On the linear response and scattering of an interacting molecule-metal system

David J. Masiello, George C Schatz

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

A many-body Green's function approach to the microscopic theory of plasmon-enhanced spectroscopy is presented within the context of localized surface-plasmon resonance spectroscopy and applied to investigate the coupling between quantum-molecular and classical-plasmonic resonances in monolayer-coated silver nanoparticles. Electronic propagators or Green's functions, accounting for the repeated polarization interaction between a single molecule and its image in a nearby nanoscale metal, are explicitly computed and used to construct the linear-response properties of the combined molecule-metal system to an external electromagnetic perturbation. Shifting and finite lifetime of states appear rigorously and automatically within our approach and reveal an intricate coupling between molecule and metal not fully described by previous theories. Self-consistent incorporation of this quantum-molecular response into the continuum-electromagnetic scattering of the molecule-metal target is exploited to compute the localized surface-plasmon resonance wavelength shift with respect to the bare metal from first principles.

Original languageEnglish
Article number064102
JournalJournal of Chemical Physics
Volume132
Issue number6
DOIs
Publication statusPublished - 2010

Fingerprint

Metals
Scattering
Molecules
scattering
metals
Surface plasmon resonance
molecules
surface plasmon resonance
Green's function
Green's functions
Spectroscopy
electromagnetic scattering
Silver
spectroscopy
Monolayers
silver
Polarization
electromagnetism
Nanoparticles
continuums

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

On the linear response and scattering of an interacting molecule-metal system. / Masiello, David J.; Schatz, George C.

In: Journal of Chemical Physics, Vol. 132, No. 6, 064102, 2010.

Research output: Contribution to journalArticle

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