U.S. Department of Energy Office of Scientific and Technical Information
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
In this work, 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.
Shu, Yinan, et al. "Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited <sup>2</sup>Σ<sup>+</sup> state of OH by molecular hydrogen." Journal of Chemical Physics, vol. 151, no. 10, Sep. 2019. https://doi.org/10.1063/1.5111547
Shu, Yinan, Kryven, Joanna, Sampaio de Oliveira-Filho, Antonio Gustavo, Zhang, Linyao, Song, Guo-Liang, Li, Shaohong L., Meana-Pañeda, Rubén, Fu, Bina, Bowman, Joel M., & Truhlar, Donald G. (2019). Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited <sup>2</sup>Σ<sup>+</sup> state of OH by molecular hydrogen. Journal of Chemical Physics, 151(10). https://doi.org/10.1063/1.5111547
Shu, Yinan, Kryven, Joanna, Sampaio de Oliveira-Filho, Antonio Gustavo, et al., "Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited <sup>2</sup>Σ<sup>+</sup> state of OH by molecular hydrogen," Journal of Chemical Physics 151, no. 10 (2019), https://doi.org/10.1063/1.5111547
@article{osti_1612364,
author = {Shu, Yinan and Kryven, Joanna and Sampaio de Oliveira-Filho, Antonio Gustavo and Zhang, Linyao and Song, Guo-Liang and Li, Shaohong L. and Meana-Pañeda, Rubén and Fu, Bina and Bowman, Joel M. and Truhlar, Donald G.},
title = {Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited <sup>2</sup>Σ<sup>+</sup> state of OH by molecular hydrogen},
annote = {In this work, 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.},
doi = {10.1063/1.5111547},
url = {https://www.osti.gov/biblio/1612364},
journal = {Journal of Chemical Physics},
issn = {ISSN 0021-9606},
number = {10},
volume = {151},
place = {United States},
publisher = {American Institute of Physics (AIP)},
year = {2019},
month = {09}}
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil (CAPES); USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0015997
Other Award/Contract Number:
306830/2018-3 421077/2018-2
OSTI ID:
1612364
Alternate ID(s):
OSTI ID: 1562133
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 151; ISSN 0021-9606