Size-dependence of the enhanced Raman scattering of pyridine adsorbed on Agn (n = 2-8, 20) clusters

Lasse Jensen, Lin Lin Zhao, George C Schatz

Research output: Contribution to journalArticle

163 Citations (Scopus)

Abstract

We present a time-dependent density functional theory (TDDFT) study of the size-dependence of the absorption and Raman scattering properties of pyridine-interacting with small silver nanoclusters Agn (n = 2-8, 20). By employing a recently developed short-time approximation for the Raman scattering cross section we simulate both the normal and the "surface"-enhanced Raman spectra. The absorption spectra of the small silver clusters are studied both in the gas phase and embedded in rare gas matrices. We find that both the absorption and Raman properties depend strongly on cluster size and adsorption site. The normal Raman spectra of Ag n-pyridine complexes resemble that of isolated pyridine, with enhancements which increase as cluster size increases. In contrast to this, both the enhancement and the appearance of the "surface"-enhanced Raman spectrum show a very strong dependence on cluster size. The total enhancements for the complexes are between 103 and 104 and quite surprisingly the strongest enhancement is found for the Ag2-Py complex. However, the enhancement trends can be correlated with the distance of the molecule to the center of the metal cluster and with the resonance polarizability in a way that is suggestive of electromagnetic enhancements, so the enhancement mechanism for these small clusters is similar to what is found for larger particles.

Original languageEnglish
Pages (from-to)4756-4764
Number of pages9
JournalJournal of Physical Chemistry C
Volume111
Issue number12
DOIs
Publication statusPublished - Mar 29 2007

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Pyridine
Raman scattering
pyridines
Raman spectra
augmentation
Silver
Noble Gases
Nanoclusters
silver
Inert gases
Density functional theory
Absorption spectra
Gases
metal clusters
Metals
pyridine
nanoclusters
scattering cross sections
Adsorption
rare gases

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Size-dependence of the enhanced Raman scattering of pyridine adsorbed on Agn (n = 2-8, 20) clusters. / Jensen, Lasse; Zhao, Lin Lin; Schatz, George C.

In: Journal of Physical Chemistry C, Vol. 111, No. 12, 29.03.2007, p. 4756-4764.

Research output: Contribution to journalArticle

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