Spontaneous bond dissociation cascades induced by Ben clusters (n = 2,4)

Abstract

High-level single and multireference ab initio calculations show that the Be₄ cluster behaves as a very efficient Lewis acid when interacting with conventional Lewis bases such as ammonia, water or hydrogen fluoride, to the point that the corresponding acid–base interaction triggers a sequential dissociation of all the bonds of the Lewis base. Notably, this behavior is already found for the simplest beryllium cluster, the Be₂ dimer. However, whereas for Be₂ the first dissociation process involves a low activation barrier which is above the reactants, for Be₄ all the bond dissociation processes involve barriers below the entrance channel leading to a cascade of successive exothermic processes, which end up spontaneously in a global minimum in which the bonding patterns of both the base and the Lewis acid are completely destroyed. Indeed, the global minimum, in all cases, is stabilized by three-center Be–H–Be bonds and covalent interactions between the Be atoms and the basic center of the base, which replace the initial metallic bond stabilizing the Be₄ cluster. As a consequence, in the global minimum the basic atoms (N, O and F) behave as hyper-coordinated centers. Also importantly, the Be₄ cluster and its complexes present RHF–UHF instabilities (not reported before for Be₄), which require the use of multireference methods to correctly describe them.