Time Domain Simulations of Single Molecule Raman Scattering

Apra, Edoardo; Bhattarai, Ashish; Crampton, Kevin T.; Bylaska, Eric J.; Govind, Niranjan; Hess, Wayne P.; El-Khoury, Patrick Z.

doi:10.1021/acs.jpca.8b05912

Time Domain Simulations of Single Molecule Raman Scattering

Journal Article · 20 September 2018 · Journal of Physical Chemistry A

DOI:https://doi.org/10.1021/acs.jpca.8b05912· OSTI ID:1773365

^[1]; Bhattarai, Ashish ^[1]; Crampton, Kevin T. ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

BATTELLE (PACIFIC NW LAB)

Non-equilibrium 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 basis set 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 non-equilibrium chemical phenomena. These effects are well-captured using the described AIMD-based single molecule Raman spectral simulations.

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1773365

Report Number(s):: PNNL-SA-135554

Journal Information:: Journal of Physical Chemistry A, Vol. 122, Issue 37

Country of Publication:: United States

Language:: English

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