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NATO ASI series. Series B : Physics

Nonperturbative Treatment of Molecule-Radiation Interactions — A Coupled Equations Approach

André D. Bandrauk

Published Jan 1, 1990• 0 citations
Publisher
DOI
10.1007/978-1-4757-9334-5_18

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The response of a collision-broadened gas sample to driving coherent radiation is studied theoretically, taking into account effects of coherent excitations of two or more atoms (or molecules). In analogy to the Bloch-type master equation for one-atom coherences, describing the motion of a single atom "dressed" by the relevant (incident and detected) field modes, a master equation is derived for two-atom coherences, including an effective interaction of the Bethe-Salpeter---type, accounting for the mutual interaction of the coherently driven pair. The master equation includes also all symmetrization effects owing to resonance exchange between identical atoms, and is limited to nonreactive gas atoms (or molecules) undergoing binary collisions, including otherwise all (internal and translational) relaxation effects. The self-energy kernels are expressed in a nonperturbative fashion, in terms of binary-collision scattering amplitudes, and include renormalization effects due to coincidence of radiative couplings with the collisions (optical and radiative collisions). The concept of two-atom coherences is generalized to higher coherence ranks by constructing a hierarchy of master equations, including vertex operators that upgrade or downgrade the coherence rank, as a prelude to a diagrammatic method for calculating continuous-wave spectra. This hierarchy is compared with prevalent Agarwal-type master equations, based on the Dicke pseudospin method, and used in the study of two-level atoms.
An elementary account is given of the absorption and emission of radiation by molecules employing a particular formulation of Schrödinger theory which facilitates the treatment of radiative line widths and level shifts. The familiar Fermi golden rule for transition rates, the Rabi Bloch-Siegert absorption profile, and the Weisskopf-Wigner approximation for spontaneous decay are obtained under appropriate conditions in the context of a common perspective. Comparisons are made with other recently devised perturbative and nonperturbative formulations of electromagnetic transition phenomena which correctly include radiative line widths and level shifts, and the importance of proper treatment of the normalization and phase of the Schrödinger wave function in this connection is emphasized.