TY - JOUR
T1 - Simulating Ensemble-Averaged Surface-Enhanced Raman Scattering
AU - Chulhai, Dhabih V.
AU - Chen, Xing
AU - Jensen, Lasse
N1 - Funding Information:
This work was supported by the NSF Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CHE-1414466). We acknowledge support received from Research Computing and Cyberinfrastructure, a unit of Information Technology Services at Penn State.
Publisher Copyright:
© 2016 American Chemical Society.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2016/9/22
Y1 - 2016/9/22
N2 - The ability to simulate surface-enhanced Raman scattering (SERS) is a vital tool in elucidating the chemistry of molecules near the vicinity of plasmonic metal nanoparticles. However, typical methods do not include the dynamics of the molecule(s) of interest and are often limited to a single or few molecules. In this work, we combine molecular dynamics simulations with the dressed-tensor formalism to simulate the SERS spectra of Ag nanoparticles coated with a full monolayer of pyridine molecules. This method allows us to simulate the ensemble-averaged SERS spectra of more realistic large scale systems, while accounting for the organization of molecules in the hotspots. Through these simulations, we find that the preferential binding location and orientation of the molecules, the choice of electrodynamics method, and the inclusion of field gradient effects influence both the enhancement distribution and the spectral signatures. We also show that both the translational and rotational motions of a pyridine molecule near a nanoparticle junction may be effectively tracked through its SERS spectrum.
AB - The ability to simulate surface-enhanced Raman scattering (SERS) is a vital tool in elucidating the chemistry of molecules near the vicinity of plasmonic metal nanoparticles. However, typical methods do not include the dynamics of the molecule(s) of interest and are often limited to a single or few molecules. In this work, we combine molecular dynamics simulations with the dressed-tensor formalism to simulate the SERS spectra of Ag nanoparticles coated with a full monolayer of pyridine molecules. This method allows us to simulate the ensemble-averaged SERS spectra of more realistic large scale systems, while accounting for the organization of molecules in the hotspots. Through these simulations, we find that the preferential binding location and orientation of the molecules, the choice of electrodynamics method, and the inclusion of field gradient effects influence both the enhancement distribution and the spectral signatures. We also show that both the translational and rotational motions of a pyridine molecule near a nanoparticle junction may be effectively tracked through its SERS spectrum.
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U2 - 10.1021/acs.jpcc.6b02159
DO - 10.1021/acs.jpcc.6b02159
M3 - Article
AN - SCOPUS:84988589029
VL - 120
SP - 20833
EP - 20842
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 37
ER -