact constraints in density functional theory.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Sun, Jianwei; Burke, Kieron

2014-05-14

Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is not an approximation to it. We further derive a strongly and optimally tightened bound on the exchange enhancement factor of a two-electron density, which is satisfied by the local density approximation but is violated by all published GGA's or meta-GGA's. Finally, some consequences of the non-uniform density-scaling behavior for the asymptotics of the exchange enhancement factor of a GGA or meta-GGA are given.

Collective relaxation processes in atoms, molecules and clusters

NASA Astrophysics Data System (ADS)

Kolorenč, Přemysl; Averbukh, Vitali; Feifel, Raimund; Eland, John

2016-04-01

Electron correlation is an essential driver of a variety of relaxation processes in excited atomic and molecular systems. These are phenomena which often lead to autoionization typically involving two-electron transitions, such as the well-known Auger effect. However, electron correlation can give rise also to higher-order processes characterized by multi-electron transitions. Basic examples include simultaneous two-electron emission upon recombination of an inner-shell vacancy (double Auger decay) or collective decay of two holes with emission of a single electron. First reports of this class of processes date back to the 1960s, but their investigation intensified only recently with the advent of free-electron lasers. High fluxes of high-energy photons induce multiple excitation or ionization of a system on the femtosecond timescale and under such conditions the importance of multi-electron processes increases significantly. We present an overview of experimental and theoretical works on selected multi-electron relaxation phenomena in systems of different complexity, going from double Auger decay in atoms and small molecules to collective interatomic autoionization processes in nanoscale samples.

Correlation between electron work functions of multiphase Cu-8Mn-8Al and de-alloying corrosion

NASA Astrophysics Data System (ADS)

Punburi, P.; Tareelap, N.; Srisukhumbowornchai, N.; Euaruksakul, C.; Yordsri, V.

2018-05-01

Low energy electron emission microscopy (LEEM) was used to measure local transition energy that was directly correlated to electron work function (EWF) of multiphase manganese-aluminum bronze alloys. We developed color mapping to distinguish the EWF of multiple phases and clarified that the EWF were in the following order: EWF of α > EWF of β > EWF of κ (EWFα > EWFβ > EWFκ). De-alloying corrosion took place due to the micro-galvanic cell at grain boundaries before it propagated into the β phase that had lower EWF than the α phase. The α phase was a stable phase because it contained high Cu while the β phase contained high Al and Mn. In addition, XRD analysis showed that the texture coefficient of the β phase revealed that almost all of the grains had (2 2 0) orientation, the lowest EWF compared to (1 1 1) and (2 0 0). Furthermore, transmission electron microscopy illustrated that there were fine Cu3Mn2Al precipitates in the Cu2MnAl matrix of the β phase. These precipitates formed micro-galvanic cells which played an important role in accelerating de-alloying corrosion.

Relationship between SEP Peak intensity and CME Acceleration, Speed and Width

NASA Astrophysics Data System (ADS)

Xie, H.; St Cyr, O. C.; Makela, P. A.; Gopalswamy, N.

2017-12-01

We study the large solar energetic particle (SEP) events that were detected by GOES in the >10 MeV energy channel during December 2006 to January 2016. Data used in this study includes the Solar Electron Proton Telescope (SEPT) and High Energy Telescopes (HET) on STEREO A and B, the Electron, Proton, and Alpha Monitor (EPAM) on ACE, and the Energetic and Relativistic Nuclei and Electron instrument (ERNE) on SOHO. By choosing the smallest connection angles between SEP solar locations and magnetic foot-points of each spacecraft, we divide SEP events as SOHO SEPs or STEREO SEPs. We then compute the SEP peak intensity I0 at the center of the Gausssian using the Gausssian expression from Richardson et al. (2014) and study the relationship between SEP electron and proton peak intensity and CME acceleration, speed and width. By using I0 derived from multi-spacecraft observations we found that the correlations between SEP peak intensity and CME acceleration and speed improved. We also found that this correlation can be further improved by taking into account the effects of CME width and its solar source latitude. The implication for the SEP forecast of our obtained results will be discussed.

Femtosecond dynamics of correlated many-body states in C60 fullerenes

NASA Astrophysics Data System (ADS)

Usenko, Sergey; Schüler, Michael; Azima, Armin; Jakob, Markus; Lazzarino, Leslie L.; Pavlyukh, Yaroslav; Przystawik, Andreas; Drescher, Markus; Laarmann, Tim; Berakdar, Jamal

2016-11-01

Fullerene complexes may play a key role in the design of future molecular electronics and nanostructured devices with potential applications in light harvesting using organic solar cells. Charge and energy flow in these systems is mediated by many-body effects. We studied the structure and dynamics of laser-induced multi-electron excitations in isolated C60 by two-photon photoionization as a function of excitation wavelength using a tunable fs UV laser and developed a corresponding theoretical framework on the basis of ab initio calculations. The measured resonance line width gives direct information on the excited state lifetime. From the spectral deconvolution we derive a lower limit for purely electronic relaxation on the order of {τ }{el}={10}-3+5 fs. Energy dissipation towards nuclear degrees of freedom is studied with time-resolved techniques. The evaluation of the nonlinear autocorrelation trace gives a characteristic time constant of {τ }{vib}=400+/- 100 fs for the exponential decay. In line with the experiment, the observed transient dynamics is explained theoretically by nonadiabatic (vibronic) couplings involving the correlated electronic, the nuclear degrees of freedom (accounting for the Herzberg-Teller coupling), and their interplay.

PREFACE: Strongly correlated electron systems Strongly correlated electron systems

NASA Astrophysics Data System (ADS)

Saxena, Siddharth S.; Littlewood, P. B.

2012-07-01

This special section is dedicated to the Strongly Correlated Electron Systems Conference (SCES) 2011, which was held from 29 August-3 September 2011, in Cambridge, UK. SCES'2011 is dedicated to 100 years of superconductivity and covers a range of topics in the area of strongly correlated systems. The correlated electronic and magnetic materials featured include f-electron based heavy fermion intermetallics and d-electron based transition metal compounds. The selected papers derived from invited presentations seek to deepen our understanding of the rich physical phenomena that arise from correlation effects. The focus is on quantum phase transitions, non-Fermi liquid phenomena, quantum magnetism, unconventional superconductivity and metal-insulator transitions. Both experimental and theoretical work is presented. Based on fundamental advances in the understanding of electronic materials, much of 20th century materials physics was driven by miniaturisation and integration in the electronics industry to the current generation of nanometre scale devices. The achievements of this industry have brought unprecedented advances to society and well-being, and no doubt there is much further to go—note that this progress is founded on investments and studies in the fundamentals of condensed matter physics from more than 50 years ago. Nevertheless, the defining challenges for the 21st century will lie in the discovery in science, and deployment through engineering, of technologies that can deliver the scale needed to have an impact on the sustainability agenda. Thus the big developments in nanotechnology may lie not in the pursuit of yet smaller transistors, but in the design of new structures that can revolutionise the performance of solar cells, batteries, fuel cells, light-weight structural materials, refrigeration, water purification, etc. The science presented in the papers of this special section also highlights the underlying interest in energy-dense materials, which make use of 'small' electrons packed to the highest possible density. These are by definition 'strongly correlated'. For example: good photovoltaics must be efficient optical absorbers, which means that photons will generate tightly bound electron-hole pairs (excitons) that must then be ionised at a heterointerface and transported to contacts; efficient solid state refrigeration depends on substantial entropy changes in a unit cell, with large local electrical or magnetic moments; efficient lighting is in a real sense the inverse of photovoltaics; the limit of an efficient battery is a supercapacitor employing mixed valent ions; fuel cells and solar to fuel conversion require us to understand electrochemistry on the scale of a single atom; and we already know that the only prospect for effective high temperature superconductivity involves strongly correlated materials. Even novel IT technologies are now seen to have value not just for novel function but also for efficiency. While strongly correlated electron systems continue to excite researchers and the public alike due to the fundamental science issues involved, it seems increasingly likely that support for the science will be leveraged by its impact on energy and sustainability. Strongly correlated electron systems contents Strongly correlated electron systemsSiddharth S Saxena and P B Littlewood Magnetism, f-electron localization and superconductivity in 122-type heavy-fermion metalsF Steglich, J Arndt, O Stockert, S Friedemann, M Brando, C Klingner, C Krellner, C Geibel, S Wirth, S Kirchner and Q Si High energy pseudogap and its evolution with doping in Fe-based superconductors as revealed by optical spectroscopyN L Wang, W Z Hu, Z G Chen, R H Yuan, G Li, G F Chen and T Xiang Structural investigations on YbRh2Si2: from the atomic to the macroscopic length scaleS Wirth, S Ernst, R Cardoso-Gil, H Borrmann, S Seiro, C Krellner, C Geibel, S Kirchner, U Burkhardt, Y Grin and F Steglich Confinement of chiral magnetic modulations in the precursor region of FeGeH Wilhelm, M Baenitz, M Schmidt, C Naylor, R Lortz, U K Rößler, A A Leonov and A N Bogdanov Antiferromagnetism in metals: from the cuprate superconductors to the heavy fermion materialsSubir Sachdev, Max A Metlitski and Matthias Punk Superconducting gap structure of the 115s revisitedF Ronning, J-X Zhu, Tanmoy Das, M J Graf, R C Albers, H B Rhee and W E Pickett Nonmagnetic ground states and phase transitions in the caged compounds PrT2Zn20 (T = Ru, Rh and Ir)T Onimaru, K T Matsumoto, N Nagasawa, Y F Inoue, K Umeo, R Tamura, K Nishimoto, S Kittaka, T Sakakibara and T Takabatake New universality class of quantum criticality in Ce- and Yb-based heavy fermionsShinji Watanabe and Kazumasa Miyake

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

Madanian, H.; Cravens, T. E.; Burch, J.

The plasma environment near comet 67P/Churyumov–Gerasimenko (67P/CG) is dynamically affected by various factors, including the incident solar wind and outgassing from the nucleus. The Rosetta spacecraft MAGnetometer (MAG) instrument observations near perihelion showed crossing events into a magnetic field-free region at about 170 km from the nucleus in 2015 July at 1.26 au from the Sun. At each crossing, the magnitude of the magnetic field dropped by more than 20 nT to near zero. We compared the Ion and Electron Sensor (IES) electron differential flux energy spectrum inside and outside the crossing boundaries. The IES observations show a modest butmore » consistent drop in electron flux for energies between 40 eV and a few hundred eV at each cavity crossing event. This drop in the electron spectra might be due to the absence or attenuation of solar wind electrons inside the observed diamagnetic regions, which might or might not be a diamagnetic cavity. There is no apparent simple linear correlation between the electron count rate measured by the IES at different energies and the magnitude of the magnetic field, however; at all energies, the highest electron count rates are recorded at the highest magnetic field magnitudes. From model-data comparisons it seems that inside diamagnetic regions, pure coma photoelectrons are not sufficient to explain the observations and that a trapping mechanism and/or infused solar wind electrons are necessary to explain the observed electron fluxes.« less

The electron affinity of Al13H cluster: high level ab initio study

NASA Astrophysics Data System (ADS)

Moc, Jerzy

2014-11-01

Al13H clusters have been considered candidates for cluster assembled materials. Here we have carried out benchmark calculations for the Al13H cluster, both neutral and anionic, with the aim of verifying the nature of stationary points on the potential energy surface, studying dynamics of H atom and determining an adiabatic electron affinity. A range of correlated methods applied include second-order perturbation theory (MP2), spin-component-scaled MP2, coupled electron pair (CEPA) and coupled cluster singles and doubles with perturbative triple corrections (CCSD(T)). These methods are used in combination with the correlation consistent basis sets through aug-cc-pVTZ including extrapolation to the complete basis set (CBS) limit. Performance of several different flavours of density functional theory (DFT) such as generalised gradient approximation (GGA), hybrid GGA, meta-GGA and hybrid-meta-GGA is assessed with respect to the ab initio correlated reference data. The harmonic force constant analysis is systematically performed with the MP2 and DFT methods. The MP2 results show that for neutral Al13H only the hollow structure is a potential energy minimum, with the bridged structure being a transition state for the H shift from the hollow site to the adjacent hollow site. The CCSD(T)/aug-cc-pVTZ (CCSD(T)/CBS) estimate of the energy barrier to this H shift is 2.6 (2.9) kcal/mol, implying that the H atom movement over the Al13H cluster surface is facile. By contrast, the DFT force constant analysis results suggest additional terminal and bridged minima structures. For the anion Al13H-, exhibiting 'stiffer' potential energy surface compared to the neutral, the existence of the hollow and terminal isomers is consistent with the earlier photoelectron spectroscopy assignment. The adiabatic electron affinity of Al13H is determined to be 2.00 and 1.95 eV (the latter including the ΔZPE correction) based on the CCSD(T) energies extrapolated to the CBS limit, whereas the respective CCSD(T)/CBS thermodynamic EA values are 2.79 and 2.80 eV.

Optical Design and Performance of the Taiwan Inelastic X-Ray Scattering Beamline (BL12XU) at SPring-8

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

Cai, Y.Q.; Chow, P.; Chen, C.C.

2004-05-12

As part of the Taiwan x-ray facility at SPring-8, we have designed, constructed and commissioned a dedicated Inelastic X-ray Scattering (IXS) beamline (BL12XU) for both resonant and non-resonant experiments on electronic excitations in correlated electron systems with energy resolution from 10-1000 meV. At the Si(555) near-backscattering energy of 9.886 keV, a total energy resolution of 70 meV has been achieved with flux of 1.5x1011 phs/sec/50meV. The optical design and performance of the beamline are presented and discussed with selected results from recent commissioning experiments.

On possibility of time reversal symmetry violation in neutrino elastic scattering on polarized electron target

NASA Astrophysics Data System (ADS)

Sobków, W.; Błaut, A.

2018-03-01

In this paper we indicate a possibility of utilizing the elastic scattering of Dirac low-energy (˜ 1 MeV) electron neutrinos (ν _es) on a polarized electron target (PET) in testing the time reversal symmetry violation (TRSV). We consider a scenario in which the incoming ν _e beam is a superposition of left chiral (LC) and right chiral (RC) states. LC ν _e interact mainly by the standard V-A and small admixture of non-standard scalar S_L, pseudoscalar P_L, tensor T_L interactions, while RC ones are only detected by the exotic V + A and S_R, P_R, T_R interactions. As a result of the superposition of the two chiralities the transverse components of ν e spin polarization (T-even and T-odd) may appear. We compute the differential cross section as a function of the recoil electron azimuthal angle and scattered electron energy, and show how the interference terms between standard V-A and exotic S_R, P_R, T_R couplings depend on the various angular correlations among the transversal ν _e spin polarization, the polarization of the electron target, the incoming neutrino momentum and the outgoing electron momentum in the limit of relativistic ν _e. We illustrate how the maximal value of recoil electrons azimuthal asymmetry and the asymmetry axis location of outgoing electrons depend on the azimuthal angle of the transversal component of the ν _e spin polarization, both for the time reversal symmetry conservation (TRSC) and TRSV. Next, we display that the electron energy spectrum and polar angle distribution of the recoil electrons are also sensitive to the interference terms between V-A and S_R, P_R, T_R couplings, proportional to the T-even and T-odd angular correlations among the transversal ν _e polarization, the electron polarization of the target, and the incoming ν _e momentum, respectively. We also discuss the possibility of testing the TRSV by observing the azimuthal asymmetry of outgoing electrons, using the PET without the impact of the transversal ν polarization related to the production process. In this scenario the predicted effects depend only on the interferences between S_R and T_R couplings. Our model-independent analysis is carried out for the flavor ν _e. To make such tests feasible, the intense (polarized) artificial ν _e source, PET and the appropriate detector measuring the directionality of the outgoing electrons and/or the recoil electrons energy with a high resolution have to be identified.

Self-organised silicide nanodot patterning by medium-energy ion beam sputtering of Si(100): local correlation between the morphology and metal content.

PubMed

Redondo-Cubero, A; Galiana, B; Lorenz, K; Palomares, F J; Bahena, D; Ballesteros, C; Hernandez-Calderón, I; Vázquez, L

2016-11-04

We have produced self-organised silicide nanodot patterns by medium-energy ion beam sputtering (IBS) of silicon targets with a simultaneous and isotropic molybdenum supply. Atomic force microscopy (AFM) studies show that these patterns are qualitatively similar to those produced thus far at low ion energies. We have determined the relevance of the ion species on the pattern ordering and properties. For the higher ordered patterns produced by Xe(+) ions, the pattern wavelength depends linearly on the ion energy. The dot nanostructures are silicide-rich as assessed by x-ray photoelectron spectroscopy (XPS) and emerge in height due to their lower sputtering yield, as observed by electron microscopy. Remarkably, a long wavelength corrugation is observed on the surface which is correlated with both the Mo content and the dot pattern properties. Thus, as assessed by electron microscopy, the protrusions are Mo-rich with higher and more spaced dots on their surface whereas the valleys are Mo-poor with smaller dots that are closer to each other. These findings indicate that there is a correlation between the local metal content of the surface and the nanodot pattern properties both at the nanodot and the large corrugation scales. These results contribute to advancing the understanding of this interesting nanofabrication method and aid in developing a comprehensive theory of nanodot pattern formation and evolution.

Study of the Anatomy of the X-Ray and Neutron Production Scaling Laws in the Plasma Focus (Particle Energy Spectrum and Optimization Criteria).

DTIC Science & Technology

1979-11-01

plasma focus operations have been experimentally analyzed in terms of (A) The fine structure of the axial-current channel during maximum of compression. (B) Correlation coefficient, for neutron yield n (by D2 discharges) and the multiplicity of the electron beam pulses; (C) Different values of the electrode voltage. The current distribution near the axial plasma column during the explosive decay of the column has been monitored and correlated with the electron beam production. Plasma focus discharges by our mode of operation generate high-intensity

Algorithmic implementation of particle-particle ladder diagram approximation to study strongly-correlated metals and semiconductors

NASA Astrophysics Data System (ADS)

Prayogi, A.; Majidi, M. A.

2017-07-01

In condensed-matter physics, strongly-correlated systems refer to materials that exhibit variety of fascinating properties and ordered phases, depending on temperature, doping, and other factors. Such unique properties most notably arise due to strong electron-electron interactions, and in some cases due to interactions involving other quasiparticles as well. Electronic correlation effects are non-trivial that one may need a sufficiently accurate approximation technique with quite heavy computation, such as Quantum Monte-Carlo, in order to capture particular material properties arising from such effects. Meanwhile, less accurate techniques may come with lower numerical cost, but the ability to capture particular properties may highly depend on the choice of approximation. Among the many-body techniques derivable from Feynman diagrams, we aim to formulate algorithmic implementation of the Ladder Diagram approximation to capture the effects of electron-electron interactions. We wish to investigate how these correlation effects influence the temperature-dependent properties of strongly-correlated metals and semiconductors. As we are interested to study the temperature-dependent properties of the system, the Ladder diagram method needs to be applied in Matsubara frequency domain to obtain the self-consistent self-energy. However, at the end we would also need to compute the dynamical properties like density of states (DOS) and optical conductivity that are defined in the real frequency domain. For this purpose, we need to perform the analytic continuation procedure. At the end of this study, we will test the technique by observing the occurrence of metal-insulator transition in strongly-correlated metals, and renormalization of the band gap in strongly-correlated semiconductors.

Nightside electron flux measurements at Mars by the Phobos-2 HARP instrument

NASA Technical Reports Server (NTRS)

Shutte, N.; Gringauz, K.; Kiraly, P.; Kotova, G.; Nagy, A. F.; Rosenbauer, H.; Szego, K.; Verigin, M.

1995-01-01

All the available nightside electron data obtained during circular orbits at Mars from the Phobos-2 Hyperbolic Retarded Potential Analyzer (HARP) instrument have been examined in detail and are summarized in this paper. An electron flux component with energies exceeding that of the unperturbed solar wind was observed inside the magnetosheath, indicating the presence of acceleration mechanism(s). The character of the electron fluxes measured in the magnetotail cannot be classified in any simple manner, however, there is a correlation between the electron fluxes measured well inside this region and the unperturbed solar wind ram pressure.

Overbias light emission due to higher-order quantum noise in a tunnel junction.

PubMed

Xu, F; Holmqvist, C; Belzig, W

2014-08-08

Understanding tunneling from an atomically sharp tip to a metallic surface requires us to account for interactions on a nanoscopic scale. Inelastic tunneling of electrons generates emission of photons, whose energies intuitively should be limited by the applied bias voltage. However, experiments [G. Schull et al., Phys. Rev. Lett. 102, 057401 (2009) indicate that more complex processes involving the interaction of electrons with plasmon polaritons lead to photon emission characterized by overbias energies. We propose a model of this observation in analogy to the dynamical Coulomb blockade, originally developed for treating the electronic environment in mesoscopic circuits. We explain the experimental finding quantitatively by the correlated tunneling of two electrons interacting with a LRC circuit modeling the local plasmon-polariton mode. To explain the overbias emission, the non-Gaussian statistics of the tunneling dynamics of the electrons is essential.

Intrinsic electronic defects and multiple-atom processes in the oxidic semiconductor Ga2O3

NASA Astrophysics Data System (ADS)

Schmeißer, Dieter; Henkel, Karsten

2018-04-01

We report on the electronic structure of gallium oxide (Ga2O3) single crystals as studied by resonant photoelectron spectroscopy (resPES). We identify intrinsic electronic defects that are formed by mixed-atomic valence states. We differentiate three coexisting defect states that differ in their electronic correlation energy and their spatial localization lengths. Their relative abundance is described by a fractional ionicity with covalent and ionic bonding contributions. For Ga2O3, our analyses of the resPES data enable us to derive two main aspects: first, experimental access is given to determine the ionicity based on the original concepts of Pauling and Phillips. Second, we report on multi-atomic energy loss processes in the Ga2p core level and X-ray absorption data. The two experimental findings can be explained consistently in the same context of mixed-atomic valence states and intrinsic electronic defects.

Lattice distortion and electron charge redistribution induced by defects in graphene

DOE PAGES

Zhang, Wei; Lu, Wen -Cai; Zhang, Hong -Xing; ...

2016-09-14

Lattice distortion and electronic charge localization induced by vacancy and embedded-atom defects in graphene were studied by tight-binding (TB) calculations using the recently developed three-center TB potential model. We showed that the formation energies of the defects are strongly correlated with the number of dangling bonds and number of embedded atoms, as well as the magnitude of the graphene lattice distortion induced by the defects. Lastly, we also showed that the defects introduce localized electronic states in the graphene which would affect the electron transport properties of graphene.

Inclusion of electron correlation for the target wave function in low-energy e sup minus +N sub 2 scattering

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

Meyer, H.; Pal, S.; Riss, U.V.

1992-07-01

The interaction of a scattering electron with a correlated but frozen'' target may be called the correlated static-exchange interaction. There are two prior investigations (J.R. Rumble, W.J. Stevens, and D. Truhlar, J. Phys. B 17, 3151 (1984); C Weatherford, F.B. Brown, and A. Temkin, Phys. Rev. A 35, 4561 (1987)) on scattering off the correlated static-exchange potential. Both of these investigations concentrated on {ital e}{sup {minus}}+N{sub 2} scattering, and both have found that the correlated static-exchange potential is less attractive than the static-exchange potential. We will show, however, that the correlated static-exchange potential is more attractive than the static-exchange one---atmore » least for {ital e}{sup {minus}}+N{sub 2} scattering in {sup 2}{Pi}{sub {ital g}} symmetry. The two prior investigations were misled by an improper degree of correlation and by an improper treatment of the exchange.« less

SPIN CORRELATIONS OF THE FINAL LEPTONS IN THE TWO-PHOTON PROCESSES γγ → e+e-, μ+μ-, τ+τ-

NASA Astrophysics Data System (ADS)

Lyuboshitz, Valery V.; Lyuboshitz, Vladimir L.

2014-12-01

The spin structure of the process γγ → e+e- is theoretically investigated. It is shown that, if the primary photons are unpolarized, the final electron and positron are unpolarized as well but their spins are strongly correlated. For the final (e+e-) system, explicit expressions for the components of the correlation tensor are derived, and the relative fractions of singlet and triplet states are found. It is demonstrated that in the process γγ → e+e- one of the Bell-type incoherence inequalities for the correlation tensor components is always violated and, thus, spin correlations of the electron and positron in this process have the strongly pronounced quantum character. Analogous consideration can be wholly applied as well to the two-photon processes γγ → μ+μ- and γγ → τ+τ-, which become possible at considerably higher energies.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO(-).

PubMed

Roy, Soumendra K; Jian, Tian; Lopez, Gary V; Li, Wei-Li; Su, Jing; Bross, David H; Peterson, Kirk A; Wang, Lai-Sheng; Li, Jun

2016-02-28

The observation of the gaseous UFO(-) anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO(-) is linear with an O-U-F structure and a (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO-

NASA Astrophysics Data System (ADS)

Roy, Soumendra K.; Jian, Tian; Lopez, Gary V.; Li, Wei-Li; Su, Jing; Bross, David H.; Peterson, Kirk A.; Wang, Lai-Sheng; Li, Jun

2016-02-01

The observation of the gaseous UFO- anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO- is linear with an O-U-F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

Insights in the electronic structure and redox reaction energy in LiFePO{sub 4} battery material from an accurate Tran-Blaha modified Becke Johnson potential

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

Araujo, Rafael B., E-mail: rafael.barros@physics.uu.se; Almeida, J. de S; Instituto de Física, Universidade Federal da Bahia, Salvador, Bahia

The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO{sub 4} and FePO{sub 4} which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, thatmore » the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO{sub 4} and FePO{sub 4}. However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system.« less

Multi-Wavelength Spectroscopic Observations of a White Light Flare Produced Directly by Non-thermal Electrons

NASA Astrophysics Data System (ADS)

Lee, Kyoung-Sun; Imada, Shinsuke; Watanabe, Kyoko; Bamba, Yumi; Brooks, David

2017-08-01

An X1.6 flare on 2014 October 22 was observed by multiple spectrometers in UV, EUV and X-ray (Hinode/EIS, IRIS, and RHESSI), and multi-wavelength imaging observations (SDO/AIA and HMI). We analyze a bright kernel that produces a white light (WL) flare with continuum enhancement and a hard X-ray (HXR) peak. Taking advantage of the spectroscopic observations of IRIS and Hinode/EIS, we measure the temporal variation of the plasma properties in the bright kernel in the chromosphere and corona. We find that explosive evaporation was observed when the WL emission occurred. The temporal correlation of the WL emission, HXR peak, and evaporation flows indicates that the WL emission was produced by accelerated electrons. We calculated the energy flux deposited by non-thermal electrons (observed by RHESSI) and compared it to the dissipated energy estimated from a chromospheric line (Mg II triplet) observed by IRIS. The deposited energy flux from the non-thermal electrons is about (3-7.7)x1010 erg cm-2 s-1 for a given low-energy cutoff of 30-40 keV, assuming the thick-target model. The energy flux estimated from the changes in temperature in the chromosphere measured using the Mg II subordinate line is about (4.6-6.7)×109 erg cm-2 s-1: ˜6%-22% of the deposited energy. This comparison of estimated energy fluxes implies that the continuum enhancement was directly produced by the non-thermal electrons.

Ab initio study on the ground and low-lying states of BAlk (Alk = Li, Na, K) molecules.

PubMed

Xiao, Ke-La; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang

2014-10-02

The potential energy curves (PECs) and dipole moment functions of (1)Π, (3)Π, (1)Σ(+), and (3)Σ(+) states of BAlk (Alk = Li, Na, K) are calculated using multireference configuration interaction method and large all-electron basis sets. The effects of inner-shell correlation electron for BAlk are considered. The ro-vibrational energy levels are obtained by solving the Schrödinger equation of nuclear motion based on the ab initio PECs. The spectroscopic parameters are determined from the ro-vibrational levels with Dunham expansion. The PECs are fitted into analytical potential energy functions using the Morse long-range potential function. The dipole moment functions for the states of BAlk are presented. The transition dipole moments for (1)Σ(+) → (1)Π and (3)Σ(+) → (3)Π states of BAlk are obtained. The interactions between the outermost electron of Alk and B 2p electrons for (1)Π, (3)Π, (1)Σ(+), and (3)Σ(+) states are also analyzed, respectively.

Effects of energy chirp on bunch length measurement in linear accelerator beams

NASA Astrophysics Data System (ADS)

Sabato, L.; Arpaia, P.; Giribono, A.; Liccardo, A.; Mostacci, A.; Palumbo, L.; Vaccarezza, C.; Variola, A.

2017-08-01

The effects of assumptions about bunch properties on the accuracy of the measurement method of the bunch length based on radio frequency deflectors (RFDs) in electron linear accelerators (LINACs) are investigated. In particular, when the electron bunch at the RFD has a non-negligible energy chirp (i.e. a correlation between the longitudinal positions and energies of the particle), the measurement is affected by a deterministic intrinsic error, which is directly related to the RFD phase offset. A case study on this effect in the electron LINAC of a gamma beam source at the Extreme Light Infrastructure-Nuclear Physics (ELI-NP) is reported. The relative error is estimated by using an electron generation and tracking (ELEGANT) code to define the reference measurements of the bunch length. The relative error is proved to increase linearly with the RFD phase offset. In particular, for an offset of {{7}\\circ} , corresponding to a vertical centroid offset at a screen of about 1 mm, the relative error is 4.5%.

Substituent Effects in the Benzene Dimer are Due to Direct Interactions of the Substituents with the Unsubstituted Benzene

PubMed Central

Wheeler, Steven E.; Houk, K. N.

2009-01-01

The prevailing views of substituent effects in the sandwich configuration of the benzene dimer are flawed. For example, in the polar/π model of Cozzi and co-workers (J. Am. Chem. Soc. 1992, 114, 5729), electron-withdrawing substituents enhance binding in the benzene dimer by withdrawing electron density from the π-cloud of the substituted ring, reducing the repulsive electrostatic interaction with the non-substituted benzene. Conversely, electron-donating substituents donate excess electrons into the π-system and diminish the π-stacking interaction. We present computed interaction energies for the sandwich configuration of the benzene dimer and 24 substituted dimers, as well as sandwich complexes of substituted benzenes with perfluorobenzene. While the computed interaction energies correlate well with σm values for the substituents, interaction energies for related model systems demonstrate that this trend is independent of the substituted ring. Instead, the observed trends are consistent with direct electrostatic and dispersive interactions of the substituents with the unsubstituted ring. PMID:18652453

Ab Initio Quantum Monte Carlo Simulation of the Warm Dense Electron Gas in the Thermodynamic Limit

DOE PAGES

Dornheim, Tobias; Groth, Simon; Sjostrom, Travis; ...

2016-10-07

Here we perform ab initio quantum Monte Carlo (QMC) simulations of the warm dense uniform electron gas in the thermodynamic limit. By combining QMC data with the linear response theory, we are able to remove finite-size errors from the potential energy over the substantial parts of the warm dense regime, overcoming the deficiencies of the existing finite-size corrections by Brown et al. [Phys. Rev. Lett. 110, 146405 (2013)]. Extensive new QMC results for up to N = 1000 electrons enable us to compute the potential energy V and the exchange-correlation free energy F xc of the macroscopic electron gas withmore » an unprecedented accuracy of | Δ V | / | V | , | Δ F xc | / | F | xc ~ 10 $-$3. Finally, a comparison of our new data to the recent parametrization of F xc by Karasiev et al. [Phys. Rev. Lett. 112, 076403 (2014)] reveals significant deviations to the latter.« less

Energy and angular distributions of electron emission from diatomic molecules by bare ion impact

NASA Astrophysics Data System (ADS)

Mondal, A.; Mandal, C. R.; Purkait, M.

2015-06-01

The three-Coulomb wave model has been used extensively to study the energy and angular distributions of double-differential cross sections (DDCS) of electron emissions from hydrogen and nitrogen molecules by bare ion impact at intermediate and high energies. In the present model, we have expressed the molecular triple differential cross section in terms of the corresponding atomic triple differential cross section multiplied by the occupation number and the average Rayleigh interference factor, which accounts for the two-center interference effect. Here we have used an active electron approximation of the molecule as a whole in the initial channel. To account for the effect of passive electrons, we have constructed a model potential that satisfies the initial conditions and the corresponding wavefunction has been calculated from the model Hamiltonian of the active electron in the target. In the final channel, we have used a hydrogenic model with an effective nuclear charge that is calculated from its binding energy. In this model, the correlated motion of the particles in the exit channel of the reaction is considered by an adequate product of three-Coulomb functions. The emitted electron, the incident projectile ion and the residual ion are considered to be in same plane. The obtained results are compared with other recent theoretical and experimental findings. There is an overall agreement of the calculations with the experimental data for electron emission cross sections.

Correlation-driven insulator-metal transition in near-ideal vanadium dioxide films

DOE PAGES

Gray, A. X.; Jeong, J.; Aetukuri, N. P.; ...

2016-03-18

We use polarization- and temperature-dependent x-ray absorption spectroscopy, in combination with photoelectron microscopy, x-ray diffraction, and electronic transport measurements, to study the driving force behind the insulator-metal transition in VO 2. We show that both the collapse of the insulating gap and the concomitant change in crystal symmetry in homogeneously strained single-crystalline VO 2 films are preceded by the purely electronic softening of Coulomb correlations within V-V singlet dimers. Furthermore, this process starts 7 K (±0.3 K) below the transition temperature, as conventionally defined by electronic transport and x-ray diffraction measurements, and sets the energy scale for driving the near-room-temperaturemore » insulator-metal transition in this technologically promising material.« less

Evolution and Control of 2219 Aluminum Microstructural Features through Electron Beam Freeform Fabrication

NASA Technical Reports Server (NTRS)

Taminger, Karen M.; Hafley, Robert A.; Domack, Marcia S.

2006-01-01

Electron beam freeform fabrication (EBF3) is a new layer-additive process that has been developed for near-net shape fabrication of complex structures. EBF3 uses an electron beam to create a molten pool on the surface of a substrate. Wire is fed into the molten pool and the part translated with respect to the beam to build up a 3-dimensional structure one layer at a time. Unlike many other freeform fabrication processes, the energy coupling of the electron beam is extremely well suited to processing of aluminum alloys. The layer-additive nature of the EBF3 process results in a tortuous thermal path producing complex microstructures including: small homogeneous equiaxed grains; dendritic growth contained within larger grains; and/or pervasive dendritic formation in the interpass regions of the deposits. Several process control variables contribute to the formation of these different microstructures, including translation speed, wire feed rate, beam current and accelerating voltage. In electron beam processing, higher accelerating voltages embed the energy deeper below the surface of the substrate. Two EBF3 systems have been established at NASA Langley, one with a low-voltage (10-30kV) and the other a high-voltage (30-60 kV) electron beam gun. Aluminum alloy 2219 was processed over a range of different variables to explore the design space and correlate the resultant microstructures with the processing parameters. This report is specifically exploring the impact of accelerating voltage. Of particular interest is correlating energy to the resultant material characteristics to determine the potential of achieving microstructural control through precise management of the heat flux and cooling rates during deposition.

Ab initio conformational analysis of N-formyl ?-alanine amide including electron correlation

NASA Astrophysics Data System (ADS)

Yu, Ching-Hsing; Norman, Mya A.; Schäfer, Lothar; Ramek, Michael; Peeters, Anik; van Alsenoy, Christian

2001-06-01

The conformational properties of N-formyl L-alanine amide (ALA) were investigated using RMP2/6-311G∗∗ ab initio gradient geometry optimization. One hundred forty four structures of ALA were optimized at 30° grid points in its φ(N-C(α)), ψ(C(α)-C‧) conformational space. Using cubic spline functions, the grid structures were then used to construct analytical representations of complete surfaces, in φ,ψ-space, of bond lengths, bond angles, torsional sensitivity and electrostatic atomic charges. Analyses show that, in agreement with previous studies, the right-handed helical conformation, αR, is not a local energy minimum of the potential energy surface of ALA. Comparisons with protein crystallographic data show that the characteristic differences between geometrical trends in dipeptides and proteins, previously found for ab initio dipeptide structures obtained without electron correlation, are also found in the electron-correlated geometries. In contrast to generally accepted features of force fields used in empirical molecular modeling, partial atomic charges obtained by the CHELPG method are found to be not constant, but to vary significantly throughout the φ,ψ-space. By comparing RHF and MP2 structures, the effects of dispersion forces on ALA were studied, revealing molecular contractions for those conformations, in which small adjustments of torsional angles entail large changes in non-bonded distances.

Spectral characteristics of plasma sheet ion and electron populations during disturbed geomagnetic conditions

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

Christon, S.P., Williams, D.J.; Mitchell, D.G.; Huang, C.Y.

1991-01-01

The authors have determined the spectral characteristics of central plasma sheet ions and electrons observed during 71 hours when geomagnetic activity was at moderate to high levels (AE {ge} 100nT). Particle data from the low-energy proton and electron differential energy analyzer and the medium energy particle instrument on ISEE 1 are combined to obtain differential energy spectra (measured in units of particles/cm{sup 2} s sr keV) in the kinetic energy range {approximately}30 eV/e to {approximately}1 MeV at geocentric radial distances >12R{sub e}. Nearly isotropic central plasma sheet total ion and electron populations were chosen for analysis and were measured tomore » be continuous particle distributions from the lowest to highest energies. During these high AE periods the >24 keV particle fluxes and the temperature of the entire particle distribution kT are significantly higher than during low AE periods (AE < 100 nT). The temperatures kT{sub i} and kT{sub e} are highly correlated during both quiet and disturbed periods. The active period spectral shape appears softer for ions and somewhat harder for electrons than during quiet periods. They find that the observed active period spectrum typically is complex and cannot be represented in general by a single functional form, as during quiet periods when it can be represented by the kappa distribution function. In a limited energy range near the knee of the ion spectra, the spectral shape can often be fit with a Maxwellian form, thus rolling over faster than the typical quiet time spectrum. Electron spectra also display this spectral characteristic, although at a lower occurence frequency than for ions. The electron spectra are predominantly kappalike at energies near and above the knee. The authors conclude that both ions and electrons participate in at least two separate accerlation mechanisms as geomagnetic activity evolves from low AE to high AE values.« less

Resonances in the cumulative reaction probability for a model electronically nonadiabatic reaction

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

Qi, J.; Bowman, J.M.

1996-05-01

The cumulative reaction probability, flux{endash}flux correlation function, and rate constant are calculated for a model, two-state, electronically nonadiabatic reaction, given by Shin and Light [S. Shin and J. C. Light, J. Chem. Phys. {bold 101}, 2836 (1994)]. We apply straightforward generalizations of the flux matrix/absorbing boundary condition approach of Miller and co-workers to obtain these quantities. The upper adiabatic electronic potential supports bound states, and these manifest themselves as {open_quote}{open_quote}recrossing{close_quote}{close_quote} resonances in the cumulative reaction probability, at total energies above the barrier to reaction on the lower adiabatic potential. At energies below the barrier, the cumulative reaction probability for themore » coupled system is shifted to higher energies relative to the one obtained for the ground state potential. This is due to the effect of an additional effective barrier caused by the nuclear kinetic operator acting on the ground state, adiabatic electronic wave function, as discussed earlier by Shin and Light. Calculations are reported for five sets of electronically nonadiabatic coupling parameters. {copyright} {ital 1996 American Institute of Physics.}« less

Relativistic atomic structure calculations and electron impact excitations of Fe23+

NASA Astrophysics Data System (ADS)

El-Maaref, A. A.

2016-02-01

Relativistic calculations using the multiconfiguration Dirac-Fock method for energy levels, oscillator strengths, and electronic dipole transition probabilities of Li-like iron (Fe23+) are presented. A configuration state list with the quantum numbers nl, where n = 2 - 7 and l = s , p , d , f , g , h , i has been considered. Excitations up to three electrons and correlation contributions from higher orbitals up to 7 l have been included. Contributions from core levels have been taken into account, EOL (extended optimal level) type calculations have been applied, and doubly excited levels are considered. The calculations have been executed by using the fully relativistic atomic structure package GRASP2K. The present calculations have been compared with the available experimental and theoretical sources, the comparisons show a good agreement between the present results of energy levels and oscillator strengths with the literature. In the second part of the present study, the atomic data (energy levels, and radiative parameters) have been used to calculate the excitation and deexcitation rates of allowed transitions by electron impact, as well as the population densities of some excited levels at different electron temperatures.

Basis convergence of range-separated density-functional theory.

PubMed

Franck, Odile; Mussard, Bastien; Luppi, Eleonora; Toulouse, Julien

2015-02-21

Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with cardinal number X of the Dunning basis sets cc - p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

Magnetic correlations in La(2-x)Sr(x)CuO4 from NQR relaxation and specific heat

NASA Technical Reports Server (NTRS)

Borsa, F.; Rigamonti, A.

1990-01-01

La-139 and Cu-63 Nuclear Quadrupole Resonance (NQR) relaxation measurements in La(2-x)Sr(x)CuO4 for O = to or less than 0.3 and in the temperature range 1.6 + 450 K are analyzed in terms of Cu(++) magnetic correlations and dynamics. It is described how the magnetic correlations that would result from Cu-Cu exchange are reduced by mobile charge defects related to x-doping. A comprehensive picture is given which explains satisfactorily the x and T dependence of the correlation time, of the correlation length and of the Neel temperature T(sub n)(x) as well as being consistent with known electrical resistivity and magnetic susceptibility measurements. It is discussed how, in the superconducting samples, the mobile defects also cause the decrease, for T yields T(sub c)(+) of the hyperfine Cu electron-nucleus effective interaction, leading to the coexistence of quasi-localized, reduced magnetic moments from 3d Cu electrons and mobile oxygen p-hole carriers. The temperature dependence of the effective hyperfine field around the superconducting transition yields an activation energy which could be related to the pairing energy. New specific heat measurements are also presented and discussed in terms of the above picture.

Many-body theory of effective mass in degenerate semiconductors

NASA Astrophysics Data System (ADS)

Tripathi, G. S.; Shadangi, S. K.

2018-03-01

We derive the many-body theory of the effective mass in the effective mass representation (EMR). In the EMR, we need to solve the equation of motion of an electron in the presence of electron-electron interactions, where the wavefunction is expanded over a complete set of Luttinger-Kohn wavefunctions. We use the Luttinger-Ward thermodynamic potential and the Green’s function perturbation to derive an expression for the band effective mass by taking into account the electron-electron interactions. Both quasi-particle and the correlation contributions are considered. We show that had we considered only the quasi-particle contribution, we would have missed important cancellations. Thus the correlated motion of electrons has important effects in the renormalization of the effective mass. Considering the exchange self-energy in the band model, we derive a tractable expression for the band effective mass. We apply the theory to n-type degenerate semiconductors, PbTe and SnTe, and analyze the impact of the theory on the anisotropic effective mass of the conduction bands in these systems.

Development and performance of a suprathermal electron spectrometer to study auroral precipitations

NASA Astrophysics Data System (ADS)

Ogasawara, Keiichi; Grubbs, Guy; Michell, Robert G.; Samara, Marilia; Stange, Jason L.; Trevino, John A.; Webster, James; Jahn, Jörg-Micha

2016-05-01

The design, development, and performance of Medium-energy Electron SPectrometer (MESP), dedicated to the in situ observation of suprathermal electrons in the auroral ionosphere, are summarized in this paper. MESP employs a permanent magnet filter with a light tight structure to select electrons with proper energies guided to the detectors. A combination of two avalanche photodiodes and a large area solid-state detector (SSD) provided 46 total energy bins (1 keV resolution for 3-20 keV range for APDs, and 7 keV resolution for >20 keV range for SSDs). Multi-channel ultra-low power application-specific integrated circuits are also verified for the flight operation to read-out and analyze the detector signals. MESP was launched from Poker Flat Research Range on 3 March 2014 as a part of ground-to-rocket electrodynamics-electrons correlative experiment (GREECE) mission. MESP successfully measured the precipitating electrons from 3 to 120 keV in 120-ms time resolution and characterized the features of suprathermal distributions associated with auroral arcs throughout the flight. The measured electrons were showing the inverted-V type spectra, consistent with the past measurements. In addition, investigations of the suprathermal electron population indicated the existence of the energetic non-thermal distribution corresponding to the brightest aurora.

Development and performance of a suprathermal electron spectrometer to study auroral precipitations.

PubMed

Ogasawara, Keiichi; Grubbs, Guy; Michell, Robert G; Samara, Marilia; Stange, Jason L; Trevino, John A; Webster, James; Jahn, Jörg-Micha

2016-05-01

The design, development, and performance of Medium-energy Electron SPectrometer (MESP), dedicated to the in situ observation of suprathermal electrons in the auroral ionosphere, are summarized in this paper. MESP employs a permanent magnet filter with a light tight structure to select electrons with proper energies guided to the detectors. A combination of two avalanche photodiodes and a large area solid-state detector (SSD) provided 46 total energy bins (1 keV resolution for 3-20 keV range for APDs, and 7 keV resolution for >20 keV range for SSDs). Multi-channel ultra-low power application-specific integrated circuits are also verified for the flight operation to read-out and analyze the detector signals. MESP was launched from Poker Flat Research Range on 3 March 2014 as a part of ground-to-rocket electrodynamics-electrons correlative experiment (GREECE) mission. MESP successfully measured the precipitating electrons from 3 to 120 keV in 120-ms time resolution and characterized the features of suprathermal distributions associated with auroral arcs throughout the flight. The measured electrons were showing the inverted-V type spectra, consistent with the past measurements. In addition, investigations of the suprathermal electron population indicated the existence of the energetic non-thermal distribution corresponding to the brightest aurora.

Development and Performance of a Suprathermal Electron Spectrometer to Study Auroral Precipitations

NASA Technical Reports Server (NTRS)

Ogasawara, Keiichi; Grubbs, Guy, II; Michell, Robert G.; Samara, Maria; Stange, Jason L.; Trevino, John A.; Webster, James; Jahn, Jorg-Micha

2016-01-01

The design, development, and performance of Medium-energy Electron SPectrometer (MESP), dedicated to the in situ observation of suprathermal electrons in the auroral ionosphere, are summarized in this paper. MESP employs a permanent magnet filter with a light tight structure to select electrons with proper energies guided to the detectors. A combination of two avalanche photodiodes and a large area solid-state detector (SSD) provided 46 total energy bins (1 keV resolution for 3-20 keV range for APDs, and 7 keV resolution for greater than 20 keV range for SSDs). Multi-channel ultra-low power application-specific integrated circuits are also verified for the flight operation to read-out and analyze the detector signals. MESP was launched from Poker F1at Research Range on 3 March 2014 as a part of ground-to-rocket electrodynamics-electrons correlative experiment (GREECE) mission. MESP successfully measured the precipitating electrons from 3 to 120 keV in 120-ms time resolution and characterized the features of suprathermal distributions associated with auroral arcs throughout the flight. The measured electrons were showing the inverted-V type spectra, consistent with the past measurements. In addition, investigations of the suprathermal electron population indicated the existence of the energetic non-thermal distribution corresponding to the brightest aurora.

Development and performance of a suprathermal electron spectrometer to study auroral precipitations

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

Ogasawara, Keiichi, E-mail: kogasawara@swri.edu; Stange, Jason L.; Trevino, John A.

2016-05-15

The design, development, and performance of Medium-energy Electron SPectrometer (MESP), dedicated to the in situ observation of suprathermal electrons in the auroral ionosphere, are summarized in this paper. MESP employs a permanent magnet filter with a light tight structure to select electrons with proper energies guided to the detectors. A combination of two avalanche photodiodes and a large area solid-state detector (SSD) provided 46 total energy bins (1 keV resolution for 3−20 keV range for APDs, and 7 keV resolution for >20 keV range for SSDs). Multi-channel ultra-low power application-specific integrated circuits are also verified for the flight operation tomore » read-out and analyze the detector signals. MESP was launched from Poker Flat Research Range on 3 March 2014 as a part of ground-to-rocket electrodynamics-electrons correlative experiment (GREECE) mission. MESP successfully measured the precipitating electrons from 3 to 120 keV in 120-ms time resolution and characterized the features of suprathermal distributions associated with auroral arcs throughout the flight. The measured electrons were showing the inverted-V type spectra, consistent with the past measurements. In addition, investigations of the suprathermal electron population indicated the existence of the energetic non-thermal distribution corresponding to the brightest aurora.« less

Monte Carlo explicitly correlated second-order many-body perturbation theory

NASA Astrophysics Data System (ADS)

Johnson, Cole M.; Doran, Alexander E.; Zhang, Jinmei; Valeev, Edward F.; Hirata, So

2016-10-01

A stochastic algorithm is proposed and implemented that computes a basis-set-incompleteness (F12) correction to an ab initio second-order many-body perturbation energy as a short sum of 6- to 15-dimensional integrals of Gaussian-type orbitals, an explicit function of the electron-electron distance (geminal), and its associated excitation amplitudes held fixed at the values suggested by Ten-no. The integrals are directly evaluated (without a resolution-of-the-identity approximation or an auxiliary basis set) by the Metropolis Monte Carlo method. Applications of this method to 17 molecular correlation energies and 12 gas-phase reaction energies reveal that both the nonvariational and variational formulas for the correction give reliable correlation energies (98% or higher) and reaction energies (within 2 kJ mol-1 with a smaller statistical uncertainty) near the complete-basis-set limits by using just the aug-cc-pVDZ basis set. The nonvariational formula is found to be 2-10 times less expensive to evaluate than the variational one, though the latter yields energies that are bounded from below and is, therefore, slightly but systematically more accurate for energy differences. Being capable of using virtually any geminal form, the method confirms the best overall performance of the Slater-type geminal among 6 forms satisfying the same cusp conditions. Not having to precompute lower-dimensional integrals analytically, to store them on disk, or to transform them in a nonscalable dense-matrix-multiplication algorithm, the method scales favorably with both system size and computer size; the cost increases only as O(n4) with the number of orbitals (n), and its parallel efficiency reaches 99.9% of the ideal case on going from 16 to 4096 computer processors.

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.

Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms

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

Pederson, Mark R., E-mail: mark.pederson@science.doe.gov

2015-02-14

A recent modification of the Perdew-Zunger self-interaction-correction to the density-functional formalism has provided a framework for explicitly restoring unitary invariance to the expression for the total energy. The formalism depends upon construction of Löwdin orthonormalized Fermi-orbitals which parametrically depend on variational quasi-classical electronic positions. Derivatives of these quasi-classical electronic positions, required for efficient minimization of the self-interaction corrected energy, are derived and tested, here, on atoms. Total energies and ionization energies in closed-shell singlet atoms, where correlation is less important, using the Perdew-Wang 1992 Local Density Approximation (PW92) functional, are in good agreement with experiment and non-relativistic quantum-Monte-Carlo results albeitmore » slightly too low.« less

Temporal correlations between impulsive ultraviolet and hard X-ray bursts in solar flares observed with high time resolution

NASA Technical Reports Server (NTRS)

Cheng, Chung-Chieh; Vanderveen, K.; Orwig, L. E.; Tandberg-Hanssen, E.

1988-01-01

The impulsive phase of solar flares has been simultaneously observed in the ultraviolet O V line, the UV continuum, and hard X-rays with a time resolution of 0.128 s by the SMM satellite. A close time correspondence between the three impulsive components is found, with the best correlation being at the peak of the impulsive phase. Individual bursts or fast features in the O V and the UV continuum are shown to lag behind the corresponding hard X-ray features. None of the considered energy transport mechanisms (thermal conduction, a nonthermal electron beam, electron hole boring, UV radiation, and Alfven waves) are able to consistently account for the observed temporal correlations.

Structure and electronic properties of ion pairs accompanying cyclic morpholinium cation and alkylphosphite anion based ionic liquids

NASA Astrophysics Data System (ADS)

Verma, Prakash L.; Singh, Priti; Gejji, Shridhar P.

2017-07-01

Molecular insights for the formation of ion pairs accompanying the cyclic ammonium cation based room temperature ionic liquids (RTILs) composed of alkyl substituted N-methylmorpholinium (RMMor) and alkylphosphite [(Rsbnd O)2PHdbnd O] (Rdbnd ethyl, butyl, hexyl, octyl) anion have been derived from the M06-2x level of theory. Electronic structures, binding energies, and spectral characteristics of the ion pairs underlying these RTILs have been characterized. The ion pair formation is largely governed by Csbnd H⋯O and other intermolecular interactions. Calculated binding energies increase with the increasing alkyl chain on either cation or alkylphosphite anion. The cation-anion binding reveals signature in the frequency down-(red) shift of the characteristic anionic Pdbnd O stretching whereas the Psbnd H stretching exhibits a shift in the opposite direction in vibrational spectra which has further been rationalized through molecular electron density topography. Correlations of measured electrochemical stability with the separation of frontier orbital energies and binding energies in the ion pairs have further been established.

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

PubMed Central

Jing, Linhong; Nash, John J.

2009-01-01

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

SU-E-T-379: Evaluation of An EPID-Based System for Daily Dosimetry Check by Comparison with a Widely-Used Ionization Chamber-Based Device

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

McDonald, D; Koch, N; Peng, J

2015-06-15

Purpose: To examine the feasibility of using Varian’s EPID-based Machine Performance Check (MPC) system to track daily machine output through comparison with Sun Nuclear’s DailyQA3 (DQA) device. Methods: Daily machine outputs for two photon energies (6 and 16MV) and five electron energies (6, 9, 12, 16, 20MeV) were measured for one month using both MPC and DQA. Baselines measurements for MPC were taken at the start of the measurement series, while DQA baselines were set at an earlier date. In order to make absolute comparisons with MPC, all DQA readings were referenced to the average of the first three DQAmore » readings in that series, minimizing systematic differences between the measurement techniques due to baseline differences. In addition to daily output measurements, weekly averages were also calculated and compared. Finally, the electron energy dependence of each measurement technique was examined by comparing energy-specific measurements to the average electron output of all energies each day. Results: For 6 and 16MV photons, the largest absolute percent differences between MPC and DQA were 0.60% and 0.73%, respectively. Weekly averages were within 0.17% and 0.23%, respectively. For all five electron energies, the greatest absolute percent differences between MPC and DQA for each energy ranged from 0.49%–0.83%. Weekly averages ranged from 0.07%–0.28%. DQA energy-specific electron readings matched the average electron output within 0.29% for all days and all energies. MPC energy-specific readings matched the average within 0.21% for 9–20MeV. However, 6MeV showed a larger distribution about the average with four days showing a difference greater than 0.30% and a maximum difference of 0.51%. Conclusion: MPC output measurements correlated well with the widely-used DQA3 for most beam energies, making it a reliable back up technique for daily output monitoring. However, MPC may display an energy dependence for lower electrons energies, requiring additional investigation.« less

Enhancing the nonlinear thermoelectric response of a correlated quantum dot in the Kondo regime by asymmetrical coupling to the leads

NASA Astrophysics Data System (ADS)

Pérez Daroca, Diego; Roura-Bas, Pablo; Aligia, Armando A.

2018-04-01

We study the low-temperature properties of the differential response of the current to a temperature gradient at finite voltage in a single-level quantum dot including electron-electron interaction, nonsymmetric couplings to the leads, and nonlinear effects. The calculated response is significantly enhanced in setups with large asymmetries between the tunnel couplings. In the investigated range of voltages and temperatures with corresponding energies up to several times the Kondo energy scale, the maximum response is enhanced nearly an order of magnitude with respect to symmetric coupling to the leads.

Power Series Approximation for the Correlation Kernel Leading to Kohn-Sham Methods Combining Accuracy, Computational Efficiency, and General Applicability

NASA Astrophysics Data System (ADS)

Erhard, Jannis; Bleiziffer, Patrick; Görling, Andreas

2016-09-01

A power series approximation for the correlation kernel of time-dependent density-functional theory is presented. Using this approximation in the adiabatic-connection fluctuation-dissipation (ACFD) theorem leads to a new family of Kohn-Sham methods. The new methods yield reaction energies and barriers of unprecedented accuracy and enable a treatment of static (strong) correlation with an accuracy of high-level multireference configuration interaction methods but are single-reference methods allowing for a black-box-like handling of static correlation. The new methods exhibit a better scaling of the computational effort with the system size than rivaling wave-function-based electronic structure methods. Moreover, the new methods do not suffer from the problem of singularities in response functions plaguing previous ACFD methods and therefore are applicable to any type of electronic system.