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

• Published in: The Journal of chemical physics 2019-09, Vol.151 (10)
• Main Authors: 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.
• Format: Article
• Language: English
• Subjects: Adiabatic flow; Algorithms; Computation; Coupling (molecular); Couplings; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Molecular orbitals; Perturbation theory; Physics; Potential energy; Representations
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5111547

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.