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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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4990673· OSTI ID:1535320
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [1]
  1. Missouri Univ. of Science and Technology, Rolla, MO (United States). Dept. of Chemistry
  2. Kyoto Univ., Kyoto (Japan). Dept. of Chemistry
  3. Univ. Federal do Espírito Santo, Espírito Santo (Brazil). Dept. de Física
  4. Inst. Tecnológico de Aeronáutica, São Paulo (Brazil). Dept. de Química
  5. Tianjin Univ., Tianjin (China). School of Pharmaceutical Science and Technology; Univ. of Vienna, Vienna (Austria). Inst. for Theoretical Chemistry
+ Show Author Affiliations

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. In this work, 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.

Research Organization:
Univ. of Missouri, Columbia, MO (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0010616
OSTI ID:
1535320
Alternate ID(s):
OSTI ID: 1378819
Journal Information:
Journal of Chemical Physics, Vol. 147, Issue 9; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

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Cited By (2)

Rotationally inelastic scattering of O 3 –Ar: state-to-state rates with the multiconfigurational time dependent Hartree method journal January 2020
Accurate rovibrational energies of ozone isotopologues up to J = 10 utilizing artificial neural networks journal July 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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