Author/Authors :
Joelsson، نويسنده , , L.M.T. and Forecast، نويسنده , , R. and Schmidt، نويسنده , , J.A. and Meusinger، نويسنده , , C. and Nilsson، نويسنده , , E.J.K. and Ono، نويسنده , , S. and Johnson، نويسنده , , M.S.، نويسنده ,
Abstract :
The 13CH3D/12CH4 kinetic isotope effect, α 13 CH 3 D , of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α 13 CH 3 D 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 α 13 CH 3 D 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.
