Resonance Raman scattering in molecular dimers

A systematic study is initiated of resonance Raman scattering in molecular systems with overlapping electronic absorption bands. Resonance Raman spectra, excitation profiles, and depolarization ratios are calculated for a simple molecular dimer in which the two overlapping Franck–Condon progressions are related through the permutational symmetry of the dimer. The model used is highly idealized, but can be solved exactly for a complete range of intermolecular coupling strengths. In the weak and strong intermolecular coupling regions, the exact results are compared with the physically more transparent results obtained from a low‐order perturbation treatment. The spectra and profiles show properties characteristic of both totally symmetric and nontotally symmetric modes. The profiles and polarization dispersion curves are subject to both electronic and vibronic interference effects. Anomalous extrema of the depolarization ratio are often found to coincide with minima rather than maxima in the excitation prof...

[1]  W. Siebrand,et al.  Excitation profiles for totally symmetric modes in resonance Raman scattering , 1975 .

[2]  O. S. Mortensen.  Polarization dispersion in resonance Raman scattering , 1975 .

[3]  W. Siebrand,et al.  Theory of resonance Raman scattering. An improved formulation of the vibronic expansion method , 1975 .

[4]  F. Galluzzi,et al.  Resonance Raman scattering and vibronic coupling in aquo‐ and cyano‐cobalamin , 1974 .

[5]  D. V. Labeke,et al.  Étude Théorique de L'effet Raman de Résonance des Molécules Diatomiques et Polyatomiques , 1974 .

[6]  F. Inagaki,et al.  Excitation profile of the resonance Raman effect of β-carotene , 1974 .

[7]  W. Siebrand,et al.  Vibrational structure of resonance raman spectra , 1973 .

[8]  M. Zgierski.  Strong coupling in dimers , 1973 .

[9]  L. Bernard,et al.  Effet Raman de resonance par excitation dans le continuum d'absorption : sections efficaces relatives de diffusion , 1971 .

[10]  W. M. McClain.  Excited State Symmetry Assignment Through Polarized Two‐Photon Absorption Studies of Fluids , 1971 .

[11]  A. Witkowski,et al.  Decoupling conditions for the vibronic equation in dimers , 1970 .

[12]  R. Lefebvre,et al.  Intensity Patterns in Absorption and Fluorescence Spectra of Molecular Dimers: A Comparison between the Vibronic and the Born–Oppenheimer Approach , 1968 .

[13]  Herman A. Szymanski,et al.  Raman Spectroscopy: Theory and Practice , 1967 .

[14]  J. Ferguson,et al.  Absorption and Emission Spectra of Anthracene Dimers , 1966 .

[15]  M. Gouterman,et al.  Vibronic Coupling. II. Spectra of Dimers , 1964 .

[16]  W. Siebrand,et al.  Vibronic Coupling Criteria in Molecular Crystals , 1964 .

[17]  R. Merrifield.  Vibronic States of Dimers , 1963 .

[18]  M. Gouterman,et al.  Vibronic Coupling. I. Mathematical Treatment for Two Electronic States , 1961 .

[19]  P. Petelenz,et al.  Vibronic interpretation of silicon phthalocyanine dimer absorption spectrum , 1973 .

[20]  D. Rousseau,et al.  Raman spectra of molecules and crystals , 1972 .

[21]  O. S. Mortensen.  A relation between resonance Raman and absorption spectra , 1971 .