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

The two-state non-adiabatic potential energy matrices of the CaH(2)(+ )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+(4s(2)S) + H-2((XSg+)-S-1) ? H(S-2) + CaH+((XS+)-S-1) 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 bohr(2); in contrast, the maximum discrepancy between the theoretical result derived from the non-adiabatic PES and the experimental value is merely 0.42 bohr(2). 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.

Automated summary

The two-state non-adiabatic potential energy matrices of the CaH(2)(+) system are calculated using a diabatization approach and a neural network model. Adiabatic and non-adiabatic potential energy surfaces are then constructed based on these matrices. The reaction dynamics of the CaH2+ system is significantly influenced by non-adiabatic effects, as indicated by the comparative analysis of experimental and theoretical results.