Experimental and theoretical studies of molecular transition moments

Chalkley, Stephen Wilfred (1980) Experimental and theoretical studies of molecular transition moments. University of Southampton, Doctoral Thesis.

Abstract

Firstly, Stark effects have been observed for individual lines in the excitation spectrum of the NHD radical, recorded in the visible region with a tunable dye laser. Individual MT components have been resolved with Doppler limited resolution. The results are interpreted in terms of an interaction between the applied electric field and a ground state dipole moment determined to be 1.82±.05D'and a dipole moment in the (0,9,0) level of the A'A' state determined to be 0.19±.06D. Secondly, a simple perturbation treatment is used to reduce the number of independent transition moments (which may, in principle, be many) necessary to describe the intensity distribution of intercombination transitions (involving AS=l) in diatomic molecules. It is demonstrated that, in general, the number of independent transition moments can always be reduced to three (four for if - II transitions). The treatment is valid for weak spin-orbit interaction between electronic states, and yields formulae, by which any intercombination transition moment can be expressed in terms of one of three parameters - u//, ull,or h12. Several examples of the application of these formulae is given.

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