ROVIBRATIONAL HAMILTONIAN FOR MOLECULAR-COMPLEXES

A general form of the rovibrational Hamiltonian for molecular complexes composed of separate fragments has been derived. A method of rotating molecular axes has been developed to remove locally the main part of the Coriolis coupling on a given subspace of internal coordinates. An efficient and accurate computational method for the rovibrational states has been developed and applied to van der Waals complexes of pyridine with argon and krypton atoms. As a result, three-dimensional empirical potential energy surfaces have been fitted to the rotational transitions of these complexes. Their vibrational states have been predicted and analysed.