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Title: Non-orthogonal multi-Slater determinant expansions in auxiliary field quantum Monte Carlo

Abstract

We investigate here the use of non-orthogonal multi-Slater determinant (NOMSD) expansions as trial wavefunctions in auxiliary field quantum Monte Carlo simulations of molecular systems. We show that NOMSD trial wavefunctions with as few as twenty determinants are sufficient in order to achieve chemical accuracy across most of the G1 molecular test set. We also show that NOMSD trial wavefunctions are useful for more challenging strongly correlated systems by computing relative energies along the isomerization path of the [Cu2O2]2+ molecule. Our results for [Cu2O2]2+ compare favorably with other accurate quantum many-body methods, including density matrix renormalization group and completely renormalized coupled cluster methods.

Authors:
 [1]; ORCiD logo [2];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Rice Univ., Houston, TX (United States). Applied Physics Program. Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Rice Univ., Houston, TX (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); LLNL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)
OSTI Identifier:
1512621
Report Number(s):
LLNL-JRNL-745447
Journal ID: ISSN 0021-9606; 900954
Grant/Contract Number:  
AC52-07NA27344; DGE-1450681
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 7; 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; quantum chemistry; Slater determinant; chemical elements; correlation-consistent basis sets; self consistent field methods; isomerization; correlation energy; Monte Carlo methods

Citation Formats

Landinez Borda, Edgar Josué, Gomez, John, and Morales, Miguel A. Non-orthogonal multi-Slater determinant expansions in auxiliary field quantum Monte Carlo. United States: N. p., 2019. Web. doi:10.1063/1.5049143.
Landinez Borda, Edgar Josué, Gomez, John, & Morales, Miguel A. Non-orthogonal multi-Slater determinant expansions in auxiliary field quantum Monte Carlo. United States. doi:10.1063/1.5049143.
Landinez Borda, Edgar Josué, Gomez, John, and Morales, Miguel A. Wed . "Non-orthogonal multi-Slater determinant expansions in auxiliary field quantum Monte Carlo". United States. doi:10.1063/1.5049143. https://www.osti.gov/servlets/purl/1512621.
@article{osti_1512621,
title = {Non-orthogonal multi-Slater determinant expansions in auxiliary field quantum Monte Carlo},
author = {Landinez Borda, Edgar Josué and Gomez, John and Morales, Miguel A.},
abstractNote = {We investigate here the use of non-orthogonal multi-Slater determinant (NOMSD) expansions as trial wavefunctions in auxiliary field quantum Monte Carlo simulations of molecular systems. We show that NOMSD trial wavefunctions with as few as twenty determinants are sufficient in order to achieve chemical accuracy across most of the G1 molecular test set. We also show that NOMSD trial wavefunctions are useful for more challenging strongly correlated systems by computing relative energies along the isomerization path of the [Cu2O2]2+ molecule. Our results for [Cu2O2]2+ compare favorably with other accurate quantum many-body methods, including density matrix renormalization group and completely renormalized coupled cluster methods.},
doi = {10.1063/1.5049143},
journal = {Journal of Chemical Physics},
number = 7,
volume = 150,
place = {United States},
year = {2019},
month = {2}
}

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