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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/D0CP01754J· OSTI ID:1637265
 [1];  [2];  [3];  [4]
  1. Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
  2. Univ. of New Mexico, Albuquerque, NM (United States); Univ. Bielefeld (Germany)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
  4. Johns Hopkins Univ., Baltimore, MD (United States)
+ Show Author Affiliations
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.
Research Organization:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Organization:
USDOE; USDOE Office of Nuclear Energy (NE), Nuclear Fuel Cycle and Supply Chain. Office of Advanced Fuels Technologies; USDOE Office of Science (SC)
Grant/Contract Number:
SC0015997
OSTI ID:
1637265
Alternate ID(s):
OSTI ID: 1633364
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 24 Vol. 22; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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