Interference of rotational branches in molecular spectra

The rotational phase shift 5, which cannot exceed a mean angle of a molecular rotation during collisional time (anc), is certainly small in the case of non-adiabatic collisions. This condition is exactly that needed for anisotropic scattering (or IR absorption) spectrum narrowing, just as vibrational dephasing must be weak for an isotropic spectrum to narrow. 

Firstly, we are going to demonstrate how branch interference may be taken into account within the quasi-classical impact theory. Then we shall analyse a quasi-static case, when the exchange frequency between branches is relatively small. An alternative case, when exchange is intensive and the spectrum collapses, has been already considered in Chapter 2. Now it will be shown how the quasi-static spectrum narrows with intensification of exchange. The models of weak and strong collisions will be compared with each other and with experimental data. Finally, the mutual agreement of various theoretical approaches to the problem will be considered. 

According to Eq. (2.13), the spectra we are interested in are given by a Fourier transform of the orientational correlation functions of the corresponding order Similarly to what was done in Chapter 3, the correlation functions for linear and spherical molecules may be represented as a superposition of the partial (marginal) components 

Physical substantiation of this relationship is discussed in Appendix 6. Here, it is enough to mention that 

Time evolution of this component, as is proven in Appendix 7, is described by the kinetic equation of impact theory, which is a generalization of Eq. (3.26)  

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