title: Why does a Ga(2) dimer react spontaneously with H2, but a Ga atom does not?--A detailed quantum chemical investigation of the differences in reactivity between ga atoms and Ga(2) dimers, in combination with experimental results.
abstract: The spontaneous and photoactivated reactions between Ga(2) and H(2) in a matrix of solid Ar at 12 K have been followed by using IR spectroscopy and have been shown to give access to several isomers of the subvalent hydride Ga(2)H(2). We now present Raman spectra for this system, to complete its characterization on the basis of vibrational spectra. In addition, the differences between the reactivity of a Ga atom and a Ga(2) dimer toward H(2) are evaluated. The matrix isolation experiments have shown that Ga(2) reacts spontaneously with H(2,) at 12 K, to give the cyclic subvalent hydride Ga(micro-H)(2)Ga (D(2h) symmetry), which can be transformed into two other isomers of Ga(2)H(2) by selective photoactivation. Interestingly, the spontaneous reaction is subject to a marked isotopic effect. In total, the experimental results provide detailed information about the reaction mechanism. In contrast to Ga(2), Ga atoms do not react spontaneously with H(2); on photoactivation they instead yield the radical species GaH(2). The quantum chemical calculations presented herein start with an analysis of the structures and relative energies of the relevant species at the MP2 level, by using extended basis sets, and lead on to a discussion of the correlation diagrams for both reactions. Finally, CASSCF and MRCI methods, in combination with moderate-sized basis sets, were employed to analyze in detail the mechanisms of the two reactions. It will be shown that the computational results, in concert with the experimental findings, provide a satisfying explanation of the contrasting reactivities of Ga and Ga(2).
authors.affiliation: Institut für Physikalische Chemie der Universität Karlsruhe Fritz-Haber-Weg, Geb 30.43, 76128 Karlsruhe, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Köhn
authors.forename: Hans-Jörg
authors.initials: HJ
authors.lastname: Himmel
authors.forename: Benjamin
authors.initials: B
authors.lastname: Gaertner