PNNL

Abstract

The structural and chemical bonding motifs manifested by the competition between hydrogen and chalcogen bonding in the homodimers of chalcogen hydrides (H2X)2, where X = O, S, Se, Te have been characterized using high-level electronic structure calculations and analysis of the electron density based on Quasi-atomic orbital (QUAO) and the Symmetry-adapted perturbation theory (SAPT) methods. The QUAO analysis clearly identifies a three-center interaction responsible for either hydrogen or chalcogen bonds: in the former, the s-bond connecting the donor and hydrogen atom participating in the hydrogen bond interacts with the lone pair on the nucleophile acceptor via the hydrogen atom, while in the latter this same s-bond interacts with the nucleophile lone pair via the donor chalcogen. The number of minimum energy structures increase dramatically from one for (H2O)2, three for (H2S)2, four for (H2Se)2, and finally six for (H2Te)2. The emergence of the chalcogen-bonded arrangements appears for (H2S)2 with their subsequent energetic stabilization over the hydrogen-bonded minima manifesting in (H2Se)2 and (H2Te)2. In particular, one of the (H2S)2 , two of the (H2Se)2, and three of the (H2Te)2 dimers are chalcogen bonded. Induction plays a small but important role in stabilizing hydrogen over chalcogen-bonded structures, while dispersion is more important for chalcogen bonds.