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

Abstract

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 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]
+ Show Author Affiliations
  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:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1408517
Alternate Identifier(s):
OSTI ID: 1405209
Grant/Contract Number:  
AC02-05CH11231
Resource 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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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., 2017. Web. doi:10.1063/1.5008743.
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Robinson, Paul J., Pineda Flores, Sergio D., & Neuscamman, Eric. Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo. United States. https://doi.org/10.1063/1.5008743
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Robinson, Paul J., Pineda Flores, Sergio D., and Neuscamman, Eric. Sat . "Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo". United States. https://doi.org/10.1063/1.5008743. https://www.osti.gov/servlets/purl/1408517.
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@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 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 = {Sat Oct 28 00:00:00 EDT 2017},
month = {Sat Oct 28 00:00:00 EDT 2017}
}
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Publisher's Version of Record
https://doi.org/10.1063/1.5008743
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    Works referencing / citing this record:

    Complementary first and second derivative methods for ansatz optimization in variational Monte Carlo
    journal, January 2019

    • Otis, Leon; Neuscamman, Eric
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
    • DOI: 10.1039/c9cp02269d

    Excitation energies from diffusion Monte Carlo using selected configuration interaction nodes
    journal, July 2018

    • Scemama, Anthony; Benali, Anouar; Jacquemin, Denis
    • The Journal of Chemical Physics, Vol. 149, Issue 3
    • DOI: 10.1063/1.5041327

    Communication: A mean field platform for excited state quantum chemistry
    journal, August 2018

    • Shea, Jacqueline A. R.; Neuscamman, Eric
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    • DOI: 10.1063/1.5045056

    Reduced scaling Hilbert space variational Monte Carlo
    journal, November 2018

    • Wei, Haochuan; Neuscamman, Eric
    • The Journal of Chemical Physics, Vol. 149, Issue 18
    • DOI: 10.1063/1.5047207

    Excitation energies from diffusion Monte Carlo using selected Configuration Interaction nodes
    text, January 2018

    Reduced Scaling Hilbert Space Variational Monte Carlo
    text, January 2018

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