Studies of Nonadiabatic Dynamics in the Singlet Fission Processes of Pentacene Dimer via Tensor Train Decomposition Method

TL;DR

This paper investigates the singlet fission process in a pentacene dimer using advanced quantum chemistry and tensor train decomposition to understand vibrational effects and the super-exchange mechanism, providing detailed insights into the dynamics.

Contribution

It introduces a combined high-level quantum chemistry and tensor train decomposition approach to study nonadiabatic dynamics in singlet fission, highlighting vibrational mode roles.

Findings

Vibrational modes resonant with energy gaps significantly influence SF dynamics.

Super-exchange mechanism mediated by charge-transfer states is confirmed.

Tensor train decomposition efficiently simulates complex quantum dynamics.

Abstract

Singlet fission (SF) is a very significant photophysical phenomenon and possesses potential applications. In this work, we try to give the rather detailed theoretical investigation of the SF process in the stacked polyacene dimer by combining the high-level quantum chemistry calculations, and the quantum dynamics simulations based on the tensor train decomposition method. Starting from the construction of the linear vibronic coupling model, we explore the pure electronic dynamics and the vibronic dynamics in the SF processes. The role of vibrational modes in nonadiabatic dynamics is addressed. The results show that the super-exchange mechanism mediated by the charge-transfer state is found in both pure electronic dynamics and the nonadiabatic dynamics. Particularly, the vibrational modes with the frequency resonance with the adiabatic energy gap play very import roles in the SF dynamics. This work not only provides a deep and detailed understanding of the SF process, but also verifies the efficiency of the tensor train decomposition method that can serve as the reference dynamics method to explore the dynamics behaviors of complex systems.