Wave packet calculations on nonadiabatic effects for the O(3P)+HF(1Σ+) reaction under hyperthermal conditions

Abstract

We present wave packet calculations of total and state-to-state reaction probabilities and integral cross sections for the nonadiabatic dynamics of the O((3)P)+HF → F((2)P)+OH((2)Π) reaction at hyperthermal collision energies ranging from 1.2 to 2.4 eV. The validity of the centrifugal sudden approximation is discussed for the title reaction and a comprehensive investigation of the influence of nonadiabatic effects on the dynamics of this reactive system at high (hyperthermal) collision energies is presented. In general, nonadiabatic effects are negligible for averaged observables, such as total reaction probabilities and integral cross sections, but they are clearly observed in detailed observables such as rotationally state-resolved reaction probabilities. A critical discussion of nonadiabatic effects on the dynamics of the title reaction is carried out by comparing with the reverse reaction and the characteristics of the adiabatic and diabatic potential energy surfaces involved.

The validities of centrifugal sudden approximations in chemical reaction dynamics

“…Very recent study on N + H 2 (HD,D 2 ) demonstrated that the cheaper CS approximation has done well for this reactive system. In the wave packet calculations on the nonadiabatic O( 3 P) + HF reaction with direct and rather fast dynamics, the CS approximation showed a good agreement with the CC calculation in computing both the total and the state‐to‐state integral cross sections. The full dimensional quantum dynamics study of tetraatomic D + H 2 O and D + HOD reactions revealed that the CS approximation does not work well for these reactions.…”