The Present State of Quantum-chemical Calculations of the Intermolecular Interaction of Polyatomic Molecules

In the present review, the results of quantum-chemical calculations of the energy of the interaction of polyatomic molecules are discussed for the case of dimers. The main theoretical approaches used in the calculation of intermolecular interaction, the self-consistent field method (supermolecule approximation) and perturbation theory, are analysed briefly. The range of applicability and the advantages and disadvantages of these main approaches are evaluated. The results of non-empirical calculations of the interaction of molecules forming dimers of different kinds: with the participation of hydrogen bonds, donor–acceptor complexes, and others, are examined. The accuracy of non-empirical calculations and the influence of the basis set used are discussed, and recommendations for improving the non-empirical data are given. The possibility of constructing analytical potentials (including atom–atom potentials), which can be used to study many-particle systems, from the results of non-empirical calculations is analysed. In addition to non-empirical calculations, the possibilities provided by semi-empirical methods of calculating the intermolecular interaction of polyatomic molecules both in the self-consistent field approximation and using perturbation theory are also examined. The bibliography contains 202 references.