| Abstract: | 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. |
