title: Direct ab initio dynamics study on the rate constants and kinetic isotope effect for the reactions of H atoms with GeDn(CH3)4-n (n = 1-4).
abstract: Direct ab initio dynamic calculations are performed on the reactions of atomic hydrogen with GeD(n)(CH(3))(4-n) (n = 1-4) over the temperature range 200-2000 K at the PMP4SDTQ/6-311 +G(3df,2p)//MP2/6-31 +G(d) (for n = 2-4) and G2//MP2/6-31 +G(d) (for n = 1) levels. The corresponding k(H)/k(D) ratios are then calculated in order to determine the kinetic isotope effect for the four reactions. For the simplest GeD(4) +H reaction, the only one that has available experimental data, the calculated canonical variational transition state theory incorporates small-curvature tunneling correction (CVT/SCT) thermal rate constants, and the k(H)/k(D) values are in good agreement with the experimental values within the experimental temperature range 293-550 K. For the four GeD(n)(CH(3))(4-4) (n = 1-4) reactions, the variational effect is small over the whole temperature range, whereas the small-curvature effect is important in the lower temperature range. Finally, the overall rate constants are fitted to the three-parameter expression over the whole temperature range 200-2000 K as 5.8 x 10(8)T(1.68)exp(-929/T), 1.7 x 10(8)T(1.80)exp(-691/T), 2.58 x 10(8)T(1.71)exp(-706/T), and 1.0 x 10(7)T(2.08)exp(-544/T) cm(3) mol(-1) s(-1) for the n = 4, 3, 2, and 1 reactions. Our work may represent the first theoretical study of the kinetic isotope effect for the H-attack on the G-H bonding.
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
authors.forename: Yang
authors.initials: Y
authors.lastname: Wu
authors.forename: Yi-Hong
authors.initials: YH
authors.lastname: Ding
authors.forename: Jing-Fa
authors.initials: JF
authors.lastname: Xiao
authors.forename: Ze-Sheng
authors.initials: ZS
authors.lastname: Li
authors.forename: Xu-Ri
authors.initials: XR
authors.lastname: Huang
authors.forename: Chia-Chung
authors.initials: CC
authors.lastname: Sun