Combined quantum mechanics (TDDFT) and classical electrodynamics (Mie Theory) methods for calculating surface enhanced raman and hyper-raman spectra

Jonathan Mullin, Nicholas Valley, Martin G. Blaber, George C Schatz

Research output: Contribution to journalArticle

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Abstract

Multiscale models that combine quantum mechanics and classical electrodynamics are presented, which allow for the evaluation of surface-enhanced Raman (SERS) and hyper-Raman scattering spectra (SEHRS) for both chemical (CHEM) and electrodynamic (EM) enhancement mechanisms. In these models, time-dependent density functional theory (TDDFT) for a system consisting of the adsorbed molecule and a metal cluster fragment of the metal particle is coupled to Mie theory for the metal particle, with the surface of the cluster being overlaid with the surface of the metal particle. In model A, the electromagnetic enhancement from plasmon-excitation of the metal particle is combined with the chemical enhancement associated with a static treatment of the molecule-metal structure to determine overall spectra. In model B, the frequency dependence of the Raman spectrum of the isolated molecule is combined with the enhancements determined in model A to refine the enhancement estimate. An equivalent theory at the level of model A is developed for hyper-Raman spectra calculations. Application to pyridine interacting with a 20 nm diameter silver sphere is presented, including comparisons with an earlier model (denoted G), which combines plasmon enhanced fields with gas-phase Raman (or hyper-Raman) spectra. The EM enhancement factor for spherical particles at 357 nm is found to be 104 and 106 for SERS and SEHRS, respectively. Including both chemical and electromagnetic mechanisms at the level of model A leads to enhancements on the order of 104 and 109 for SERS and SEHRS.

Original languageEnglish
Pages (from-to)9574-9581
Number of pages8
JournalJournal of Physical Chemistry A
Volume116
Issue number38
DOIs
Publication statusPublished - Sep 27 2012

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Quantum theory
Electrodynamics
Mie scattering
electrodynamics
Density functional theory
Raman scattering
quantum mechanics
Raman spectra
density functional theory
metal particles
augmentation
Metals
Molecules
electromagnetism
multiscale models
molecules
metal clusters
Silver
pyridines
silver

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Combined quantum mechanics (TDDFT) and classical electrodynamics (Mie Theory) methods for calculating surface enhanced raman and hyper-raman spectra. / Mullin, Jonathan; Valley, Nicholas; Blaber, Martin G.; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 116, No. 38, 27.09.2012, p. 9574-9581.

Research output: Contribution to journalArticle

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