Title: Semiclassical Trajectory Studies of Reactive and Nonreactive Scattering of OH(2Σ+) by H2 Based on an Improved Full-Dimensional Ab Initio Diabatic Potential Energy Matrix

Journal Article · · ChemPhysChem
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]
  1. University of New Mexico, Albuquerque, NM (United States); OSTI
  2. University of Sao Paulo (Brazil)
  3. University of Minnesota, Minneapolis, MN (United States)
  4. University of New Mexico, Albuquerque, NM (United States)
+ Show Author Affiliations

Here we present a new full-dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A 2Σ+) with H2, and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H2O+H. The DPEM was fitted using a many-body expansion with permutationally invariant polynomials in bond-order functions to represent the many-body part. The dynamics calculations were carried out with the fewest-switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head-on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all-b results, especially for the probability of reactive quenching.

Research Organization:
University of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
Coordination for the Improvement of Higher Education Personnel (CAPES); National Council for Scientific and Technological Development (CNPq); Support Foundation to São Paulo State Research (FAPESP); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0015997
OSTI ID:
1976311
Journal Information:
ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 8 Vol. 23; ISSN 1439-4235
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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