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Title: Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo

In the regime where traditional approaches to electronic structure cannot afford to achieve accurate energy differences via exhaustive wave function flexibility, rigorous approaches to balancing different states’ accuracies become desirable. As a direct measure of a wave function’s accuracy, the energy variance offers one route to achieving such a balance. Here, we develop and test a variance matching approach for predicting excitation energies within the context of variational Monte Carlo and selective configuration interaction. In a series of tests on small but difficult molecules, we demonstrate that the approach it is effective at delivering accurate excitation energies when the wave function is far from the exhaustive flexibility limit. Results in C3, where we combine this approach with variational Monte Carlo orbital optimization, are especially encouraging.
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [3]
  1. Univ. of California, Los Angeles, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1408517
Alternate Identifier(s):
OSTI ID: 1405209

Robinson, Paul J., Pineda Flores, Sergio D., and Neuscamman, Eric. Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo. United States: N. p., Web. doi:10.1063/1.5008743.
Robinson, Paul J., Pineda Flores, Sergio D., & Neuscamman, Eric. Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo. United States. doi:10.1063/1.5008743.
Robinson, Paul J., Pineda Flores, Sergio D., and Neuscamman, Eric. 2017. "Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo". United States. doi:10.1063/1.5008743. https://www.osti.gov/servlets/purl/1408517.
@article{osti_1408517,
title = {Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo},
author = {Robinson, Paul J. and Pineda Flores, Sergio D. and Neuscamman, Eric},
abstractNote = {In the regime where traditional approaches to electronic structure cannot afford to achieve accurate energy differences via exhaustive wave function flexibility, rigorous approaches to balancing different states’ accuracies become desirable. As a direct measure of a wave function’s accuracy, the energy variance offers one route to achieving such a balance. Here, we develop and test a variance matching approach for predicting excitation energies within the context of variational Monte Carlo and selective configuration interaction. In a series of tests on small but difficult molecules, we demonstrate that the approach it is effective at delivering accurate excitation energies when the wave function is far from the exhaustive flexibility limit. Results in C3, where we combine this approach with variational Monte Carlo orbital optimization, are especially encouraging.},
doi = {10.1063/1.5008743},
journal = {Journal of Chemical Physics},
number = 16,
volume = 147,
place = {United States},
year = {2017},
month = {10}
}

Works referenced in this record:

General atomic and molecular electronic structure system
journal, November 1993
  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112