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Title: Communication: A mean field platform for excited state quantum chemistry

Abstract

We present a mean field theory for excited states that is broadly analogous to ground state Hartree-Fock theory. Like Hartree-Fock, our approach is deterministic, state-specific, applies a variational principle to a minimally correlated ansatz, produces energy stationary points, relaxes the orbital basis, has a Fock-build cost-scaling, and can serve as the foundation for correlation methods such as perturbation theory and coupled cluster theory. To emphasize this last point, we pair our mean field approach with an excited state analog of second order Møller-Plesset theory and demonstrate that in water, formaldehyde, neon, and stretched lithium fluoride, the resulting accuracy far exceeds that of configuration interaction singles and rivals that of equation of motion coupled cluster.

Authors:
 [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543877
Alternate Identifier(s):
OSTI ID: 1465891
Grant/Contract Number:  
[AC02-05CH11231; SC0017869]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 149; Journal Issue: 8]; 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

Shea, Jacqueline A. R., and Neuscamman, Eric. Communication: A mean field platform for excited state quantum chemistry. United States: N. p., 2018. Web. doi:10.1063/1.5045056.
Shea, Jacqueline A. R., & Neuscamman, Eric. Communication: A mean field platform for excited state quantum chemistry. United States. doi:10.1063/1.5045056.
Shea, Jacqueline A. R., and Neuscamman, Eric. Wed . "Communication: A mean field platform for excited state quantum chemistry". United States. doi:10.1063/1.5045056. https://www.osti.gov/servlets/purl/1543877.
@article{osti_1543877,
title = {Communication: A mean field platform for excited state quantum chemistry},
author = {Shea, Jacqueline A. R. and Neuscamman, Eric},
abstractNote = {We present a mean field theory for excited states that is broadly analogous to ground state Hartree-Fock theory. Like Hartree-Fock, our approach is deterministic, state-specific, applies a variational principle to a minimally correlated ansatz, produces energy stationary points, relaxes the orbital basis, has a Fock-build cost-scaling, and can serve as the foundation for correlation methods such as perturbation theory and coupled cluster theory. To emphasize this last point, we pair our mean field approach with an excited state analog of second order Møller-Plesset theory and demonstrate that in water, formaldehyde, neon, and stretched lithium fluoride, the resulting accuracy far exceeds that of configuration interaction singles and rivals that of equation of motion coupled cluster.},
doi = {10.1063/1.5045056},
journal = {Journal of Chemical Physics},
number = [8],
volume = [149],
place = {United States},
year = {2018},
month = {8}
}

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Cited by: 4 works
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