Issue 23, 2024

A diabatization method based upon integrating the diabatic potential gradient difference

Abstract

In this work we develop a new scheme to construct a diabatic potential energy matrix (DPEM). We propose a diabatization method which is based on integrating the diabatic potential gradient difference to diabatize adiabatic ab initio energies. This method is capable of performing high-precision adiabatic-to-diabatic transformations, with a unique advantage in effectively handling the significant fluctuations in derivative-couplings caused by conical intersection (CI) seams. The above scheme is applied to the DPEM construction of the Na(3p) + H2 → NaH + H reaction. The fitting data including adiabatic energies, energy gradients and derivative-couplings obtained from a previous benchmark DPEM are diabatized and fitted using a general neural network fitting procedure to generate the DPEM. The produced DPEM can effectively describe nonadiabatic processes involving different electronic states. We further perform quantum dynamical calculations on the new DPEM and the previous benchmark DPEM, and the obtained results demonstrate the effectiveness of our scheme.

Graphical abstract: A diabatization method based upon integrating the diabatic potential gradient difference

Supplementary files

Article information

Article type
Paper
Submitted
26 Qun 2024
Accepted
10 Agd 2024
First published
11 Agd 2024

Phys. Chem. Chem. Phys., 2024,26, 16477-16487

A diabatization method based upon integrating the diabatic potential gradient difference

F. Li, X. Liu, H. Ma and W. Bian, Phys. Chem. Chem. Phys., 2024, 26, 16477 DOI: 10.1039/D4CP00375F

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