Heterolytic and homolytic C D bond dissociation energies of three NADH models: BNAH-4,4-d 2 , HEH-4,4-d 2 and AcrD 2 in acetonitrile were first estimated by using an efficient method. The results showed that the heterolytic C D bond dissociation energies are 65.2, 70.2, and 81.9 kcal/mol and the homolytic C D bond dissociation energies are 72.66, 70.69, and 74.95 kcal/mol for BNAH-4,4-d 2 , HEH-4,4-d 2 , and AcrD 2 , respectively. According to the bond dissociation energy differences of isotope isomers, an interesting conclusion can be made that the primary kinetic isotope effects are dependent not only on the zero-point energy difference of the isotope isomers, but also on the types of C D bond dissociations, and the C D bond homolytic dissociations should have much larger primary kinetic isotope effects (26.9 28.8) than the corresponding C D bond heterolytic dissociations (3.9-5.4).
