Surface-enhanced Raman spectroscopy of benzene and benzene-d6 adsorbed on silver

  • Moskovits M
  • DiLella D
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The surface-enhanced Raman spectrum of benzene and benzene-d6 adsorbed on a Ag film, vapor-deposited onto a low-temp. substrate, is reported. Many lines which correlate with Raman-inactive and even IR and Raman-silent modes of the free mol. were obsd. with high intensity in the spectrum. The local symmetry which would cause those particular, otherwise inactive, vibrations to appear is C3v(sd), which corresponds to a benzene mol. lying flat atop an equilateral triangle of Ag atoms so that the normals to 3 alternate edges of benzene point to the centers of the 3 atoms. An alternative explanation for the activity of these normally silent modes is presented which does not depend on the adsorption site symmetry, but which postulates instead that an unusually steep elec. field gradient exists near the surface of the metal which causes modes spanned by the same representations which span the elements of a 3rd rank tensor A to become active. These, together with the vibrations which are normally Raman-active in benzene, are the same vibrations which are Raman-active in C3v(sd). An argument in support of the latter explanation is presented based upon the different response to excitation wavelength of the intensities of those modes which are active as a result of the polarizability tensor, a, as contrasted with those which become active because of A. An unequivocal choice between the 2 models cannot be made, however, on the basis of the data available. [on SciFinder (R)]

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  • M. Moskovits

  • D. P. DiLella

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