Semiclassical radiation theory provides parallel derivations of spontaneous emission and of spontaneous incoherent scattering of radiation. In the latter case, in constrast to the former, the theory is in clear disagreement with established experimental data since it predicts equal intensity for Stokes and anti-Stokes lines in Raman scattering. A new postulate of semiquantization is proposed to restore agreement with experiment without quantizing the electromagnetic field.
Semiclassical radiation theory provides parallel derivations of spontaneous emission and of spontaneous incoherent scattering of radiation. In the latter case, in constrast to the former, the theory is in clear disagreement with established experimental data since it predicts equal intensity for Stokes and anti-Stokes lines in Raman scattering. A new postulate of semiquantization is proposed to restore agreement with experiment without quantizing the electromagnetic field.
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.
In our preceding treatments of the interaction of radiation with matter, we assumed that the electric field is classical. In most cases, this assumption is validated by experiment. There are several instances, however, for which a classical field fails to give experimentally observed results, whereas a quantized field succeeds. This is true, for example, of spontaneous emission, a phenom enon which was described phenomenologically in our earlier work (see Chaps. 2 and 7). Another case involves the 2 and 2p \ states in the hydrogen atom, which are predicted to have the same energy not only by the simple theory of Chap. 1, but also by the more sophisticated Dirac theory. In both cases, a classical electric field was assumed. Experimentally, the two levels differ by approximately the Lamb shift, 1057 MHz. A fully quantized treatment of the field and atom system gives impressive agreement with the experimentally observed shift. Derivation of the fluctuations in intensity of a laser near threshold requires the quantum theory o f radiation. In addition there are other problems for which the concept of a “particle,” the photon, is either necessary or convenient. Despite a popular impression to the contrary, however the explanation of the photoelectric effect is not one of these (see Prob. 2-10).
It has recently been shown by Jaynes and collaborators that semiclassical radiation theory contains a description of spontaneous emission of radiation and of radiative level shifts. The present paper gives a gauge-invariant derivation of the radiant energy production rate, using only Maxwell's equations and the usual definitions of electric current and charge density for a many-particle material system described by Schr\"odinger's equation. A complementary derivation, using the time-dependent Schr\"odinger equation, verifies the instantaneous conservation of energy and probability during the radiation process. The semiclassical rate of spontaneous emission differs from the usual formula (Einstein's A coefficient) because it depends on the occupancy of both initial and final states of the material system. The implications of this with regard to thermal equilibrium and Planck's law are examined. If a new hypothesis is introduced, postulating the decomposition of the equilibrium radiation into incoherent components, each interacting with a specific pair of energy levels of the material system, then Planck's law is shown to hold for the total intensity of radiation. If this hypothesis is not introduced, the equilibrium conditions for different transitions are incompatible, and the semiclassical radiation theory is incapable of describing thermal equilibrium.
A semiclassical radiation theory is developed in which the spontaneous emission field of a two-level atom is a quantum entity represented by atomic operators acting in the Hilbert space of the atomic states. The theory is applied to an investigation of the coherence properties of spontaneous emission. It is found that incoherent and coherent components can be identified in the emission field, the former dominating in the early stages of the decay from the excited state and the latter dominating in the later stages or in the emission from a weakly excited atom. The single-atom coherence properties are shown to lead to well-known superradiance phenomena in the spontaneous emission from an assembly of similar atoms. The paper does not use the theory of quantum electrodynamics; it builds on knowledge at the undergraduate level of classical radiation theory and the quantum mechanics of atoms.
The semiclassical theory of spontaneous Raman scattering is reviewed. From the semiclassical theory we identify the parameters and dynamical variables involved in Raman scattering. A classical theory of stimulated Raman scattering is constructed. It is an extension of the theory of Shen and Bloembergen. We show that the system is a weakly coupled system. Because the driving term contains dynamical variables, the linewidth of the stimulated Stokes wave should be smaller than that of the spontaneous Stokes wave. Using Riemann's method, we obtain Kroll's solution rigorously, in a more general form. The steady-state limit is also derived rigorously. The conditions for the transient and steady-state gains are discussed. It is shown that for the transient case one may have an abrupt change of the Stokes gain versus incident laser power.
In Paper I [Chen et al., J. Chem. Phys. 150, 044102 (2019)], we introduced Ehrenfest+R dynamics for a two-level system and showed how spontaneous emission can be heuristically included such that, after averaging over an ensemble of Ehrenfest+R trajectories, one can recover both coherent and incoherent electromagnetic fields. In the present paper, we now show that Ehrenfest+R dynamics can also correctly describe Raman scattering, whose features are completely absent from standard Ehrenfest dynamics. Ehrenfest+R dynamics appear to be quantitatively accurate both for resonant and off-resonant Raman signals, as compared with Kramers-Heisenberg-Dirac theory.