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The Journal of Chemical Physics

Theory of the Stimulated Raman and Related Effects

A. David Buckingham

Published Jul 1, 1965• 24 citations
Publisher

Abstract

A simple description of the stimulated Raman emission of Stokes radiation, and of the induced absorption found by Stoicheff at the anti-Stokes frequency, is based on the semiclassical theory of radiation. This theory gives the well-known formulas for absorption and stimulated emission when carried to the first order in the time-dependent perturbation due to the interaction of the light beam with the molecules. If there are two light beams of frequencies ωL and ω, the second-order perturbation may be associated with stimulated emission at the Stokes frequency ω=ω−1=ωL—ωR and with induced absorption at the anti-Stokes frequency ω=ω1=ωL+ωR, where ωL is the laser frequency and ωR a Raman-active vibrational frequency; in both cases, there is a molecular transition to the excited vibrational state. The highly directional and very sharp anti-Stokes emission at ω1 arises from the conversion by molecules in intense beams at ωL and ω−1 of two ωL photons into an ω−1, ω1 pair. Like spontaneous emission from excited states, the production of this anti-Stokes radiation requires the full quantum theory of radiation for an adequate description. The emission of ω1 and the observed directional absorption of ω−1 due to the reverse conversion ω−1+ω1→2ωL are explained. The anti-Stokes emission is proportional to the Stokes intensity and to the square of that of the laser, and to the square of the molecular number density; its sharpness is due to the absence of a molecular transition. The generation of photon pairs ω−n+ωn, where ωn=ωL+nωR, can occur for all values of n, but it is most efficient for n=1, due to resonance in the appropriate molecular hyperpolarizability and to the intensity of the Stokes beam at ω−1.

DOI
10.1063/1.1696467

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A. K. McQuillan, Wallace R. L. Clements, Boris Peter Stoicheff

An experimental study of normal and stimulated Raman emission in diamond is presented, including measurements of linewidth, intensity, and angular distribution of radiation having a frequency shift of 1332.0 ${\mathrm{cm}}^{\ensuremath{-}1}$. The diamond crystal formed a Raman resonator; excitation was by a giant-pulse ruby laser. The dependence of normal Stokes emission on laser intensity and the threshold for oscillation were investigated. A value for the Raman gain ($g=6.9\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}3}$ ${\mathrm{cm}}^{\ensuremath{-}1}$ per MW/${\mathrm{cm}}^{2}$) was calculated from the measured linewidth ($\ensuremath{\Delta}\ensuremath{\nu}=2.04$ ${\mathrm{cm}}^{\ensuremath{-}1}$) and cross section for scattering, and found to be in good agreement with a value determined from the threshold for oscillation. The angular distributions of anti-Stokes and Stokes emission and absorption for parallel and convergent laser light are also in good agreement with theory: The emission cone angles are strongly dependent on the angle of convergence of the incident light, and it is established that the preferred directions for emission are those making use of the most intense first-order Stokes radiation which is peaked in the forward direction within the Raman resonator.

Physical Review A•Mar 1, 1970•88 citations
A simple description of the stimulated Raman emission of Stokes radiation, and of the induced absorption found by Stoicheff at the anti-Stokes frequency, is based on the semiclassical theory of radiation. This theory gives the well-known formulas for absorption and stimulated emission when carried to the first order in the time-dependent perturbation due to the interaction of the light beam with the molecules. If there are two light beams of frequencies ωL and ω, the second-order perturbation may be associated with stimulated emission at the Stokes frequency ω=ω−1=ωL—ωR and with induced absorption at the anti-Stokes frequency ω=ω1=ωL+ωR, where ωL is the laser frequency and ωR a Raman-active vibrational frequency; in both cases, there is a molecular transition to the excited vibrational state. The highly directional and very sharp anti-Stokes emission at ω1 arises from the conversion by molecules in intense beams at ωL and ω−1 of two ωL photons into an ω−1, ω1 pair. Like spontaneous emission from excited states, the production of this anti-Stokes radiation requires the full quantum theory of radiation for an adequate description. The emission of ω1 and the observed directional absorption of ω−1 due to the reverse conversion ω−1+ω1→2ωL are explained. The anti-Stokes emission is proportional to the Stokes intensity and to the square of that of the laser, and to the square of the molecular number density; its sharpness is due to the absence of a molecular transition. The generation of photon pairs ω−n+ωn, where ωn=ωL+nωR, can occur for all values of n, but it is most efficient for n=1, due to resonance in the appropriate molecular hyperpolarizability and to the intensity of the Stokes beam at ω−1.
A three-dimensional analysis of stimulated Raman emission is presented for a medium through which a cylindrical laser beam passes. The buildup of the Stokes radiation from the spontaneous fluctuations in the Raman medium is considered. A generalization of the fluctuation-dissipation theorem is derived relating the current-current fluctuations at the Stokes frequency to the laser-induced (negative) conductance at this frequency. The anti-Stokes radiation is treated as arising from the interaction of the laser field and the molecular vibrations accompanying the Stokes radiation. The anti-Stokes radiation emerges in a narrow cone around the familiar phase-matching direction given by ${\mathbf{\ensuremath{\beta}}}_{\ensuremath{-}}=2{\mathbf{k}}_{L}\ensuremath{-}{\mathbf{\ensuremath{\beta}}}_{+}$, where ${\mathbf{\ensuremath{\beta}}}_{\ensuremath{-}}$ and ${\mathbf{\ensuremath{\beta}}}_{+}$ are the (real parts of the) propagation constants of Stokes and anti-Stokes waves in the medium, and kL{\mathbf{k}}_{L}kL​ is the laser propagation vector. The angular width of the anti-Stokes radiation cone is evaluated.
The traditional Raman process alluded to in Chap. 13 is a three-state sequence of transitions in which radiative excitation (induced by a pump field) is followed by spontaneous emission that produces a final state differing from the initial state [Her50b] [Sho90, § 17.5]. When the final state of the sequence is more energetic than the initial state the resulting emission line (to the red of the pump wavelength) is known as a Stokes spectral line. The difference between the pump frequency and the Stokes frequency, the Raman frequency , defines the excitation energy of the final state relative to the initial state. When, instead, the final state has lower energy than the initial state, as can occur when the initial quantum state is already excited, then the emission is an anti-Stokes line, at a bluer wavelength than the pump field. The overall Raman scattering is a two-photon process. Typically Raman spectroscopy deals with molecules; the two-photon transitions are then between vibrational-rotational states, through electronically excited intermediate states, that are characterized in part by vibrational quantum number v and rotational angular momentum quantum numbers J, M . From any given excited electronic state there are many fluorescing transitions, corresponding to various vibrational and rotational quantum numbers of the final state. The wavelengths of the various Stokes and anti-Stokes lines (i.e. the Raman frequencies) characterize the particular molecular species, and so they have provided a valuable diagnostic tool for spectroscopists.
The stimulated Raman scattering (SRS), arising from the interaction between molecules of a medium and two strong light fields - a resonant field and a pumping field - is studied theoretically. The transitions of molecules between a given pair of levels is assumed to be both Raman active and infrared active. A semiclassical approach, in which the density matrix method is used for the quantum mechanical description for the medium, is employed. We expand the density matrix in various orders within which the zeroth-order is referred to as the solution of the equation of motion of the density matrix when only the resonant field is applied. -- We obtain a set of equations in second order of the density matrix element p₁₀⑵ (ω) from which the gain function can be derived. This set of equations in the special case of steady state is accidentally similar to those obtained by Mollow in his study of the power spectrum of a strong driven two-level system. We have shown that the SRS in the steady state under the resonant field interaction, is drastically reduced in general. When the flopping frequency is larger than the relaxation constants (Ω > r), we find there appears both weak positive and weak negative gains on both sides of the ordinary SRS components. Since we retain our second-order equations in a general form rather than the form for steady state, we are able to take account of the dependence on the transient zeroth solution. By employing the Laplace transform technique with the help of convolution products, we are able to solve for ρ₁₀⑵(ω) in the stationary flopping state. When the intensity of the resonant field is high, we have found theoretically that both the Stokes and anti-Stokes component become doublets and equally displaced by the amount of the flopping frequency, Ω, on the opposite sides of ordinary Stokes and anti-Stokes components, respectively. The gain maxima are approximately the order of Ω/4r times the ordinary gain of the Stokes component, where Ω/r >> 1 if the flopping exists. The gains are therefore large in comparison with the ordinary gain for SRS in the steady state.
The regular structure in frequency broadening spectrum of the self-trapped laser and Raman radiations is produced by the phase-modulation of light waves propagating in the filament with intensity-dependent index of refraction. A quantum-mechanical calculation of double quantum transition in a three-level system is shown to explain the process of self-modulation and the production of picosecond pulses in the Raman process. Coherent coupling of the laser and the Stokes waves produces mutual modulation of large amplitude, if the optical field is strong and the vibrational relaxation time is long. Numerical evaluation for CS2 gives a modulation frequency of about 1011 Hz, when an optical power of 10 kW is trapped in a filament of 2 µm radius. Besides, the effect of self-modulation on the spatial distribution of anti-Stokes emission along the filament is discussed and shown to agree with the experimental results observed by Stoicheff and his co-workers.
Coupled differential equations are formulated to model the generation of coherent anti-Stokes Raman radiation in molecular gases. They include the basic coherent interaction of incident pump and idler (Stokes) waves to generate the anti-Stokes radiation plus other radiation and absorption processes which influence saturation due to population depletion of the lowest energy level. Other factors considered are simultaneous excitation of more than one vibration frequency, a quasi-monochromatic idler beam slightly off the true Stokes frequency, and the temporal laser pulse shape. Some effects of these various physical factors on saturation are presented graphically.
An experimental study of normal and stimulated Raman emission in diamond is presented, including measurements of linewidth, intensity, and angular distribution of radiation having a frequency shift of 1332.0 ${\mathrm{cm}}^{\ensuremath{-}1}$. The diamond crystal formed a Raman resonator; excitation was by a giant-pulse ruby laser. The dependence of normal Stokes emission on laser intensity and the threshold for oscillation were investigated. A value for the Raman gain ($g=6.9\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}3}$ ${\mathrm{cm}}^{\ensuremath{-}1}$ per MW/cm2{\mathrm{cm}}^{2}cm2) was calculated from the measured linewidth ($\ensuremath{\Delta}\ensuremath{\nu}=2.04$ ${\mathrm{cm}}^{\ensuremath{-}1}$) and cross section for scattering, and found to be in good agreement with a value determined from the threshold for oscillation. The angular distributions of anti-Stokes and Stokes emission and absorption for parallel and convergent laser light are also in good agreement with theory: The emission cone angles are strongly dependent on the angle of convergence of the incident light, and it is established that the preferred directions for emission are those making use of the most intense first-order Stokes radiation which is peaked in the forward direction within the Raman resonator.