J. Phys. Chem. A, 110, 10817-10821 (2006)

DOI: 10.1021/jp062620d

Competition between Nonclassical Hydrogen-Bonded Acceptor Sites in Complexes of Neutral AH2 Radicals (A ) B, Al, and Ga): A Theoretical Investigation

An ab initio computational study of the properties of the neutral AH2 radicals (A = B, Al, Ga) as hydrogen-bond (HB) acceptors, with H−X (X = F, Cl, Br, CN, and CCH) as HB donors, is carried out at the UMP2/6-311++G(2d,2p) level. Two different minima have been found for each of the 15 possible dimers. One structure corresponds to a single-electron hydrogen-bonded complex (SEHB), with the A atom acting as an HB acceptor. The second corresponds to a dihydrogen bond complex between one of the hydrogen atoms of AH2 and the H−X molecule. Thus, all the atoms of the neutral AH2 molecule can act as HB acceptors and none as donors. The stability of the SEHB complexes decreases as BH2 > AlH2 > GaH2, while for the dihydrogen-bonded complexes the order is AlH2 > GaH2 > BH2. For the BH2 radical the SEHB complexes are stronger than the dihydrogen bonded ones, while the opposite is found for the AlH2 and GaH2systems. Regarding the HB donors, the order found for the binding energy in the two types of complexes is H2A···HF > H2A···HCl > H2A···HBr > H2A···HCN > H2A···HCCH.