Effects of Herzberg--Teller vibronic coupling on coherent excitation energy transfer

TL;DR

This paper investigates how non-Condon vibronic coupling influences quantum coherence and energy transfer in excitonic systems, revealing that it enhances coherence and energy transfer efficiency, with implications for interpreting nonlinear spectroscopy.

Contribution

It provides the first exact dissipaton-equation-of-motion simulations of non-Condon vibronic effects on quantum coherence in excitation energy transfer.

Findings

Non-Condon vibronic coupling intensifies electronic-vibrational energy transfer.

Non-Condon effects enhance total quantum coherence.

Hybrid bath dynamics offer new insights into nonlinear spectroscopy interpretation.

Abstract

In this work, we study the effects of non-Condon vibronic coupling on the quantum coherence of excitation energy transfer, via the exact dissipaton-equation-of-motion (DEOM) evaluations on excitonic model systems. Field-triggered excitation energy transfer dynamics and two dimensional coherent spectroscopy are simulated for both Condon and non-Condon vibronic couplings. Our results clearly demonstrate that the non-Condon vibronic coupling intensifies the dynamical electronic-vibrational energy transfer and enhances the total system-and-bath quantum coherence. Moreover, the hybrid bath dynamics for non-Condon effects enriches the theoretical calculation, and further sheds light on the interpretation of the experimental nonlinear spectroscopy.