Internal dynamics of (H2O)2 and (D2O)2 dimers: II. Effective operators of physical quantities with account of inversion and exchange motions

Abstract

Using the symmetry group chain methods, a model of the internal dynamics of (H2O)2 and (D2O)2 dimers that takes into account their real geometries and two nonrigid motions with the lowest energy barriers is constructed. The motions are the inversion motion (or the acceptor switching) and the exchange motion of the acceptor and donor via an intermediate trans configuration. The model rigorously describes the interactions of various motions and leads to a simple algebraic scheme of calculation of both the positions of the levels in the energy spectrum and the intensities of transitions between them. It is important that the correctness of the model is limited only by the trueness of the choice of the symmetry of the internal dynamics.