Ab initio thermochemistry of the hydrogenation of hydrocarbon radicals using silicon-, germanium-, tin-, and lead-substituted methane and isobutane

作者：Temelso Berhane; Sherrill C David^*; Merkle Ralph C; Freitas Robert A Jr

来源：Journal of Physical Chemistry A, 2007, 111(35): 8677-8688.

DOI：10.1021/jp071797k

A series of reactions of the type Y(center dot)+ XH(4) -> YH + center dot XH(3) and Y'center dot + HX(CH(3))(3) -> Y'H + center dot 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 Miller-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.

• 出版日期2007-9-6