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Title: Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo

We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently-introduced variation-after-response method, this ansatz allows a crucial orbital optimization step to be performed beyond a configuration interaction singles expansion, while only requiring calculation of two Slater determinant objects. As a result, we demonstrate this ansatz for the illustrative example of the stretched LiF molecule, for a range of excited states of formaldehyde, and finally for the more challenging ethylene-tetrafluoroethylene molecule.
Authors:
 [1] ; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), 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: 19; Related Information: http://www.qmcpack.org; 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
Contributing Orgs:
Lawrence Berkeley National Laboratory, University of California, Berkeley
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; Quantum Monte Carlo; Electronic structure theory; Charge transfer; Excited states; Electron correlation
OSTI Identifier:
1409183
Alternate Identifier(s):
OSTI ID: 1420662

Blunt, Nick S., and Neuscamman, Eric. Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo. United States: N. p., Web. doi:10.1063/1.4998197.
Blunt, Nick S., & Neuscamman, Eric. Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo. United States. doi:10.1063/1.4998197.
Blunt, Nick S., and Neuscamman, Eric. 2017. "Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo". United States. doi:10.1063/1.4998197. https://www.osti.gov/servlets/purl/1409183.
@article{osti_1409183,
title = {Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo},
author = {Blunt, Nick S. and Neuscamman, Eric},
abstractNote = {We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently-introduced variation-after-response method, this ansatz allows a crucial orbital optimization step to be performed beyond a configuration interaction singles expansion, while only requiring calculation of two Slater determinant objects. As a result, we demonstrate this ansatz for the illustrative example of the stretched LiF molecule, for a range of excited states of formaldehyde, and finally for the more challenging ethylene-tetrafluoroethylene molecule.},
doi = {10.1063/1.4998197},
journal = {Journal of Chemical Physics},
number = 19,
volume = 147,
place = {United States},
year = {2017},
month = {11}
}

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