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J Phys Chem A. 2007 Sep 6;111(35):8677-88. Epub 2007 Aug 15.

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

Author information

1
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.

Abstract

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.

PMID:
17696410
DOI:
10.1021/jp071797k

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