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Title: Beyond the Born-Oppenheimer approximation with quantum Monte Carlo methods

Abstract

Here, we develop tools that enable the study of non-adiabatic effects with variational and diffusion Monte Carlo methods. We propose a highly accurate wave function ansatz for electron-ion systems that can involve a combination of both fixed and quantum ions. We explicitly calculate the ground state energies of H 2, LiH, H 2O and FHF - using fixed-node quantum Monte Carlo with wave function nodes that explicitly depend on the ion positions. The obtained energies implicitly include the effects arising from quantum nuclei and electron-nucleus coupling. We compare our findings to the best theoretical and experimental results available and find excellent agreement.

Authors:
 [1];  [2];  [1];  [1]
  1. Univ. of Illinois, Urbana, IL (United States)
  2. Univ. of Illinois, Urbana, IL (United States); Tampere Univ. of Technology (Finland)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1565355
Alternate Identifier(s):
OSTI ID: 1179660
Grant/Contract Number:  
AC05-00OR22725; NA0001789
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. A
Additional Journal Information:
Journal Volume: 90; Journal Issue: 4; Journal ID: ISSN 1050-2947
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English

Citation Formats

Tubman, Norm M., Kylänpää, Ilkka, Hammes-Schiffer, Sharon, and Ceperley, David M. Beyond the Born-Oppenheimer approximation with quantum Monte Carlo methods. United States: N. p., 2014. Web. doi:10.1103/physreva.90.042507.
Tubman, Norm M., Kylänpää, Ilkka, Hammes-Schiffer, Sharon, & Ceperley, David M. Beyond the Born-Oppenheimer approximation with quantum Monte Carlo methods. United States. doi:10.1103/physreva.90.042507.
Tubman, Norm M., Kylänpää, Ilkka, Hammes-Schiffer, Sharon, and Ceperley, David M. Tue . "Beyond the Born-Oppenheimer approximation with quantum Monte Carlo methods". United States. doi:10.1103/physreva.90.042507. https://www.osti.gov/servlets/purl/1565355.
@article{osti_1565355,
title = {Beyond the Born-Oppenheimer approximation with quantum Monte Carlo methods},
author = {Tubman, Norm M. and Kylänpää, Ilkka and Hammes-Schiffer, Sharon and Ceperley, David M.},
abstractNote = {Here, we develop tools that enable the study of non-adiabatic effects with variational and diffusion Monte Carlo methods. We propose a highly accurate wave function ansatz for electron-ion systems that can involve a combination of both fixed and quantum ions. We explicitly calculate the ground state energies of H2, LiH, H2O and FHF- using fixed-node quantum Monte Carlo with wave function nodes that explicitly depend on the ion positions. The obtained energies implicitly include the effects arising from quantum nuclei and electron-nucleus coupling. We compare our findings to the best theoretical and experimental results available and find excellent agreement.},
doi = {10.1103/physreva.90.042507},
journal = {Physical Review. A},
number = 4,
volume = 90,
place = {United States},
year = {2014},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 13 works
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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