A numerically exact description of ultrafast vibrational decoherence in vibration-coupled electron transfer

• 成果类型: Article
• 署名作者: Wang, Yuanheng; Benny, Alfy; Le De, Brieuc; Chin, Alex W.; Scholes, Gregory D.
• 署名单位: Princeton University; Sorbonne Universite; Centre National de la Recherche Scientifique (CNRS)
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-14090
• DOI: 10.1073/pnas.2416542122
• 发表日期: 2025-03-04
• 关键词: matrix renormalization-group; vibronic transitions; polyatomic-molecules; dynamical symmetry; exciton dynamics; coherence; state; spectroscopy

摘要

Broadband pump-probe spectroscopy has been widely used to measure vibrational de- coherence associated with the reaction coordinate in photoinduced ultrafast vibration- coupled electron transfer (VCET) reactions. These experiments provide insight into the interplay of intramolecular coordinates along the reaction coordinate. However, a general theoretical foundation for analyzing, and even for explaining rigorously, these data is lacking. In this work, we study vibrational decoherence in a model VCET reaction using the nearly exact time-dependent density matrix renormalization group simulation method. We explore how analyzing the density matrix with quantum information measures can help elucidate the evolution of vibrational coherence in simulations of dynamics. We examine how vibrational coherence is affected by electron transfer on the timescale of approximately 100 femtoseconds. Our results suggest that electron transfer, in the nonadiabatic model, changes the vibrational equilibrium position abruptly-an example of a quantum quench event. This explains the concomitant vibrational decoherence. We find that abrupt vibrational decoherence can be mitigated by wavepacket motion occurring on the timescale of the electron transfer.