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Theoretical Study on the Gas‐Phase S N 2 Reaction of Microhydrated Fluoride with Methyl Fluoride
Author(s) -
Chen JienLian,
Hu WeiPing
Publication year - 2012
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201200128
Subject(s) - chemistry , kinetic isotope effect , deuterium , fluoride , hydrogen fluoride , reaction rate constant , gas phase , quantum tunnelling , isotope , analytical chemistry (journal) , computational chemistry , inorganic chemistry , kinetics , organic chemistry , atomic physics , physics , optoelectronics , quantum mechanics
The rate constants for the gas‐phase S N 2 reaction of F − (H 2 O) with CH 3 F have been calculated using the dual‐level variational transition state theory including multidimensional tunneling from 50 to 500 K. Tunneling was found to dominate the reaction below 200 K. The deuterium, 13 C, and 14 C kinetic isotope effects (KIEs) and solvent (D 2 O) isotope effects (SKIEs) were also calculated in the same temperature range. The results indicated that the deuterium and heavy water substitutions resulted in inverse KIEs (0.6∼0.8 ) while the 13 C and 14 C substitutions resulted in normal KIEs (1.0∼1.2) at room temperature. The calculated carbon KIEs increased significantly below 80 K due to the differences in the magnitude of the tunneling effects for different isotopic substitutions.