Calculation of the Probabilities of Molecular Transitions in Modeling Interisomeric Structural Transformations

The problems of a computational procedure in modeling structural isomer–isomer transitions in multiatomic molecules are considered. A number of approximations that allow one to considerably simplify calculation of the probabilities of these transformations are suggested. In comparison with traditional calculations of potential surfaces and determination of their saddle points, in the proposed approach the relationship between the electronic and vibrational components of a general problem is virtually changed. A particular emphasis is put on the vibrational part, which seems to be more physical. It is shown that the problem of structural isomer–isomer conversions can be solved without resorting at all to explicit calculation of the contribution of an electronic matrix element to the probability of transition. There is no need to study in detail the shapes of potential surfaces; it suffices only to know the positions of their minima. The calculation of multidimensional vibrational integrals is replaced by calculation of one-dimensional integrals. The results obtained form a basis for constructing methods for modeling the dynamic spectra of complex molecules considering their structural transformations.