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Theoretical kinetic isotope effects for the hydride transfer from formate to carbon dioxide: A comparison of theory with experiment
Author(s) -
Jones Jeffrey P.,
Urbauer Jeffrey L.
Publication year - 1991
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540120912
Subject(s) - kinetic isotope effect , chemistry , deuterium , hydride , ab initio , basis set , hydrogen atom , ground state , computational chemistry , mndo , atomic physics , hydrogen , molecule , density functional theory , physics , organic chemistry , alkyl
Heavy atom and deuterium isotope effects for the hydride transfer from formate to carbon dioxide were determined using MNDO, AM1, and PM3 semiempirical methods and the ab initio RHF/3‐21G*, 3‐21 + G, 6‐31G*, and 6‐31 + G* basis sets. Frequencies were also determined for ground state structures using 6‐31G* basis set at the MP2 level of theory. The calculated isotope effects compared favorably with the experimentally determined values of Hermes et al. ( Biochemistry , 23 , 5479 (1984)). The calculated ground state frequencies were high for most vibrational modes as compared with measured values, however some ab initio methods underestimate the carbon hydrogen stretching frequencies. The heavy atom isotope effects were influenced to a large extent by the excitation factor, the mass factor and the moment of inertia factor of the Bigeleisen equation.