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Role of tunneling of hydrogen in photoenolization of a ketone
Author(s) -
Sengupta Debasis,
Chandra A. K.
Publication year - 1994
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560520607
Subject(s) - wkb approximation , quantum tunnelling , hydrogen , chemistry , deuterium , ketone , quantum mechanics , computational chemistry , atomic physics , physics , organic chemistry
Photoenolization of a ketone in its lowest triplet state was examined using the AM 1 semiempirical molecular orbital method with complete geometry optimization at the configuration interaction level in the restricted Hartree–Fock frame. The theoretical barrier fits with a polynomial given by Eq. (1) and the probability of tunneling of hydrogen was calculated by the WKB method. The density of states above the zero‐point level was estimated by the Whitten–Rabinovitch approximation. Rate constants for the hydrogen and deuterium‐abstraction processes via tunneling were then computed at different temperatures. © 1994 John Wiley & Sons, Inc.