Time development of sers from pyridine, pyrimidine, pyrazine, and cyanide adsorbed on ag electrodes during an oxidation-reduction cycle

Abstract The time development of surface enhanced Raman scattering (SF.RS) from pyridinc, pyrimidine, pyrazine, and cyanide adsorbed on Ag electrodes has been recorded during an oxidation-reduction cycle by using an optical multichannel analyzer. The OMA system, capable of detecting spectra over a range of 400 cm−1 in 25 ms, was employed to monitor changes in Raman intensities, frequency shifts, and linewidths. Whereas measurements on pyridine confirm previously reported results and resolve some controversial questions, results on pyrazine provide new insight into the SERS mechanism. Because of the inversion symmetry of pyrazine, the Raman and infrared active modes are separated, but no significant distinction is observed in the SERS time development of Raman active compared to infrared active modes. In SERS from cyanide, large changes in the C - N stretching frequency have been observed.

[1]  B. Pettinger,et al.  Raman spectra of pyridine adsorbed on silver (100) and (111) electrode surfaces , 1978 .

[2]  I. Nenner,et al.  Temporary negative ions and electron affinities of benzene and N‐heterocyclic molecules: pyridine, pyridazine, pyrimidine, pyrazine, and s‐triazine , 1975 .

[3]  M. Albrecht,et al.  Metal surface Raman spectroscopy: Theory , 1979 .

[4]  M. Fleischmann,et al.  Raman spectra of pyridine adsorbed at a silver electrode , 1974 .

[5]  Michael R. Philpott,et al.  Effect of surface plasmons on transitions in molecules , 1975 .

[6]  A. Otto,et al.  Raman spectra of (CN) - adsorbed at a silver surface , 1978 .

[7]  Frederick W. King,et al.  Theory of Raman scattering by molecules adsorbed on electrode surfaces , 1978 .

[8]  L. H. Jones.  Nature of Bonding in Metal Cyanide Complexes as Related to Intensity and Frequency of Infrared Absorption Spectra , 1963 .

[9]  B. Conway,et al.  Orientation behavior of adsorbed pyridine and pyrazine at the mercury-water interface in relation to solution thermodynamic properties , 1974 .

[10]  F. Miller,et al.  Infra-red and Raman spectra ot the diazines , 1957 .

[11]  Andreas Otto,et al.  Surface roughness induced electronic raman scattering , 1980 .

[12]  G. Eesley,et al.  Enhanced Raman scattering on metal surfaces , 1979 .

[13]  H. Metiu,et al.  Classical theory of light scattering by an adsorbed molecule. I. Theory , 1979 .

[14]  M. Albrecht,et al.  The nature of an electrochemically roughened silver surface and its role in promoting anomalous Raman scattering intensity , 1978 .

[15]  B. Conway,et al.  Entropy and structural effects in the electrochemical adsorption of pyridine at mercury , 1969 .

[16]  S. Efrima,et al.  Resonant Raman scattering by adsorbed molecules , 1979 .

[17]  H. Metiu,et al.  Classical theory of light scattering by a molecule located near a solid surface , 1978 .

[18]  M. Albrecht,et al.  Anomalously intense Raman spectra of pyridine at a silver electrode , 1977 .

[19]  K. Innes,et al.  Electronic states of azabenzenes: A critical review , 1967 .

[20]  M. Fleischmann,et al.  Thiocyanate adsorption and corrosion at silver electrodes. A Raman spectroscopic study , 1977 .

[21]  R. Hester,et al.  The dependence of the intensity of Raman bands of pyridine at a silver electrode on the wavelength of excitation , 1978 .

[22]  T. Furtak.  Anomalously intense Raman scattering at the solid-electrolyte interface , 1978 .

[23]  W. K. Wilmarth,et al.  Infra-red spectroscopic detection of bridging cyanide groups , 1961 .

[24]  D. L. Jeanmaire,et al.  Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode , 1977 .

[25]  H. Metiu,et al.  Light scattering by a molecule near a solid surface. II. Model calculations , 1979 .

[26]  M. Fleischmann,et al.  Raman spectroscopy at electrode‐electrolyte interfaces , 1976 .

[27]  T. P. Lewis,et al.  Polarographic reduction of the azines , 1970 .

[28]  C. Moore,et al.  Chemical and biochemical applications of lasers , 1974 .

[29]  J. Tsang,et al.  Anomalous surface enhanced molecular Raman scattering from inelastic tunneling spectroscopy junctions , 1979 .

[30]  M. Klein,et al.  Raman scattering from carbon monoxide adsorbed on evaporated silver films , 1979 .

[31]  Lazar' Mateevich Sverdlov,et al.  Vibrational spectra of polyatomic molecules , 1974 .

[32]  R. Clark,et al.  The Far-Infrared Spectra of Metal-Halide Complexes of Pyridine and Related Ligands , 1965 .

[33]  R. M. Velasco,et al.  Conformation properties of one isolated polyelectrolyte chain in D dimensions , 1977 .

[34]  E. Yeager,et al.  The Raman spectrum of an adsorbed species on electrode surface , 1978 .

[35]  Elias Burstein,et al.  “Giant” Raman scattering by adsorbed molecules on metal surfaces , 1979 .

[36]  W. Griffith.  Cyanide complexes of the transition metals , 1962 .