The influence of rotational motion on intersystem crossing in isolated molecules

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Abstract
We have calculated the effect of molecular rotation on the rate constant for intersystem crossing in a large isolated molecule by constructing a simple displaced oscillator model. The effects of the changes in moments of inertia, Coriolis coupling, and of intramanifold rotation–vibration coupling are included in the model. Because of the sum rule constraining sums of products of Clebsch–Gordon coefficients the above are the only mechanisms for rotation to influence intersystem crossing. These effects are seen to be small for physically reasonable values for the parameters of the theory. This is consistent with some recent experimental work by Michel and Tramer.