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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4994827· OSTI ID:1511692
 [1];  [2];  [2];  [2];  [2]
  1. Duke Univ., Durham, NC (United States); none
  2. Duke Univ., Durham, NC (United States)
+ Show Author Affiliations
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.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ. of the Commonwealth System of Higher Education, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0012575
OSTI ID:
1511692
Alternate ID(s):
OSTI ID: 1396313
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 147; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (8)

FIG. 1(p. 4)figure FIG. 1
TABLE I(p. 5)table TABLE I
TABLE II(p. 5)table TABLE II
TABLE III(p. 5)table TABLE III
TABLE IV(p. 5)table TABLE IV
TABLE V(p. 6)table TABLE V
TABLE VI(p. 6)table TABLE VI
FIG. 2(p. 7)figure FIG. 2

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74 ATOMIC AND MOLECULAR PHYSICS