title: Calculations predict a large inverse H/D kinetic isotope effect on the rate of tunneling in the ring opening of cyclopropylcarbinyl radical.
abstract: B3LYP/6-31G* calculations have been performed, to compute the kinetic isotope effects (KIEs) on the rate of ring opening of cyclopropylcarbinyl radical (1) to 3-buten-1-yl radical (2) at 20 K by tunneling. The most striking result of our small curvature tunneling calculations is the prediction of a 2.7-fold increase in the rate of reaction by substitution of D(2) for H(2) at C(1). The origin of this very surprising, inverse KIE on the rate of tunneling is discussed.
authors.affiliation: Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle #305070, Denton, Texas 76203-5017, USA.
authors.forename: Xue
authors.initials: X
authors.lastname: Zhang
authors.forename: Ayan
authors.initials: A
authors.lastname: Datta
authors.forename: David A
authors.initials: DA
authors.lastname: Hrovat
authors.forename: Weston Thatcher
authors.initials: WT
authors.lastname: Borden