Theoretical Investigation of the Kinetics for the Reactions of Atomic Hydrogen with GeH(4-n)Cln (n = 0, 1, 2, 3)

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The reactions of H atoms with GeH 4, GeH 3 Cl, GeH 2 Cl 2, and GeHCl 3 have been studied systematically using ab initio molecular orbital theory. Theoretical analysis provides conclusive evidence that the main process occurring in each case is hydrogen abstraction from the Ge−H bonds. The reaction thermal rate constants for the temperature range 200−3000 K are deduced by canonical variational transition state theory (CVT) with small curvature tunneling (SCT) correction method. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior. Three-parameter rate−temperature formulas have been fitted as follows: k 1 = 3.09 × 10 -17 T 2.16 exp(−286.74/ T ), k 2 = 1.94 × 10 -17 T 2.18 exp(−276.82/ T ), k 3 = 4.19 × 10 -18 T 2.37 exp(−227.64/ T ), and k 4 = 2.02 × 10 -17 T 1.98 exp(−218.51/ T ) for the reactions of H with GeH 4, GeH 3 Cl, GeH 2 Cl 2, and GeHCl 3, respectively (in units of cm 3 molecule -1 s -1 ). Studies show that chlorine substitution has a very slight effect on the strength and reactivity of the Ge−H bonds in GeH (4 - n ) Cl n ( n = 1−3).