Nonequilibrium Chemical Effects in Single-Molecule SERS Revealed by Ab Initio Molecular Dynamics Simulations

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• 作者：Sean A. Fischer ; Edoardo ApràNiranjan Govind ; Wayne P. Hess ; Patrick Z. El-Khoury
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：February 16, 2017
• 年：2017
• 卷：121
• 期：6
• 页码：1344-1350
• 全文大小：494K
• ISSN：1520-5215

文摘

Recent developments in nanophotonics have paved the way for achieving significant advances in the realm of single-molecule chemical detection, imaging, and dynamics. In particular, surface-enhanced Raman scattering (SERS) is a powerful analytical technique that is now routinely used to identify the chemical identity of single molecules. Understanding how nanoscale physical and chemical processes affect single-molecule SERS spectra and selection rules is a challenging task and is still actively debated. Herein, we explore underappreciated chemical phenomena in ultrasensitive SERS. We observe a fluctuating excited electronic state manifold, governed by the conformational dynamics of a molecule (4,4′-dimercaptostilbene, DMS) interacting with a metallic cluster (Ag₂₀). This affects our simulated single-molecule SERS spectra; the time trajectories of a molecule interacting with its unique local environment dictates the relative intensities of the observable Raman-active vibrational states. Ab initio molecular dynamics of a model Ag₂₀–DMS system are used to illustrate both concepts in light of recent experimental results.