Issue 34, 2023

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.

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

Article information

Article type
Paper
Submitted
26 Cax 2023
Accepted
09 Leq 2023
First published
12 Leq 2023

Phys. Chem. Chem. Phys., 2023,25, 22744-22754

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

D. He, W. Li, Q. Li, S. Chen, L. Wang, Y. Liu and M. Wang, Phys. Chem. Chem. Phys., 2023, 25, 22744 DOI: 10.1039/D3CP02416D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements