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

Abstract

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.

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
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  1. Duke Univ., Durham, NC (United States)
Publication Date:
Research Org.:
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 Org.:
USDOE
OSTI Identifier:
1511692
Alternate Identifier(s):
OSTI ID: 1396313
Grant/Contract Number:  
SC0012575
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Jin, Ye, Yang, Yang, Zhang, Du, Peng, Degao, and Yang, Weitao. Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials. United States: N. p., 2017. Web. doi:10.1063/1.4994827.
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Jin, Ye, Yang, Yang, Zhang, Du, Peng, Degao, & Yang, Weitao. Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials. United States. https://doi.org/10.1063/1.4994827
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Jin, Ye, Yang, Yang, Zhang, Du, Peng, Degao, and Yang, Weitao. Tue . "Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials". United States. https://doi.org/10.1063/1.4994827. https://www.osti.gov/servlets/purl/1511692.
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@article{osti_1511692,
title = {Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials},
author = {Jin, Ye and Yang, Yang and Zhang, Du and Peng, Degao and Yang, Weitao},
abstractNote = {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.},
doi = {10.1063/1.4994827},
journal = {Journal of Chemical Physics},
number = 13,
volume = 147,
place = {United States},
year = {Tue Oct 03 00:00:00 EDT 2017},
month = {Tue Oct 03 00:00:00 EDT 2017}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.4994827
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Cited by: 4 works
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Figures / Tables:

FIG. 1 FIG. 1: Potential basis convergence tests with the pp-RPA-OEP from three density sources are shown here. The first two singlet and triplet excitations are calculated using butadiene. The number on the x-axis represents different potential basis sets, shown in Table I. Aug-cc-pVDZ is chosen as the atomic basis set, asmore » shown in the previous work.« less
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    FIG. 1 (p. 4)figure
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    TABLE V (p. 6)table
    TABLE VI (p. 6)table
    FIG. 2 (p. 7)figure
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