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Soviet Physics Uspekhi

Raman scattering of light near and far from resonance

P. P. Shorygin

Published Jan 31, 1973• 53 citations

Abstract

The review deals with various variants of classification of the types of secondary emission of light by molecules; cases are distinguished in which the secondary emission occurs without additional processes that find their way between photon emission and absorption; the advisability of differentiating between the cases of resonance fluorescence and resonance scattering is noted. Reference is made to papers that have made contributions to the development of quantum-mechanical and classical theory of Raman scattering and to the development of the concepts of the relations between electron-vibrational absorption spectra, fluorescence spectra, and scattering excitation near and near and far resonance. Conditions are considered of excitation of the spectrum at different relations between the electronic-oscillator damping constant, the atom vibration frequency, the rotational frequencies, and the difference between the frequency of the incident light and the frequency of the electronic transition. The conditions for the excitation of typical light scattering, typical resonance fluorescence, and certain intermediate types, in which individual features of scattering are combined with certain features of fluorescence (phenomena of the transition type) are noted. The results of investigations of different models of the scattering centers, their advantages, shortcomings, and limits of applicability are compared. The most interesting results of the experimental investigations of resonant scattering of light by molecules and crystals are noted.

DOI: 10.1070/pu1973v016n01abeh005152

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The review deals with various variants of classification of the types of secondary emission of light by molecules; cases are distinguished in which the secondary emission occurs without additional processes that find their way between photon emission and absorption; the advisability of differentiating between the cases of resonance fluorescence and resonance scattering is noted. Reference is made to papers that have made contributions to the development of quantum-mechanical and classical theory of Raman scattering and to the development of the concepts of the relations between electron-vibrational absorption spectra, fluorescence spectra, and scattering excitation near and near and far resonance. Conditions are considered of excitation of the spectrum at different relations between the electronic-oscillator damping constant, the atom vibration frequency, the rotational frequencies, and the difference between the frequency of the incident light and the frequency of the electronic transition. The conditions for the excitation of typical light scattering, typical resonance fluorescence, and certain intermediate types, in which individual features of scattering are combined with certain features of fluorescence (phenomena of the transition type) are noted. The results of investigations of different models of the scattering centers, their advantages, shortcomings, and limits of applicability are compared. The most interesting results of the experimental investigations of resonant scattering of light by molecules and crystals are noted.

An analysis is made of some features of spontaneous resonance Raman scattering representing a noise signal which is amplified by a strong field in a nonlinear medium. A detailed review is made of the experimental results obtained in investigations of the spectra of stimulated preresonance and resonance Raman scattering in nonlasing and lasing systems. It is shown that, depending on the experimental conditions, these spectra may be due to transitions between vibrational levels of molecules which are in the ground or first excited electronic states. The example of several compounds is used to demonstrate the information which can be derived from such spectra. Possible practical applications of studies of such spectra are indicated. The physical basis of the theory of stimulated resonance Raman scattering is discussed and conclusions are drawn on the nature and mechanism of this Raman effect.

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Time dependent description of resonance Raman scattering is performed for a general system, by a density matrix reformulation of damping theory originally used for resonance fluorescence of atom. Radiative damping in the intermediate states can be described in terms of "damping operator" in realistic situations. In large ergodic systems, the scattering reduces to luminescence if the relaxation time within the excited states is much shorter than the radiative lifetime. In a typical case, time resolved emission spectra consist of various stages (i) scattering complex where absorption and emission are inseparable, (ii) dynamical and then (iii) kinetic relaxations giving rise to the hot luminescence, which finally converges to (iv) the ordinary luminescence from relaxed excited states. Hot luminescence does not appear within a motionally narrowed line. The interpretation of spectra depends also on the method of observation.

The theory of resonance Raman effect, resonantly enhanced two-photon absorption, and resonance fluorescence---valid also for strong fields---is treated in a unified and simplified way. Dressed states, Bloch equations, and perturbation theory are used to calculate line positions, and integrated intensities both for steady state and transient excitation. The case of adiabatic following is solved explicitly; it occurs when an off-resonance incident pulse is turned on and off slowly. It leads to the identification of Raman scattering, two-photon absorption, and Rayleigh scattering with an adiabatic process while fluorescence and consecutive two-photon absorption with nonadiabaticity. Time-dependent spectra are defined in a rigorous way. Our formulas agree in the various limits with those that appear in the literature.