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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4971377· OSTI ID:1535290
ORCiD logo [1];  [2]; ORCiD logo [3]
  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
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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.

Research Organization:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0002139; SC-0002139
OSTI ID:
1535290
Alternate ID(s):
OSTI ID: 1335710
Journal Information:
Journal of Chemical Physics, Vol. 145, Issue 22; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

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Cited By (4)

Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions journal January 2020
Bethe–Salpeter correlation energies of atoms and molecules journal October 2018
Stretched or noded orbital densities and self-interaction correction in density functional theory journal May 2019
Bethe–Salpeter correlation energies of atoms and molecules text January 2018

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