Many-body theory of surface-enhanced Raman scattering
| dc.creator | Masiello, David J. | |
| dc.creator | Schatz, George C. | |
| dc.date | 2008-09-18 | |
| dc.date.accessioned | 2026-07-07T10:10:33Z | |
| dc.date.available | 2026-07-07T10:10:33Z | |
| dc.description | 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. | |
| dc.description | under review at Physical Review A since June 11, 2008 | |
| dc.identifier | https://arxiv.org/abs/0809.3207 | |
| dc.identifier | http://arxiv.org/abs/0809.3207 | |
| dc.identifier | Physical Review A, 78 042505 (2008) | |
| dc.identifier | doi:10.1103/PhysRevA.78.042505 | |
| dc.identifier.uri | http://salesiana.dossiersoluciones.com/handle/123456789/171629 | |
| dc.subject | Quantum Physics | |
| dc.title | Many-body theory of surface-enhanced Raman scattering | |
| dc.type | text |