J. A. Creighton

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAnomalously intense Raman spectra of pyridine at a silver electrodeM. Grant Albrecht and J. Alan CreightonCite this: J. Am. Chem. Soc. 1977, 99, 15, 5215–5217Publication Date (Print):June 1, 1977Publication History Published online1 May 2002Published inissue 1 June 1977https://pubs.acs.org/doi/10.1021/ja00457a071https://doi.org/10.1021/ja00457a071research-articleACS PublicationsRequest reuse permissionsArticle Views8485Altmetric-Citations2380LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Intense Raman scattering by pyridine molecules adsorbed on silver or gold aqueous sol particles of dimensions comparable to the wavelength is reported. The degree of intensity enhancement is strongly dependent on the excitation wavelength, with a sharp resonance Raman maximum for excitation at the wavelength of the Mie extinction maximum of the metal particles, and for the silver sols the Raman maximum is shown to follow the extinction maximum to longer wavelengths with increase in particle size. A new resonance Raman phenomenon is thus proposed which is the Raman component of resonant Mie scattering, and in which the polarizability of the metal particles is modulated by the vibrations of the adsorbed molecules. These observations confirm that surface plasma oscillations are involved in the intense Raman scattering already reported for molecules adsorbed at roughened silver surfaces. The metal dielectric function requirements for resonant Mie scattering enable the optimum excitation wavelength for plasma resonance-enhanced Raman studies at the surface of other metals to be estimated.

The ultraviolet–visible absorption spectra are given for 10 nm diameter colloidal particles of 52 of the metallic elements, calculated from the optical constants of the metals by means of Mie theory. For most of the elements the spectra cover the range 200–900 nm. Well resolved absorption bands are observed for colloidal Sc, Ti, V, Y, Cd, Eu, Yb, Hg and Th as well as for colloids of Cu, Ag, Au and the s-block metals. However, for the majority of the colloidal metallic elements in this size range there is only a continuous absorption in the visible range, rising to broad and poorly resolved absorption bands in the ultraviolet near 200 nm. The difference in the way that the spectra of colloidal particles of different metals change when the particle shape is varied from spherical to spheroidal is investigated systematically in the dipole approximation. This is achieved by means of contour plots of the absorbance cross-section for the particles vs. the real and imaginary parts of the dielectric function for the metals, and this method of investigation is extended also to hollow spherical particles. The results suggest that Ca, Sr, Ba, Eu, Yb, Th and possibly Sc, Ti, V and Y may merit experimental investigation as new metals for exhibiting surface-enhanced Raman scattering.