A theory for collision-induced transitions in the subset of quantum states |e〉 is developed, where the full molecular basis is |a eau〉. The only assumption is that changes in a u occur much more quickly than those in ae. The choice of ae and au is in general arbitrary, and it is shown how to make this separation based on the type of experimental measurement under consideration. For example, an evaluation of an atom-vibrotor problem (i.e., ae=n, au=jmj) is considered. In conjuction with this illustration an analysis of the breathing sphere (BS) approximation is carried out. It is concluded that a modified BS method (i.e., use of the diagonal rotational potential) should be valid when the random phase approximation holds for the rotational scattering amplitude.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry