Some anomalies of the SER spectra of symmetrical molecules adsorbed on transition metal substrates: consideration by the dipole-quadrupole SERS theory

The SERS spectra of pyridine, pyrazine and benzene, adsorbed on Ni and some other transition metals are analyzed from the point of view of the dipole–quadrupole SERS theory. There are some anomalies in the regularities of these spectra with respect to those with the molecules adsorbed on Ag, Cu and...

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Bibliographic Details
Published in:Journal of Raman spectroscopy 2005-06, Vol.36 (6-7), p.522-532
Main Author: Polubotko, A. M.
Format: Article
Language:English
Subjects:
Anomalies
Benzene
dipole
Nickel
Pyrazines
Pyridines
quadrupole
Quadrupole interaction
Raman intensities
Spectra
surface-enhanced Raman scattering
Transition metals
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Summary:The SERS spectra of pyridine, pyrazine and benzene, adsorbed on Ni and some other transition metals are analyzed from the point of view of the dipole–quadrupole SERS theory. There are some anomalies in the regularities of these spectra with respect to those with the molecules adsorbed on Ag, Cu and Au. The breathing mode may not be the most enhanced. Although quadrupole interactions were not found precisely in the spectra of pyridine and pyrazine, they manifest in the SERS spectra of benzene adsorbed on silica‐supported Ni. From the analysis of the enhancement coefficient and some another points, we consider that these anomalies may be associated with the larger influence of the dipole interaction or a smaller role of the quadrupole interactions for the considered molecules and metals and also with some features of the complex dielectric constants in the above systems. Further, a strong influence of the minor quadrupole moments on the enhancement factor of strongly distorted benzene was found. This result is very important, because it indicates the complexity of the SERS dipole–quadrupole theory. Copyright © 2005 John Wiley & Sons, Ltd.
ISSN:0377-0486
1097-4555
DOI:10.1002/jrs.1344