Many-body theory of surface-enhanced Raman scattering

David J. Masiello, George C Schatz

Research output: Contribution to journalArticle

69 Citations (Scopus)

Abstract

A many-body Green's function approach to the microscopic theory of surface-enhanced Raman scattering is presented. Interaction effects between a general molecular system and a spatially anisotropic metal particle supporting plasmon excitations in the presence of an external radiation field are systematically included through many-body perturbation theory. Reduction of the exact effects of molecular-electronic correlation to the level of Hartree-Fock mean-field theory is made for practical initial implementation, while description of collective oscillations of conduction electrons in the metal is reduced to that of a classical plasma density; extension of the former to a Kohn-Sham density-functional or second-order Møller-Plesset perturbation theory is discussed; further specialization of the latter to the random-phase approximation allows for several salient features of the formalism to be highlighted without need for numerical computation. Scattering and linear-response properties of the coupled system subjected to an external perturbing electric field in the electric-dipole interaction approximation are investigated. Both damping and finite-lifetime effects of molecular-electronic excitations as well as the characteristic fourth-power enhancement of the molecular Raman scattering intensity are elucidated from first principles. It is demonstrated that the presented theory reduces to previous models of surface-enhanced Raman scattering and leads naturally to a semiclassical picture of the response of a quantum-mechanical molecular system interacting with a spatially anisotropic classical metal particle with electronic polarization approximated by a discretized collection of electric dipoles.

Original languageEnglish
Article number042505
JournalPhysical Review A
Volume78
Issue number4
DOIs
Publication statusPublished - Oct 16 2008

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molecular electronics
metal particles
Raman spectra
electric dipoles
perturbation theory
approximation
conduction electrons
radiation distribution
plasma density
excitation
Green's functions
damping
interactions
formalism
life (durability)
oscillations
electric fields
augmentation
polarization
scattering

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Many-body theory of surface-enhanced Raman scattering. / Masiello, David J.; Schatz, George C.

In: Physical Review A, Vol. 78, No. 4, 042505, 16.10.2008.

Research output: Contribution to journalArticle

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