Cooperativity between hydrogen bonds and beryllium bonds in (H2O)nBeX2 (n=1-3, X = H, F) complexes. A new perspective

The interaction of BeX2 (X = H, F) with water molecules has been analyzed at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d, p) level of theory. The formation of strong beryllium bonds between water molecules and the BeX2 derivative triggers significant electron density redistribution within the whole system, resulting in significant changes in the proton donor and proton acceptor capacity of the water molecules involved. Hence, significant cooperative and anti-cooperative effects are present, explaining why there is no case in which the global minimum corresponds to a tetracoordinated beryllium atom. In fact, the most stable clusters can be viewed as the result of the attachment of BeX2 to the water trimer and the water dimer, respectively, and not as the result of the solvation of the BeX2 molecule. We have also shown that the decomposition of the interaction energy into atomic components is a reliable quantitative tool to describe all the closed-shell interactions present in the clusters investigated herein, namely hydrogen bonds, beryllium bonds and dihydrogen bonds. Indeed, we have shown that the changes in the atomic energy components are correlated with the changes in the strength of these interactions, and they provide a quantitative measure of cooperative effects directly in terms of energies.