The impact of non-adiabatic effects on reaction dynamics: a study based on the adiabatic and non-adiabatic potential energy surfaces of CaH2+

Abstract

The two-state non-adiabatic potential energy matrices of the CaH₂⁺ system are calculated via a diabatization approach by using a neural network model. Subsequently, the adiabatic and non-adiabatic potential energy surfaces (PESs) are constructed based on these non-adiabatic potential energy matrices. Furthermore, based on the adiabatic and non-adiabatic PESs, the Ca⁺(4s²S) + H₂(X¹Σ⁺_g) → H(²S) + CaH⁺(X¹Σ⁺) reaction is studied using the time-dependent wave packet method. Comparative analysis of the experimental and theoretical integral reaction cross-sections (ICSs) indicates that the maximum deviation between the results obtained from the adiabatic PES and the corresponding experimental value is 12.7 bohr²; in contrast, the maximum discrepancy between the theoretical result derived from the non-adiabatic PES and the experimental value is merely 0.42 bohr². The potential well along the reaction path acts as a ‘filter’, selectively guiding intermediates with longer lifetimes in the potential well back to the reactant channel. This phenomenon indicates that the non-adiabatic effects significantly influence the reaction dynamics of the CaH₂⁺ system.