On the theory of the relaxation matrix and its application to microwave transient phenomena

The phenomenological relaxation times T1 and T2 measured in microwave transient experiments are expressed in terms of specific molecular relaxation matrix elements. Conditions for this simple T1, T2 description are also given. The system is described in terms of a kinetic equation for the density matrix, which provides a unified treatment of the microwave transient behavior, spectral line shapes, and double resonance phenomena. Spatial degeneracy of the states and m dependence of T1 and T2 are discussed in detail. The recently developed semiclassical theory of molecular collisions is then applied to obtain expressions for the relevant relaxation times.