Effect of Halogen at the Divalent Sulfur Atom on the Properties of Complexes with a Chalcogen and Hydrogen Bond

Abstract

Binary complexes with a chalcogen (A complexes) and hydrogen (B complexes) bond formed by SHX molecules (X = F, Cl, Br, OH) of divalent sulfur and a water molecule have been calculated by the MP2/aug-cc-pVTZ quantum chemical method. An NBO analysis was performed for complexes of both types along with the topological analysis of electron density and decomposition of the binding energy into components. The quantum chemical calculations showed that the binding energies, interorbital interaction energies of monomers, and electron densities at the critical point (3, –1) of intermolecular contact are close in the A and B complexes. The main contribution to stabilization of the complexes is made by the electrostatic interaction; in the B complexes, however, the contribution of the charge transfer component is also significant. The dispersion energy plays a significant role in the binding of monomers in complexes of both types. According to the calculations, the interconversion of A and B complexes occurs with a very low activation barrier.