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Title: On the nonadiabatic collisional quenching of OH(A) by H2: a four coupled quasi-diabatic state description

Abstract

A four-state diabatic potential energy matrix (DPEM), Hd, for the description of the nonadiabatic quenching of OH(A2Σ+) by collisions with H2 is reported. The DPEM is constructed as a fit to adiabatic energies, energy gradients, and derivative couplings obtained exclusively from multireference configuration interaction wave functions. A four-adiabatic-electronic-state representation is used in order to describe all energetically accessible regions of the nuclear coordinate space. Partial permutation-inversion symmetry is incorporated into the representation. Here, the fit is based on electronic structure data at 42 882 points, described by over 1.6 million least squares equations with a root mean square (mean unsigned) error of 178(83) cm–1. Comparison of ab initio and Hd determined minima, saddle points, and energy minimized points on C2v, Cs, C∞v, and C1 (noncoplanar) portions of two conical intersection seams are used to establish the accuracy of the Hd.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Johns Hopkins Univ., Baltimore, MD (United States)
  2. Univ. of New Mexico, Albuquerque, NM (United States); Univ. Bielefeld (Germany)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE), Nuclear Fuel Cycle and Supply Chain. Office of Advanced Fuels Technologies; USDOE Office of Science (SC)
OSTI Identifier:
1637265
Alternate Identifier(s):
OSTI ID: 1633364
Grant/Contract Number:  
SC0015997
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 24; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 79 ASTRONOMY AND ASTROPHYSICS; photochemistry; conical; intersections

Citation Formats

Malbon, Christopher L., Zhao, Bin, Guo, Hua, and Yarkony, David R. On the nonadiabatic collisional quenching of OH(A) by H2: a four coupled quasi-diabatic state description. United States: N. p., 2020. Web. https://doi.org/10.1039/D0CP01754J.
Malbon, Christopher L., Zhao, Bin, Guo, Hua, & Yarkony, David R. On the nonadiabatic collisional quenching of OH(A) by H2: a four coupled quasi-diabatic state description. United States. https://doi.org/10.1039/D0CP01754J
Malbon, Christopher L., Zhao, Bin, Guo, Hua, and Yarkony, David R. Mon . "On the nonadiabatic collisional quenching of OH(A) by H2: a four coupled quasi-diabatic state description". United States. https://doi.org/10.1039/D0CP01754J. https://www.osti.gov/servlets/purl/1637265.
@article{osti_1637265,
title = {On the nonadiabatic collisional quenching of OH(A) by H2: a four coupled quasi-diabatic state description},
author = {Malbon, Christopher L. and Zhao, Bin and Guo, Hua and Yarkony, David R.},
abstractNote = {A four-state diabatic potential energy matrix (DPEM), Hd, for the description of the nonadiabatic quenching of OH(A2Σ+) by collisions with H2 is reported. The DPEM is constructed as a fit to adiabatic energies, energy gradients, and derivative couplings obtained exclusively from multireference configuration interaction wave functions. A four-adiabatic-electronic-state representation is used in order to describe all energetically accessible regions of the nuclear coordinate space. Partial permutation-inversion symmetry is incorporated into the representation. Here, the fit is based on electronic structure data at 42 882 points, described by over 1.6 million least squares equations with a root mean square (mean unsigned) error of 178(83) cm–1. Comparison of ab initio and Hd determined minima, saddle points, and energy minimized points on C2v, Cs, C∞v, and C1 (noncoplanar) portions of two conical intersection seams are used to establish the accuracy of the Hd.},
doi = {10.1039/D0CP01754J},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 24,
volume = 22,
place = {United States},
year = {2020},
month = {6}
}

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