TY - JOUR
T1 - Relative rate study of the kinetic isotope effect in the (CH3D)-C-13 + Cl reaction
AU - Joelsson, L. M. T.
AU - Forecast, R.
AU - Schmidt, J. A.
AU - Meusinger, C.
AU - Heimdal Nilsson, Elna
AU - Ono, S.
AU - Johnson, M. S.
PY - 2014
Y1 - 2014
N2 - The (CH3D)-C-13/(CH4)-C-12 kinetic isotope effect, alpha((CH3D)-C-13), of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. alpha((CH3D)-C-13) is found to be 1.60 +/- 0.04. In addition, a quantum chemistry/transition state theory model with tunneling correction is constructed and the primary cause for alpha((CH3D)-C-13) is found to be the substantially reduced reactivity of the D atom, which, in turn, can be explained by a significant increase in the reaction barrier due to changes in the vibrational zero point energy and to a lesser extent tunneling. (C) 2014 Elsevier B.V. All rights reserved.
AB - The (CH3D)-C-13/(CH4)-C-12 kinetic isotope effect, alpha((CH3D)-C-13), of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. alpha((CH3D)-C-13) is found to be 1.60 +/- 0.04. In addition, a quantum chemistry/transition state theory model with tunneling correction is constructed and the primary cause for alpha((CH3D)-C-13) is found to be the substantially reduced reactivity of the D atom, which, in turn, can be explained by a significant increase in the reaction barrier due to changes in the vibrational zero point energy and to a lesser extent tunneling. (C) 2014 Elsevier B.V. All rights reserved.
U2 - 10.1016/j.cplett.2014.05.022
DO - 10.1016/j.cplett.2014.05.022
M3 - Article
SN - 0009-2614
VL - 605
SP - 152
EP - 157
JO - Chemical Physics Letters
JF - Chemical Physics Letters
ER -