Open AccessFewest switches surface hopping with Baeck-An couplings
Author(s) -
Mariana T. do Casal,
Josene M. Toldo,
Max Pinheiro,
Mario Barbatti
Publication year - 2022
Publication title -
open research europe
Language(s) - English
Resource type - Journals
ISSN - 2732-5121
DOI - 10.12688/openreseurope.13624.2
Subject(s) - surface hopping , time dependent density functional theory , coupling (piping) , physics , adiabatic process , vibronic coupling , potential energy surface , surface (topology) , singlet state , excitation , statistical physics , density functional theory , quantum mechanics , excited state , materials science , ab initio , geometry , mathematics , metallurgy
In the Baeck-An (BA) approximation, first-order nonadiabatic coupling vectors are given in terms of adiabatic energy gaps and the second derivative of the gaps with respect to the coupling coordinate. In this paper, a time-dependent (TD) BA approximation is derived, where the couplings are computed from the energy gaps and their second time-derivatives. TD-BA couplings can be directly used in fewest switches surface hopping, enabling nonadiabatic dynamics with any electronic structure methods able to provide excitation energies and energy gradients. Test results of surface hopping with TD-BA couplings for ethylene and fulvene show that the TD-BA approximation delivers a qualitatively correct picture of the dynamics and a semiquantitative agreement with reference data computed with exact couplings. Nevertheless, TD-BA does not perform well in situations conjugating strong couplings and small velocities. Considered the uncertainties in the method, TD-BA couplings could be a competitive approach for inexpensive, exploratory dynamics with a small trajectories ensemble. We also assessed the potential use of TD-BA couplings for surface hopping dynamics with time-dependent density functional theory (TDDFT), but the results are not encouraging due to singlet instabilities near the crossing seam with the ground state.