Coupled 3D (J ≥ 0) Time-Dependent Wave Packet Calculation for the F + H₂ Reaction on Accurate Ab Initio Multi-State Diabatic Potential Energy Surfaces

Abstract

We had calculated adiabatic potential energy surfaces (PESs), nonadiabatic, and spin−orbit (SO) coupling terms among the lowest three electronic states (1 2 A′, 2 2 A′, and 1 2 A″) of the F + H 2 system using the multireference configuration interaction (MRCI) level of theory, and the adiabatic-to-diabatic transformation equations were solved to formulate the diabatic Hamiltonian matrix [J. Chem. Phys. 2020, 153, 174301] for the entire region of the nuclear configuration space. The accuracy of such diabatic PESs is explored by performing scattering calculations to evaluate integral cross sections (ICSs) and rate constants. The nonadiabatic and SO effects are studied by utilizing coupled 3D time-dependent wave packet formalism with zero and nonzero total angular momentum on multiple adiabatic/diabatic surfaces calculation. We depict the convergence profiles of reaction probabilities for the reactive as well as nonreactive processes on various electronic states at different collision energies with respect to total angular momentum including all helicity quantum numbers. Finally, total ICSs are calculated as functions of collision energies for the initial rovibrational state (v = 0, j = 0) of the H 2 molecule along with the temperature-dependent rate coefficient, where those quantities are compared with previous theoretical and experimental results.

Quantum Dynamics of O(3P)+HBr→OH+Br Reaction: Integral Cross Sections and Rate Constants and their Initial State Dependence

“…We note in passing that recently there have been reports of using hyperspherical coordinates in place of the Jacobi coordinates in wave packet dynamical calculations. [35][36][37][38][39] Body-fixed coordinates [40][41] are then employed to describe the system. The z-axis of the body-fixed frame is chosen to point along R (i. e., R-embedding [42] ).…”