Chemical Physics Letters, Vol.351, No.3-4, 267-274, 2002
Direct ab initio dynamics study on the reaction paths and rate constants of hydrogen atoms with methylgermanes GeH3CH3 and GeH2(CH3)(2)
Direct ab initio dynamical calculations at the PMP4SDTQ/6-311 + G(3df, 2p)//MP2/6-31 + G(d) level have been performed on the reactions of atomic hydrogen with methylgermanes, GeH3CH3 and GeH2(CH3)(2), over the temperature range 200-2000 K The obtained CVT/SCT thermal rate constants are in good agreement with available experimental values. The results show that the variational effect and small-curvature tunneling effects are unimportant for the two reactions over the whole temperature range, The rate constants are fitted to the three-parameter expressions over the whole temperature range 200-2000 K: k(GeH3CH3 + H) = 1.815 x 10(8)T(1.817) exp(-691/T) cm(3) mol(-1) s(-1) and k[GeH2 (CH3)(2) + H] = 2.448 x 10(8)T(1.727) exp(-639/T) cm(3) mol(-1) s(-1). (C) 2002 Published by Elsevier Science B.V.