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Title: An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3

Abstract

To offer an in-depth understanding of the HO3 radical and its dissociation to OH + O2, a six-dimensional potential energy surface (PES) has been constructed by fitting 2087 energy points for the electronic ground state of HO3 (X2A") using the permutation invariant polynomial-neural network (PIP-NN) approach. The energy points were calculated using an explicitly-correlated and Davidson-corrected multi-reference configuration interaction approach with the correlation-consistent polarized valence double zeta basis (MRCI(Q)-F12/VDZ-F12). On the PES, the trans-HO3 isomer is found to be the global minimum, 33.0 cm-1 below the cis-HO3 conformer, which is consistent with previous high-level theoretical investigations. The dissociation to the OH + O2 asymptote from both conformers is shown to be barrierless. As a benchmark from a recently developed high-accuracy thermochemistry protocol, D0 for trans-HO3 is calculated to be 2.29 ± 0.36 kcal mol-1, only slightly deeper than the value of 2.08 kcal mol-1 obtained using the PES, and in reasonable agreement with the experimentally estimated value of 2.93 ± 0.07 kcal mol-1. Using this PES, low-lying vibrational energy levels of HO3 are determined using an exact quantum Hamiltonian and compared with available experimental results.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]
+ Show Author Affiliations
  1. Nanjing Univ. (China); Univ. of New Mexico, Albuquerque, NM (United States)
  2. Nanjing Univ. (China)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
  4. Missouri Univ. of Science and Technology, Rolla, MO (United States)
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China (NNSFC); National Science Foundation (NSF)
OSTI Identifier:
1598426
Alternate Identifier(s):
OSTI ID: 1526774
Grant/Contract Number:  
SC0015997; CHE-1566246
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 21; Journal Issue: 25; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hu, Xixi, Zuo, Junxiang, Xie, Changjian, Dawes, Richard, Guo, Hua, and Xie, Daiqian. An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3. United States: N. p., 2019. Web. doi:10.1039/C9CP02206F.
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Hu, Xixi, Zuo, Junxiang, Xie, Changjian, Dawes, Richard, Guo, Hua, & Xie, Daiqian. An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3. United States. doi:https://doi.org/10.1039/C9CP02206F
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Hu, Xixi, Zuo, Junxiang, Xie, Changjian, Dawes, Richard, Guo, Hua, and Xie, Daiqian. Tue . "An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3". United States. doi:https://doi.org/10.1039/C9CP02206F. https://www.osti.gov/servlets/purl/1598426.
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@article{osti_1598426,
title = {An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3},
author = {Hu, Xixi and Zuo, Junxiang and Xie, Changjian and Dawes, Richard and Guo, Hua and Xie, Daiqian},
abstractNote = {To offer an in-depth understanding of the HO3 radical and its dissociation to OH + O2, a six-dimensional potential energy surface (PES) has been constructed by fitting 2087 energy points for the electronic ground state of HO3 (X2A") using the permutation invariant polynomial-neural network (PIP-NN) approach. The energy points were calculated using an explicitly-correlated and Davidson-corrected multi-reference configuration interaction approach with the correlation-consistent polarized valence double zeta basis (MRCI(Q)-F12/VDZ-F12). On the PES, the trans-HO3 isomer is found to be the global minimum, 33.0 cm-1 below the cis-HO3 conformer, which is consistent with previous high-level theoretical investigations. The dissociation to the OH + O2 asymptote from both conformers is shown to be barrierless. As a benchmark from a recently developed high-accuracy thermochemistry protocol, D0 for trans-HO3 is calculated to be 2.29 ± 0.36 kcal mol-1, only slightly deeper than the value of 2.08 kcal mol-1 obtained using the PES, and in reasonable agreement with the experimentally estimated value of 2.93 ± 0.07 kcal mol-1. Using this PES, low-lying vibrational energy levels of HO3 are determined using an exact quantum Hamiltonian and compared with available experimental results.},
doi = {10.1039/C9CP02206F},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 25,
volume = 21,
place = {United States},
year = {2019},
month = {6}
}
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DOI:  https://doi.org/10.1039/C9CP02206F
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