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Title: Random phase approximation with second-order screened exchange for current-carrying atomic states

Abstract

The direct random phase approximation (RPA) and RPA with second-order screened exchange (SOSEX) have been implemented with complex orbitals as a basis for treating open-shell atoms. Both RPA and RPA+SOSEX are natural implicit current density functionals because the paramagnetic current density implicitly is included through the use of complex orbitals. We confirm that inclusion of the SOSEX correction improves the total energy accuracy substantially compared to RPA, especially for smaller-Z atoms. Computational complexity makes post self-consistent-field (post-SCF) evaluation of RPA-type expressions commonplace, so orbital basis origins and properties become important. Sizable differences are found in correlation energies, total atomic energies, and ionization energies for RPA-type functionals evaluated in the post-SCF fashion with orbital sets obtained from different schemes. Reference orbitals from Kohn-Sham calculations with semi-local functionals are more suitable for RPA+SOSEX to generate accurate total energies, but reference orbitals from exact exchange (non-local) yield essentially energetically degenerate open-shell atom ground states. RPA+SOSEX correlation combined with exact exchange calculated from a hybrid reference orbital set (half the exchange calculated from exact-exchange orbitals, the other half of the exchange from orbitals optimized for the Perdew-Burke-Ernzerhof (PBE) exchange functional) gives the best overall performance. Finally, numerical results show that the RPA-like functional withmore » SOSEX correction can be used as a practical implicit current density functional when current effects should be included.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Hangzhou Normal Univ., Hangzhou, Zhejiang (China). Dept. of Physics
  2. Hangzhou Normal Univ., Hangzhou, Zhejiang (China). Inst. of Service Engineering
  3. Univ. of Florida, Gainesville, FL (United States). Dept. of Physics and Dept. of Chemistry, Quantum Theory Project
Publication Date:
Research Org.:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535290
Alternate Identifier(s):
OSTI ID: 1335710
Grant/Contract Number:  
SC0002139; SC-0002139
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; physics

Citation Formats

Zhu, Wuming, Zhang, Liang, and Trickey, S. B. Random phase approximation with second-order screened exchange for current-carrying atomic states. United States: N. p., 2016. Web. doi:10.1063/1.4971377.
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Zhu, Wuming, Zhang, Liang, & Trickey, S. B. Random phase approximation with second-order screened exchange for current-carrying atomic states. United States. https://doi.org/10.1063/1.4971377
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Zhu, Wuming, Zhang, Liang, and Trickey, S. B. Tue . "Random phase approximation with second-order screened exchange for current-carrying atomic states". United States. https://doi.org/10.1063/1.4971377. https://www.osti.gov/servlets/purl/1535290.
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@article{osti_1535290,
title = {Random phase approximation with second-order screened exchange for current-carrying atomic states},
author = {Zhu, Wuming and Zhang, Liang and Trickey, S. B.},
abstractNote = {The direct random phase approximation (RPA) and RPA with second-order screened exchange (SOSEX) have been implemented with complex orbitals as a basis for treating open-shell atoms. Both RPA and RPA+SOSEX are natural implicit current density functionals because the paramagnetic current density implicitly is included through the use of complex orbitals. We confirm that inclusion of the SOSEX correction improves the total energy accuracy substantially compared to RPA, especially for smaller-Z atoms. Computational complexity makes post self-consistent-field (post-SCF) evaluation of RPA-type expressions commonplace, so orbital basis origins and properties become important. Sizable differences are found in correlation energies, total atomic energies, and ionization energies for RPA-type functionals evaluated in the post-SCF fashion with orbital sets obtained from different schemes. Reference orbitals from Kohn-Sham calculations with semi-local functionals are more suitable for RPA+SOSEX to generate accurate total energies, but reference orbitals from exact exchange (non-local) yield essentially energetically degenerate open-shell atom ground states. RPA+SOSEX correlation combined with exact exchange calculated from a hybrid reference orbital set (half the exchange calculated from exact-exchange orbitals, the other half of the exchange from orbitals optimized for the Perdew-Burke-Ernzerhof (PBE) exchange functional) gives the best overall performance. Finally, numerical results show that the RPA-like functional with SOSEX correction can be used as a practical implicit current density functional when current effects should be included.},
doi = {10.1063/1.4971377},
journal = {Journal of Chemical Physics},
number = 22,
volume = 145,
place = {United States},
year = {Tue Dec 13 00:00:00 EST 2016},
month = {Tue Dec 13 00:00:00 EST 2016}
}
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https://doi.org/10.1063/1.4971377
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    Works referencing / citing this record:

    Bethe–Salpeter correlation energies of atoms and molecules
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    • Holzer, Christof; Gui, Xin; Harding, Michael E.
    • The Journal of Chemical Physics, Vol. 149, Issue 14
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    • The Journal of Chemical Physics, Vol. 150, Issue 17
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    Bethe–Salpeter correlation energies of atoms and molecules
    text, January 2018

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