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Title: How large are nonadiabatic effects in atomic and diatomic systems?

Abstract

With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. Here, we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose, we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. Our report shows the ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei.

Authors:
 [1];  [2];  [1];  [3];  [4]; ORCiD logo [1]
  1. Univ. of Illinois, Urbana, IL (United States). Dept.of Physics
  2. Univ. of Illinois, Urbana, IL (United States). Dept.of Physics; Tampere Univ. of Technology, Tampere (Finland). Dept. of Physics
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Sciences & Technology Division
  4. Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL). Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Univ. of Illinois, Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); DOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1265837
Alternate Identifier(s):
OSTI ID: 1229683; OSTI ID: 1358612
Grant/Contract Number:  
AC05-00OR22725; FG02-12ER46875; NA0001789; CHE-13-61293; OCI-1053575; NA0002911
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Yang, Yubo, Kylänpää, Ilkka, Tubman, Norm M., Krogel, Jaron T., Hammes-Schiffer, Sharon, and Ceperley, David M. How large are nonadiabatic effects in atomic and diatomic systems?. United States: N. p., 2015. Web. doi:10.1063/1.4931667.
Yang, Yubo, Kylänpää, Ilkka, Tubman, Norm M., Krogel, Jaron T., Hammes-Schiffer, Sharon, & Ceperley, David M. How large are nonadiabatic effects in atomic and diatomic systems?. United States. doi:10.1063/1.4931667.
Yang, Yubo, Kylänpää, Ilkka, Tubman, Norm M., Krogel, Jaron T., Hammes-Schiffer, Sharon, and Ceperley, David M. Tue . "How large are nonadiabatic effects in atomic and diatomic systems?". United States. doi:10.1063/1.4931667. https://www.osti.gov/servlets/purl/1265837.
@article{osti_1265837,
title = {How large are nonadiabatic effects in atomic and diatomic systems?},
author = {Yang, Yubo and Kylänpää, Ilkka and Tubman, Norm M. and Krogel, Jaron T. and Hammes-Schiffer, Sharon and Ceperley, David M.},
abstractNote = {With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. Here, we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose, we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. Our report shows the ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei.},
doi = {10.1063/1.4931667},
journal = {Journal of Chemical Physics},
number = 12,
volume = 143,
place = {United States},
year = {2015},
month = {9}
}

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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