Direct Extraction of Excitation Energies from Ensemble Density-Functional Theory
Abstract
A very specific ensemble of ground and excited states is shown to yield an exact formula for any excitation energy as a simple correction to the energy difference between orbitals of the Kohn-Sham ground state. This alternative scheme avoids either the need to calculate many unoccupied levels as in time-dependent density functional theory (TDDFT) or the need for many self-consistent ensemble calculations. Here, the symmetry-eigenstate Hartree-exchange (SEHX) approximation yields results comparable to standard TDDFT for atoms. With this formalism, SEHX yields approximate double excitations, which are missed by adiabatic TDDFT.
- Authors:
-
- China Academy of Engineering Physics, Chengdu (China)
- Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. of California, Irvine, CA (United States)
- Univ. of Missouri, Columbia, MO (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1595127
- Alternate Identifier(s):
- OSTI ID: 1372419
- Grant/Contract Number:
- FG02-08ER46496; AC52-07NA27344; TZ2016003; DMR-1408904
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Letters
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 3; Journal ID: ISSN 0031-9007
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; Atomic spectra; Density functional theory; Electronic structure of atoms & molecules; Electronic transitions; Atoms; Ions; Density functional calculations; Electronic structure; First-principles calculations
Citation Formats
Yang, Zeng-hui, Pribram-Jones, Aurora, Burke, Kieron, and Ullrich, Carsten A. Direct Extraction of Excitation Energies from Ensemble Density-Functional Theory. United States: N. p., 2017.
Web. doi:10.1103/PhysRevLett.119.033003.
Yang, Zeng-hui, Pribram-Jones, Aurora, Burke, Kieron, & Ullrich, Carsten A. Direct Extraction of Excitation Energies from Ensemble Density-Functional Theory. United States. https://doi.org/10.1103/PhysRevLett.119.033003
Yang, Zeng-hui, Pribram-Jones, Aurora, Burke, Kieron, and Ullrich, Carsten A. Fri .
"Direct Extraction of Excitation Energies from Ensemble Density-Functional Theory". United States. https://doi.org/10.1103/PhysRevLett.119.033003. https://www.osti.gov/servlets/purl/1595127.
@article{osti_1595127,
title = {Direct Extraction of Excitation Energies from Ensemble Density-Functional Theory},
author = {Yang, Zeng-hui and Pribram-Jones, Aurora and Burke, Kieron and Ullrich, Carsten A.},
abstractNote = {A very specific ensemble of ground and excited states is shown to yield an exact formula for any excitation energy as a simple correction to the energy difference between orbitals of the Kohn-Sham ground state. This alternative scheme avoids either the need to calculate many unoccupied levels as in time-dependent density functional theory (TDDFT) or the need for many self-consistent ensemble calculations. Here, the symmetry-eigenstate Hartree-exchange (SEHX) approximation yields results comparable to standard TDDFT for atoms. With this formalism, SEHX yields approximate double excitations, which are missed by adiabatic TDDFT.},
doi = {10.1103/PhysRevLett.119.033003},
journal = {Physical Review Letters},
number = 3,
volume = 119,
place = {United States},
year = {Fri Jul 21 00:00:00 EDT 2017},
month = {Fri Jul 21 00:00:00 EDT 2017}
}
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Works referenced in this record:
A Brief Compendium of Time-Dependent Density Functional Theory
journal, July 2013
- Ullrich, Carsten A.; Yang, Zeng-hui
- Brazilian Journal of Physics, Vol. 44, Issue 1
Density functionals for coulomb systems
journal, September 1983
- Lieb, Elliott H.
- International Journal of Quantum Chemistry, Vol. 24, Issue 3
The energy density functional formalism for excited states
journal, December 1979
- Theophilou, A. K.
- Journal of Physics C: Solid State Physics, Vol. 12, Issue 24
Spurious Interactions, and Their Correction, in the Ensemble-Kohn-Sham Scheme for Excited States
journal, January 2002
- Gidopoulos, N. I.; Papaconstantinou, P. G.; Gross, E. K. U.
- Physical Review Letters, Vol. 88, Issue 3
Excitations and benchmark ensemble density functional theory for two electrons
journal, May 2014
- Pribram-Jones, Aurora; Yang, Zeng-hui; Trail, John R.
- The Journal of Chemical Physics, Vol. 140, Issue 18
Excitation energies from density-functional orbital energies
journal, December 1995
- Levy, Mel
- Physical Review A, Vol. 52, Issue 6
A Compilation of Energy Levels and Wavelengths for the Spectrum of Neutral Beryllium (Be I )
journal, September 1997
- Kramida, A.; Martin, W. C.
- Journal of Physical and Chemical Reference Data, Vol. 26, Issue 5
Double excitations within time-dependent density functional theory linear response
journal, April 2004
- Maitra, Neepa T.; Zhang, Fan; Cave, Robert J.
- The Journal of Chemical Physics, Vol. 120, Issue 13
Rayleigh-Ritz variational principle for ensembles of fractionally occupied states
journal, April 1988
- Gross, E. K. U.; Oliveira, L. N.; Kohn, W.
- Physical Review A, Vol. 37, Issue 8
Understanding band gaps of solids in generalized Kohn–Sham theory
journal, March 2017
- Perdew, John P.; Yang, Weitao; Burke, Kieron
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 11
Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy
journal, December 1982
- Perdew, John P.; Parr, Robert G.; Levy, Mel
- Physical Review Letters, Vol. 49, Issue 23
Understanding and Reducing Errors in Density Functional Calculations
journal, August 2013
- Kim, Min-Cheol; Sim, Eunji; Burke, Kieron
- Physical Review Letters, Vol. 111, Issue 7
Hohenberg-Kohn theorem for nonlocal external potentials
journal, September 1975
- Gilbert, T. L.
- Physical Review B, Vol. 12, Issue 6
Perspective: Fundamental aspects of time-dependent density functional theory
journal, June 2016
- Maitra, Neepa T.
- The Journal of Chemical Physics, Vol. 144, Issue 22
Density-functional theory for ensembles of fractionally occupied states. I. Basic formalism
journal, April 1988
- Gross, E. K. U.; Oliveira, L. N.; Kohn, W.
- Physical Review A, Vol. 37, Issue 8
Linear interpolation method in ensemble Kohn-Sham and range-separated density-functional approximations for excited states
journal, July 2015
- Senjean, Bruno; Knecht, Stefan; Jensen, Hans Jørgen Aa.
- Physical Review A, Vol. 92, Issue 1
Accurate exchange-correlation potentials and total-energy components for the helium isoelectronic series
journal, November 1994
- Umrigar, C. J.; Gonze, Xavier
- Physical Review A, Vol. 50, Issue 5
Energy levels for the stable isotopes of atomic helium( 4 He I and 3 He I)
journal, February 2006
- Morton, Donald C.; Wu, Qixue; Drake, G. Wf
- Canadian Journal of Physics, Vol. 84, Issue 2
Electron densities in search of Hamiltonians
journal, September 1982
- Levy, Mel
- Physical Review A, Vol. 26, Issue 3
Perspectives on double-excitations in TDDFT
journal, November 2011
- Elliott, Peter; Goldson, Sharma; Canahui, Chris
- Chemical Physics, Vol. 391, Issue 1
Energy levels of aluminum, Al I through Al XIII
journal, July 1979
- Martin, W. C.; Zalubas, Romuald
- Journal of Physical and Chemical Reference Data, Vol. 8, Issue 3
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Transition frequencies of the lines of , , and measured with a femtosecond laser frequency comb
journal, September 2006
- Falke, Stephan; Tiemann, Eberhard; Lisdat, Christian
- Physical Review A, Vol. 74, Issue 3
Ensemble density variational methods with self- and ghost-interaction-corrected functionals
journal, May 2014
- Pastorczak, Ewa; Pernal, Katarzyna
- The Journal of Chemical Physics, Vol. 140, Issue 18
Doppler-free two-photon absorption spectrum of potassium
journal, June 1983
- Thompson, D. C.; O'Sullivan, M. S.; Stoicheff, B. P.
- Canadian Journal of Physics, Vol. 61, Issue 6
Rigorous formulation of Slater’s transition-state theory for excited states
journal, August 1985
- Hadjisavvas, Nicolas; Theophilou, Andreas
- Physical Review A, Vol. 32, Issue 2
Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations
journal, May 2015
- Filatov, Michael; Huix-Rotllant, Miquel; Burghardt, Irene
- The Journal of Chemical Physics, Vol. 142, Issue 18
Energy levels of potassium, K I through K XIX
journal, October 1979
- Corliss, Charles; Sugar, Jack
- Journal of Physical and Chemical Reference Data, Vol. 8, Issue 4
Spin-restricted ensemble-referenced Kohn-Sham method: basic principles and application to strongly correlated ground and excited states of molecules
journal, November 2014
- Filatov, Michael
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 5, Issue 1
Exact and approximate Kohn-Sham potentials in ensemble density-functional theory
journal, October 2014
- Yang, Zeng-hui; Trail, John R.; Pribram-Jones, Aurora
- Physical Review A, Vol. 90, Issue 4
Universal variational functionals of electron densities, first-order density matrices, and natural spin-orbitals and solution of the v-representability problem
journal, December 1979
- Levy, M.
- Proceedings of the National Academy of Sciences, Vol. 76, Issue 12
Construction and application of an accurate local spin-polarized Kohn-Sham potential with integer discontinuity: Exchange-only theory
journal, January 1992
- Krieger, J. B.; Li, Yan; Iafrate, G. J.
- Physical Review A, Vol. 45, Issue 1
A dressed TDDFT treatment of the 21Ag states of butadiene and hexatriene
journal, May 2004
- Cave, Robert J.; Zhang, Fan; Maitra, Neepa T.
- Chemical Physics Letters, Vol. 389, Issue 1-3
Energy levels of magnesium, Mg I through Mg XII
journal, January 1980
- Martin, W. C.; Zalubas, Romuald
- Journal of Physical and Chemical Reference Data, Vol. 9, Issue 1
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
An Intensity Problem in the Spectrum of Potassium
journal, March 1972
- Johansson, I.; Svendenius, N.
- Physica Scripta, Vol. 5, Issue 3
Time-dependent density functional theory within the Tamm–Dancoff approximation
journal, December 1999
- Hirata, So; Head-Gordon, Martin
- Chemical Physics Letters, Vol. 314, Issue 3-4
A critical compilation of energy levels and spectral lines of neutral boron
journal, October 2007
- Kramida, A. E.; Ryabtsev, A. N.
- Physica Scripta, Vol. 76, Issue 5
A road to a multiconfigurational ensemble density functional theory without ghost interactions
journal, February 2016
- Pastorczak, Ewa; Pernal, Katarzyna
- International Journal of Quantum Chemistry, Vol. 116, Issue 11
Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle
journal, June 2013
- Pastorczak, Ewa; Gidopoulos, Nikitas I.; Pernal, Katarzyna
- Physical Review A, Vol. 87, Issue 6
Wavelengths, Transition Probabilities, and Energy Levels for the Spectra of Sodium (NaI–NaXI)
journal, December 2008
- Sansonetti, J. E.
- Journal of Physical and Chemical Reference Data, Vol. 37, Issue 4
Adiabatic connection for near degenerate excited states
journal, May 2004
- Zhang, Fan; Burke, Kieron
- Physical Review A, Vol. 69, Issue 5
An alternative optimized potential method for ensembles of excited states
journal, June 2001
- Nagy, Á
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 34, Issue 12
Excitation energies from time-dependent density functional theory using exact and approximate potentials
journal, January 2000
- Petersilka, M.; Gross, E. K. U.; Burke, Kieron
- International Journal of Quantum Chemistry, Vol. 80, Issue 4-5
Perspectives on double-excitations in TDDFT
text, January 2011
- Elliott, Peter; Goldson, Sharma; Canahui, Chris
- arXiv
Understanding and reducing errors in density functional calculations
text, January 2012
- Kim, Min-Cheol; Sim, Eunji; Burke, Kieron
- arXiv
A brief compendium of time-dependent density-functional theory
text, January 2013
- Ullrich, Carsten A.; Yang, Zeng-hui
- arXiv
Exact and approximate Kohn-Sham potentials in ensemble density-functional theory
text, January 2014
- Yang, Zeng-hui; Trail, John R.; Pribram-Jones, Aurora
- arXiv
Excitations and benchmark ensemble density functional theory for two electrons
text, January 2014
- Pribram-Jones, Aurora; Yang, Zeng-hui; Trail, John R.
- arXiv
Linear interpolation method in ensemble Kohn-Sham and range-separated density-functional approximations for excited states
text, January 2015
- Senjean, Bruno; Knecht, Stefan; Jensen, Hans Jørgen Aa.
- arXiv
Works referencing / citing this record:
Charge transfer excitations from exact and approximate ensemble Kohn-Sham theory
journal, May 2018
- Gould, Tim; Kronik, Leeor; Pittalis, Stefano
- The Journal of Chemical Physics, Vol. 148, Issue 17
Accurate double excitations from ensemble density functional calculations
journal, October 2018
- Sagredo, Francisca; Burke, Kieron
- The Journal of Chemical Physics, Vol. 149, Issue 13
Ground and excited energy levels can be extracted exactly from a single ensemble density-functional theory calculation
journal, March 2019
- Deur, Killian; Fromager, Emmanuel
- The Journal of Chemical Physics, Vol. 150, Issue 9
Exploring weight-dependent density-functional approximations for ensembles in the Hubbard dimer
journal, July 2018
- Deur, Killian; Mazouin, Laurent; Senjean, Bruno
- The European Physical Journal B, Vol. 91, Issue 7
Exploring weight-dependent density-functional approximations for ensembles in the Hubbard dimer
text, January 2018
- Deur, Killian; Mazouin, Laurent; Senjean, Bruno
- arXiv
Ground and excited energy levels can be extracted exactly from a single ensemble density-functional theory calculation
text, January 2018
- Deur, Killian; Fromager, Emmanuel
- arXiv