title: Examination of the Stabilities of Group 14 (C, Si, Ge, Sn, Pb) Congeners of Dihydroxycarbene and Dioxirane. Comparison to Formic Acid and Hydroperoxycarbene Congeners.
abstract: The relative energetics of four XH(2)O(2) (X = C, Si, Ge, Sn, Pb) isomers, dihydroxycarbene, formic acid, dioxirane, and hydroperoxycarbene, were determined using the BLYP and B3LYP density functionals with DZP and TZ2P basis sets, as well as CCSD and CCSD(T) single-point energies at the BLYP/TZ2P optimized geometries. Relative to dihydroxycarbene, formic acid was 41.8 kcal/mol lower in energy while dioxirane and hydroperoxycarbene were 51.3 and 63.6 kcal/mol higher, respectively, with CCSD(T). Furthermore, using an effective core potential (ECP) the dihydroxy congener was shown to be the most stable isomer for X = Si-Pb. The formic acid and dioxirane congeners become increasingly less stable as one descends group 14. Our results show that divalency is preferred for Si-Pb (dihydroxy congeners are the most stable) but the tetravalent formic acid congeners remain more stable than the hydroperoxy congeners, showing that divalency is not universally preferred among these isomers.
authors.affiliation: Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602-2525.
authors.forename: Nancy A.
authors.initials: NA
authors.lastname: Richardson
authors.forename: Jonathan C.
authors.initials: JC
authors.lastname: Rienstra-Kiracofe
authors.forename: Henry F.
authors.initials: HF
authors.lastname: Schaefer III