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- W1996286249 abstract "The results of a series of calculations for a wide, unrestricted variation in the force constants for the making and breaking bonds and their interaction constant are presented for the abstraction reactions of CH2D2 with Cl atoms. A wide range of asymmetrical force constants leads to a high kinetic isotope effect as has been pointed out by others for a more restricted range of consideration. These results pointedly contradict the assumed connection between a high kinetic isotope effect and a symmetrical transition state. It is found by examining the atomic displacements of the normal mode that the motion of the H or D atom in the real stretch of the transition state will often have little influence on the isotope effect because the mode can be dominated by end group motions. It is further found that a 3-center model multiplied by a constant factor to account for the contributions of the other vibrations is capable of very satisfactorily reproducing the more rigorous 6-center calculations." @default.
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- W1996286249 date "1978-01-01" @default.
- W1996286249 modified "2023-10-16" @default.
- W1996286249 title "Large kinetic isotope effects with unsymmetrical transition states" @default.
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- W1996286249 doi "https://doi.org/10.1016/0040-4020(78)80193-8" @default.
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