Thermal rate constants for chemical reactions using the corrections of zero curvature tunneling (ZCT) and of small curvature tunneling (SCT) methods are reported. The general procedure is implemented and used with high-quality ab initio computations and semiclassical reaction probabilities along the minimum energy path (MEP). The approach is based on a vibrational adiabatic reaction path and is applied to the H + Si(CH3)(4) -> H-2 + Si(CH3)(3)CH2 reaction and its isotopically substituted variants. All of the degrees of freedom are optimized, and harmonic vibrational frequencies and zero-point energies are calculated at the MP2(full) level with the cc-pVTZ basis set. Single-point energies are calculated at a higher level of theory with the same basis set, namely, CCSD(T,full). The influence of the basis set superposition error (BSSE) on the energetics is tested. The method is further exploited to predict primary and secondary kinetic isotope effects (KIEs and SKIEs, respectively). Rate constants computed with the ZCT and SCT methods over a wide temperature range (180-2000 K) show important quantum tunneling effects at low temperatures when compared to rates obtained from the purely classical transition-state theory (TST) and from the canonical variational transition state theory (CVT). For the H + Si(CH3)(4) reaction, they are given by the following expressions: k(TST/ZCT) = 9.47 X 10(-19) X T-2.65 exp(-2455.7/T) and k(CVT/SCT) = 7.81 X 10(-19) X T-2.61 exp[(2704.2/T) (in cm(3) molecule(-1) s(-1)). These calculated rates are in very good agreement with those from available experiments.