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

Shanyu Han; Antonio G.S. de Oliveira-Filho; Yinan Shu; Donald G. Truhlar; Hua Guo

doi:10.1002/cphc.202200039

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

Shanyu Han, Antonio G.S. de Oliveira-Filho, Yinan Shu, Donald G. Truhlar, Hua Guo

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

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.

Original language	English (US)
Article number	e202200039
Journal	ChemPhysChem
Volume	23
Issue number	8
DOIs	https://doi.org/10.1002/cphc.202200039
State	Published - Apr 20 2022

Bibliographical note

Funding Information:
This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE‐SC0015997. A.G.S.d.O.‐F. acknowledges support from the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) under Grant No. 306830/2018‐3 and the São Paulo Research Foundation (FAPESP) under Grant No. 2020/08553‐2. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001.

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Keywords

diabatic potential energy matrix
nonadiabatic dynamics
potential energy surfaces
quantum photochemistry
quenching of OH(A)

PubMed: MeSH publication types

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

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

abstract = "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.",

keywords = "diabatic potential energy matrix, nonadiabatic dynamics, potential energy surfaces, quantum photochemistry, quenching of OH(A)",

author = "Shanyu Han and {de Oliveira-Filho}, {Antonio G.S.} and Yinan Shu and Truhlar, {Donald G.} and Hua Guo",

note = "Funding Information: This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE‐SC0015997. A.G.S.d.O.‐F. acknowledges support from the Conselho Nacional de Desenvolvimento Cient{\'i}fico e Tecnol{\'o}gico (CNPq) under Grant No. 306830/2018‐3 and the S{\~a}o Paulo Research Foundation (FAPESP) under Grant No. 2020/08553‐2. This study was financed in part by the Coordena{\c c}{\~a}o de Aperfei{\c c}oamento de Pessoal de N{\'i}vel Superior – Brasil (CAPES) – Finance Code 001. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

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AU - de Oliveira-Filho, Antonio G.S.

AU - Shu, Yinan

AU - Truhlar, Donald G.

AU - Guo, Hua

N1 - Funding Information: This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE‐SC0015997. A.G.S.d.O.‐F. acknowledges support from the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) under Grant No. 306830/2018‐3 and the São Paulo Research Foundation (FAPESP) under Grant No. 2020/08553‐2. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001. Publisher Copyright: © 2022 Wiley-VCH GmbH.

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N2 - 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.

AB - 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.

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KW - nonadiabatic dynamics

KW - potential energy surfaces

KW - quantum photochemistry

KW - quenching of OH(A)

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