Abstract : Work is summarized in areas of: Laser Assisted Collisions; Velocity Changing collisions in Atomic Vapors; Coherent Transients; Collision Induced Extra Resonances; Breakdown of the Optical Bloch Equations; Saturation Spectroscopy; Dynamics of Two-and Three-level Atoms Interacting with Radiation Fields; Pulse Propagation. Keywords: Laser spectroscopy, Optical collisions, Radiative collisions, Two-level atom, Atomic coherence, Degenerate four-wave mixing, Saturation spectroscopy, Laser propagation,, Dressed atom, Photon echo, Bloch equations, Collision kernal, Collisions, Optical noise.
A theory is given of radiative collisions, i.e., of elementary events in which the emission of a photon occurs in the course of a collision. Special attention is paid to radiative collisions stimulated by a laser field. Simple but clear approaches formulated in the forties or fifties are described briefly. This theory applies, in particular, to collisions in a strong electromagnetic field which affect the collision dynamics. Chemical radiative collisions, i.e., chemical reactions stimulated by photons absorbed in the course of a collision, are reviewed. An analysis is made of several recent experiments in which the theoretically predicted effects were observed: these include the radiative-collisional transfer of excitation from atom to atom, nonlinear effects due to the influence of the field on the collision dynamics, and photosubstitution of one of the atoms in a halogen molecule with an inert gas atom.
Collisional processes occurring within an atomic vapor can be conveniently described in terms of collision kernels. The population kernel ${W}_{\mathrm{ii}}({\stackrel{\ensuremath{\rightarrow}}{\mathrm{v}}}^{\ensuremath{'}}\ensuremath{\rightarrow}\stackrel{\ensuremath{\rightarrow}}{\mathrm{v}})$ gives the probability density per unit time that an "active" atom in state
i undergoes a collision with a perturber that changes the active atom's velocity from ${\stackrel{\ensuremath{\rightarrow}}{\mathrm{v}}}^{\ensuremath{'}}$ to $\stackrel{\ensuremath{\rightarrow}}{\mathrm{v}}$. For active atoms in a linear superposition of states
i and
j, there is an analogous coherence kernel ${W}_{\mathrm{ij}}({\stackrel{\ensuremath{\rightarrow}}{\mathrm{v}}}^{\ensuremath{'}}\ensuremath{\rightarrow}\stackrel{\ensuremath{\rightarrow}}{\mathrm{v}}) (i\ensuremath{\ne}j)$ reflecting the effects of collisions on the off-diagonal density-matrix element ${\ensuremath{\rho}}_{\mathrm{ij}}$. In this work, we discuss the general properties of the collision kernels which characterize a two-level active atom which, owing to the action of a radiation field, is in a linear superposition of its two levels. Using arguments based on the uncertainty principle, we show that collisions can be divided roughly into the following two categories: (1) collisions having impact parameters less than some characteristic radius which may be described classically and (2) collisions having impact parameters larger than this characteristic radius which give rise to diffractive scattering and must be treated using a quantum-mechanical theory. For the population kernels, collisions of type (1) can lead to a large-angle scattering component, while those of type (2) lead to a small-angle (diffractive) scattering component. For the coherence kernel, however, assuming that the collisional interaction for states
i and
j differ appreciably, only collisions of type (2) contribute, and the coherence kernel contains a small-angle scattering component only. The absence of a large-angle scattering component in the coherence kernel is linked to a collision-induced spatial separation of the trajectories associated with states
i and
j. Interestingly enough, the width of the diffractive kernel, as measured in the laboratory frame, is found to be insensitive to the perturber to active-atom mass ratio. To illustrate these features, a specific calculation of the kernels is carried out using a hard-sphere model for the scattering. The relationship of the present description of collisions to that of traditional pressure-broadening theory in which trajectory separation effects are ignored is discussed. It is explained why traditional pressure-broadening theory correctly describes collision effects in linear spectroscopy, but fails to provide an adequate description of some saturation spectroscopy and photonecho experiments in which velocity-changing collisions associated with the coherence kernel play a significant role. An expression for the collisionally modified photon-echo amplitude is derived which clearly displays the role played by velocity-changing collisions associated with the coherence kernel.
We extend the theory of light scattering from an atom undergoing collisions to the case of strong laser fields, where the expansion in powers of $\ensuremath{\Omega}{\ensuremath{\tau}}_{c}$ that was used formerly in a series of papers by Burnett et al. breaks down. In particular we consider in detail the conditions necessary to relate the observable quantities to intense-field collisional rate constants in a dressed-state basis (such as those calculated by Light and Sz\"oke). We also show (following Rabin and Ben-Reuven) that by studying the spectrum emitted by the atoms in the presence of a strong field one may measure the collisional rates for transfer between the dressed states of atom plus radiation field.