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)=1.815×108T1.817exp(−691/T) cm3 mol−1 s−1 and k[GeH2(CH3)2+H]=2.448×108T1.727exp(−639/T) cm3 mol−1 s−1.