Multiple-overtone resonance Raman scattering and fluorescence from I2 species adsorbed on silver surfaces

Abstract

A detailed excitation profile of a Raman progression consisting of up to six overtones and a fundamental band at 123 cm−1 observed from iodide adsorbed on an electrochemically roughened silver surface at 20 K is analyzed. The excitation profile was constructed from 77 spectra obtained by tuning the laser wavelength in ∼0.25 nm steps through the spectral range 409 nm–433 nm. The shift between resonances in the excitation profile, corresponding to the spacing between vibronic levels in the excited state, is also equal to 123 cm−1 indicating that the ground state and excited state potential energy surfaces have the same shape. Only two distinct resonances spaced three vibrational quanta apart were evident in the profile for each band in the progression. Curve fitting of the Raman band shapes indicates that each overtone is composed of one sharp and one broad band, whereas the fundamental contains only one sharp component. The measured width of the fundamental was less than 2.5 cm−1 FWHM, limited by the instrument function. It is proposed that the sharp Raman bands represent a normal vibrational mode of a surface-adsorbed I2-like species with the width determined by the intrinsic vibrational dephasing in the ground state. On the other hand, the broad Raman bands reflect vibronic coupling between different I2-like species adsorbed on the same Ag cluster. The broad bandwidths result from both dephasing associated with the vibronic coupling and the intrinsic vibrational dephasing. Other weak emission bands are attributed to resonance fluorescence corresponding to direct transitions from higher vibronic levels of the excited state to the ground state. An emission at 429.9 nm is assigned to exciton recombination in small silver iodide clusters which are formed after spontaneous oxidation of the iodide-modified silver surface.