Theoretical Study of Mixed Hydrogen and Dihydrogen Bond Interactions in Clusters

Ab initio calculations were used to analyze interactions of with 1–4 molecules of NH3at the MP2/6-311++G(d,p) and the B3LYP/6-311++G(d,p) computational levels. In addition to H3B–H⋯H–NH2dihydrogen bond, the H2N–H⋯NH3hydrogen bonds were also predicted in clusters. Negative cooperativity in clusters constructed from mixed H3B–H⋯H–NH2dihydrogen and H2N–H⋯NH3hydrogen bonds are more remarkable. The negative cooperativity increases with size and number of hydrogen bonds in cluster. The B–H stretching frequencies show blue shifts with respect to cluster formation. Greater blue shift in stretching frequencies was predicted for B–H bonds which did not contribute to dihydrogen bonding with NH3molecules. The structures were analyzed with the atoms in molecules (AIM) methodology.