TY - JOUR
T1 - Examination of the Stabilities of Group 14 (C, Si, Ge, Sn, Pb) Congeners of Dihydroxycarbene and Dioxirane. Comparison to Formic Acid and Hydroperoxycarbene Congeners
AU - Richardson, Nancy A.
AU - Rienstra-Kiracofe, Jonathan C
AU - Schaefer, Henry F.
N1 - The relative energetics of four XH2O2 (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.
PY - 1999/12
Y1 - 1999/12
N2 - The relative energetics of four XH2O2 (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.
AB - The relative energetics of four XH2O2 (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.
KW - Organic acids
KW - Energy
KW - Silicon
KW - Basis sets Molecular structure
UR - https://pubs.acs.org/doi/10.1021/ic9910099
U2 - 10.1021/ic9910099
DO - 10.1021/ic9910099
M3 - Article
C2 - 11671343
VL - 38
JO - Inorganic Chemistry
JF - Inorganic Chemistry
ER -