Dihydrogen bond cooperativity in (HCCBeH)n clusters

8 pages, 9 figures, 9 tables.-- PACS: 31.15.ae; 31.15.E-; 31.15.bw; 36.40.-c; 31.30.jp; 31.15.amA theoretical study has been carried out on the clusters formed by the association of ethynylhydroberyllium (HCC-BeH) monomers. The monomer presents a linear disposition with a dipole moment of 0.94 D. Clusters from two to six monomers have been calculated for three different configurations (linear, cyclic with dihydrogen bonds, and cyclic with hydrogen bonds to the (pi)-cloud), the third one being the most stable. The electronic properties of the clusters have been analyzed by means of the atoms in molecules and natural bond orbitals methodologies. Cooperative effects, similar to the ones described for standard hydrogen bonded clusters, are observed in those configurations where dihydrogen bonds are the main interacting force.M. Solimannejad acknowledges the travel grant provided by CSIC and Arak University. This work was carried out with financial support from the Ministerio de Ciencia y Tecnología (Grant Nos. CTQ2006-14487-C02-01/BQU and CTQ2007-61901/BQU ) and Comunidad Autónoma de Madrid (Project MADRISOLAR, Reference No. S-0505 /PPQ/0225).Peer reviewe

Theoretical study of dihydrogen bonds in HnMH⋯HArF and HnMH⋯HKrF complexes (n = 1-3; M = Be, Al, Ga, Si, Ge)

An ab initio computational study of the properties of 10 dihydrogen-bonded complexes of HnMH (M = Be, Al, Ga, Si, Ge) with the rare gas derivatives HArF and HKrF has been carried out at the MP2(full)/6-311++G(2d,2p) level of theory. Red shifts of H-Rg and Rg-F along with blue shifts of M-H vibrational stretching frequency were predicted. Variations of the 1H chemical shielding of the HRgF molecules versus the H⋯H distance of the complexes were also studied. © 2005 Elsevier B.V. All rights reserved.Peer Reviewe

Ab initio study of complexes pairing HRgX and H2 (Rg = Ar, Kr and X = F, Cl, CN)

MP2/aug-cc-pVTZ calculations are used to analyze the interaction between hydrogen molecule and rare gas containing compounds HRgX (Rg = Ar, Kr and X = F, Cl, CN). One T-shape C2v minima are located on the potential energy surface of each complex. Binding energies of the complexes corrected with BSSE are in the range of 1.3-2.9 kJ/mol at the MP2/aug-cc-pVTZ computational level, being the H2⋯HArF the most strongly bound and H2⋯HKrCN the least. Blue shift of H-Rg stretching frequencies within each subunit caused by complexation is predicted in the range of 30-200 cm-1. The atoms in molecules (AIM) theory was applied in order to analyze the physical nature of the stabilization of these complexes. © 2007 Elsevier B.V. All rights reserved.Peer Reviewe