Ab initio thermochemistry of the hydrogenation of hydrocarbon radicals using silicon-, germanium-, tin-, and lead-substituted methane and isobutane.
A series of reactions of the type Y. + XH(4) --> YH + .XH(3) and Y'. + HX(CH(3))(3) --> Y'H + .X(CH(3))(3), where Y = H, CH(3); Y' = CH(3), C(CH(3))(3); and X = Si, Ge, Sn, Pb are studied using state-of-the-art ab initio electronic structure methods. Second-order Møller-Plesset perturbation theory; the coupled-cluster singles, doubles, and perturbative triples method; and density functional theory are used with correlation-consistent basis sets (cc-pVNZ, where N = D, T, Q) and their pseudopotential analogs (cc-pVNZ-PP) to determine the transition-state geometries, activation barriers, and thermodynamic properties of these reactions. Trends in the barrier heights as a function of the group IVA atom (Si, Ge, Sn, and Pb) are examined. With respect to kinetics and thermodynamics, the use of a hydrogen attached to a group IVA element as a possible hydrogen donation tool in the mechanosynthesis of diamondoids appears feasible.
Temelso
Berhane
B
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Sherrill
C David
CD
Merkle
Ralph C
RC
Freitas
Robert A
RA