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Title: 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:
 [1];  [2];  [3];  [4]
  1. China Academy of Engineering Physics, Chengdu (China)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of California, Irvine, CA (United States)
  4. 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. doi: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. doi: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 = {2017},
month = {7}
}

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Cited by: 8 works
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