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Raman scattering in resonance with short‐ and long‐lived vibronic states
Author(s) -
Tubino R.,
Mulazzis E.,
Birman J. L.
Publication year - 1984
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250150302
Subject(s) - raman scattering , raman spectroscopy , vibronic spectroscopy , chemistry , resonance (particle physics) , fourier transform , hamiltonian (control theory) , vibronic coupling , coherent anti stokes raman spectroscopy , atomic physics , x ray raman scattering , molecular physics , molecule , physics , optics , quantum mechanics , mathematical optimization , mathematics , organic chemistry
Depending on the nature of the electronic absorption spectrum, that is, whether there are resolved vibronic transitions or broad and structureless bands, the scattering time associated with the Raman process can be long (10 −8 –10 −12 s) or short (<10 −12 s). In the first case the resonance Raman spectrum is characterized by a strong and non‐systematic dependence of first and higher order processes on the exciting wavelenghth; In the latter case the resonance Raman spectrum exhibits a strong, but systematic, frequency dependence of the intensities, which also show a regular decrease with the order of the process. These effects have been interpreted in terms of the Fourier transform of the correlator function which describes the time dependence of the secondary emission, evaluated for intermediate and long times and for the short time limit, respectively, Calculations for the gaseous I 2 molecule using a simplified model Hamiltonian are reported and compared with the experimental data.