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:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
- 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)
- 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. https://doi.org/10.1063/1.5045056
Shea, Jacqueline A. R., and Neuscamman, Eric. Wed .
"Communication: A mean field platform for excited state quantum chemistry". United States. https://doi.org/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 = {Wed Aug 22 00:00:00 EDT 2018},
month = {Wed Aug 22 00:00:00 EDT 2018}
}
Web of Science
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