skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on November 16, 2018

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