Examination of the Stabilities of Group 14 (C, Si, Ge, Sn, Pb) Congeners of Dihydroxycarbene and Dioxirane. Comparison to Formic Acid and Hydroperoxycarbene Congeners.
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.
Richardson
Nancy A.
NA
Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602-2525.
Rienstra-Kiracofe
Jonathan C.
JC
Schaefer III
Henry F.
HF