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Title: Investigation of the ozone formation reaction pathway: Comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI

Abstract

The association/dissociation reaction path for ozone (O2 + O ↔ O3) is notoriously difficult to describe accurately using ab initio electronic structure theory, due to the importance of both strong and dynamic electron correlations. Experimentally, spectroscopic studies of the highest lying recorded vibrational states combined with the observed negative temperature dependence of the kinetics of oxygen isotope exchange reactions confirm that the reaction is barrierless, consistent with the latest potential energy surfaces. Previously reported potentials based on Davidson-corrected internally contracted multireference configuration interaction (MRCI) suffer from a spurious reef feature in the entrance channel even when extrapolated towards the complete basis set limit. Here, we report an analysis of comparisons between a variety of electronic structure methods including internally contracted and uncontracted MRCI (with and without Davidson corrections), as well as full configuration interaction quantum Monte Carlo, fixed-node diffusion Monte Carlo, and density matrix renormalization group.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [1]
  1. Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409, USA
  2. Department of Chemistry, Kyoto University, Kyoto, Japan
  3. Departamento de Física, Universidade Federal do Espírito Santo, Vitória 29075-910, Espírito Santo, Brazil
  4. Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos, 12.228-900 São Paulo, Brazil
  5. School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People’s Republic of China; Institute for Theoretical Chemistry, University of Vienna, Währingerstrasse 17, A-1090 Vienna, Austria
Publication Date:
Research Org.:
Univ. of Missouri, Columbia, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535320
Alternate Identifier(s):
OSTI ID: 1378819
Grant/Contract Number:  
SC0010616
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Powell, Andrew D., Dattani, Nikesh S., Spada, Rene F. K., Machado, Francisco B. C., Lischka, Hans, and Dawes, Richard. Investigation of the ozone formation reaction pathway: Comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI. United States: N. p., 2017. Web. doi:10.1063/1.4990673.
Powell, Andrew D., Dattani, Nikesh S., Spada, Rene F. K., Machado, Francisco B. C., Lischka, Hans, & Dawes, Richard. Investigation of the ozone formation reaction pathway: Comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI. United States. doi:10.1063/1.4990673.
Powell, Andrew D., Dattani, Nikesh S., Spada, Rene F. K., Machado, Francisco B. C., Lischka, Hans, and Dawes, Richard. Thu . "Investigation of the ozone formation reaction pathway: Comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI". United States. doi:10.1063/1.4990673. https://www.osti.gov/servlets/purl/1535320.
@article{osti_1535320,
title = {Investigation of the ozone formation reaction pathway: Comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI},
author = {Powell, Andrew D. and Dattani, Nikesh S. and Spada, Rene F. K. and Machado, Francisco B. C. and Lischka, Hans and Dawes, Richard},
abstractNote = {The association/dissociation reaction path for ozone (O2 + O ↔ O3) is notoriously difficult to describe accurately using ab initio electronic structure theory, due to the importance of both strong and dynamic electron correlations. Experimentally, spectroscopic studies of the highest lying recorded vibrational states combined with the observed negative temperature dependence of the kinetics of oxygen isotope exchange reactions confirm that the reaction is barrierless, consistent with the latest potential energy surfaces. Previously reported potentials based on Davidson-corrected internally contracted multireference configuration interaction (MRCI) suffer from a spurious reef feature in the entrance channel even when extrapolated towards the complete basis set limit. Here, we report an analysis of comparisons between a variety of electronic structure methods including internally contracted and uncontracted MRCI (with and without Davidson corrections), as well as full configuration interaction quantum Monte Carlo, fixed-node diffusion Monte Carlo, and density matrix renormalization group.},
doi = {10.1063/1.4990673},
journal = {Journal of Chemical Physics},
number = 9,
volume = 147,
place = {United States},
year = {2017},
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