Time Domain Simulations of Single Molecule Raman Scattering

The Journal of Physical Chemistry. a
Edoardo ApràPatrick Z El-Khoury

Abstract

Nonequilibrium chemical phenomena are known to play an important role in single molecule microscopy and spectroscopy. Herein, we explore these effects through ab initio molecular dynamics (AIMD)-based Raman spectral simulations. We target an isolated aromatic thiol (thiobenzonitrile, TBN) as a prototypical molecular system. We first show that the essential features contained in the ensemble-averaged Raman spectrum of TBN can be reproduced by averaging over 18 short AIMD trajectories spanning a total simulation time of ∼60 ps. This involved more than 90 000 polarizability calculations at the B3LYP/def2-TZVP level of theory. We then illustrate that the short trajectories (∼3.3 ps total simulation time), where the accessible phase space is not fully sampled, provide a starting point for understanding key features that are often observed in measurements targeting single molecules. Our results suggest that a complete understanding of single molecule Raman scattering needs to account for molecular conformational flexibility and nonequilibrium chemical phenomena in addition to local optical fields and modified selection rules. The former effects are well-captured using the described AIMD-based single molecule Raman spectral simulations.

References

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Oct 4, 2017·Nano Letters·Ashish BhattaraiPatrick Z El-Khoury

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Citations

Apr 15, 2020·Applied Spectroscopy·Edoardo ApràPatrick Z El-Khoury
Dec 4, 2020·Journal of Chemical Theory and Computation·Johann Mattiat, Sandra Luber
Jul 27, 2021·The Journal of Physical Chemistry. C, Nanomaterials and Interfaces·Patrick Z El-Khoury, Zachary D Schultz
Dec 6, 2018·The Journal of Physical Chemistry Letters·Ashish BhattaraiPatrick Z El-Khoury
Mar 12, 2020·The Journal of Physical Chemistry Letters·Chih-Feng WangPatrick Z El-Khoury
Jul 25, 2019·The Journal of Physical Chemistry. a·Edoardo ApràPatrick Z El-Khoury
Dec 3, 2021·Accounts of Chemical Research·Patrick Z El-Khoury

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