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Updated: Jun 19, 2025

Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems
Published on: April 28, 2016
Local electric field in nanocavities dictates the vibrational relaxation dynamics of interfacial molecules
Xiaoxuan Zheng1, Quanbing Pei1, Junjun Tan2
1Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China Hefei Anhui 230026 China yiluo@ustc.edu.cn shujiye@ustc.edu.cn.
Abstract:
Plasmonic nanocavities enable the generation of strong light-matter coupling and exhibit great potential in plasmon-mediated chemical reactions (PMCRs). Although an electric field generated by nanocavities (E n) has recently been reported, its effect on the vibrational energy relaxation (VER) of the molecules in the nanocavities has not been explored. In this study, we reveal the impact of an electric field sensed by molecules (para-substituted thiophenol derivatives) in a nanocavity (E f) on VER processes by employing advanced time-resolved femtosecond sum frequency generation vibrational spectroscopy (SFG-VS) supplemented by electrochemical measurements. The magnitude of E n is almost identical (1.0 ± 0.2 V nm-1) beyond the experimental deviation while E f varies from 0.3 V nm-1 to 1.7 V nm-1 depending on the substituent. An exponential correlation between E f and the complete recovery time of the ground vibrational C[double bond, length as m-dash]C state (T 2) of the phenyl ring is observed. Substances with a smaller T 2 are strongly correlated with the reported macroscopic chemical reactivity. This finding may aid in enriching the current understanding of PMCRs and highlights the possibility of regulating vibrational energy flow into desired reaction coordinates by using a local electric field.
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