Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited 2ς+ state of OH by molecular hydrogen

Yinan Shu, Joanna Kryven, Antonio Gustavo Sampaio De Oliveira-Filho, Linyao Zhang, Guo Liang Song, Shaohong L. Li, Rubén Meana-Pañeda, Bina Fu, Joel M. Bowman, Donald G. Truhlar

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Abstract

We have employed extended multiconfiguration quasidegenerate perturbation theory, fourfold-way diabatic molecular orbitals, and configurational uniformity to develop a global three-state diabatic representation of the potential energy surfaces and their couplings for the electronically nonadiabatic reaction OH* + H2 → H2O + H, where * denotes electronic excitation to the A 2ς+ state. To achieve sign consistency of the computed diabatic couplings, we developed a graphics processing unit-accelerated algorithm called the cluster-growing algorithm. Having obtained consistent signs of the diabatic couplings, we fit the diabatic matrix elements (which consist of the diabatic potentials and the diabatic couplings) to analytic representations. Adiabatic potential energy surfaces are generated by diagonalizing the 3 × 3 diabatic potential energy matrix. The comparisons between the fitted and computed diabatic matrix elements and between the originally computed adiabatic potential energy surfaces and those generated from the fits indicate that the current fit is accurate enough for dynamical studies, and it may be used for quantal or semiclassical dynamics calculations.

Original languageEnglish (US)
Article number104311
JournalJournal of Chemical Physics
Volume151
Issue number10
DOIs
StatePublished - Sep 14 2019

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 No. DE-SC0015997. A.G.S.de O.-F. acknowledges support from the Coordena????o de Aperfei??oamento de Pessoal de N?-vel Superior-Brasil (CAPES)-Finance Code 001 and the Conselho Nacional de Desenvolvimento Cient?-fico e Tecnol?gico (CNPq) under Grant Nos. 306830/2018-3 and 421077/2018-2.

Publisher Copyright:
© 2019 Author(s).

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