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Relative rate study of the kinetic isotope effect in the (CH3D)-C-13 + Cl reaction

Joelsson, L. M. T.; Forecast, R.; Schmidt, J. A.; Meusinger, C.; Heimdal Nilsson, Elna LU ; Ono, S. and Johnson, M. S. (2014) In Chemical Physics Letters 605. p.152-157
Abstract
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.
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Physics Letters
volume
605
pages
152 - 157
publisher
Elsevier
external identifiers
  • wos:000338401900030
  • scopus:84901930732
ISSN
0009-2614
DOI
10.1016/j.cplett.2014.05.022
language
English
LU publication?
yes
id
66092dda-a593-4f6c-b12a-6eb2ce37d735 (old id 4605798)
date added to LUP
2014-09-04 12:22:03
date last changed
2017-10-22 04:21:31
@article{66092dda-a593-4f6c-b12a-6eb2ce37d735,
  abstract     = {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.},
  author       = {Joelsson, L. M. T. and Forecast, R. and Schmidt, J. A. and Meusinger, C. and Heimdal Nilsson, Elna and Ono, S. and Johnson, M. S.},
  issn         = {0009-2614},
  language     = {eng},
  pages        = {152--157},
  publisher    = {Elsevier},
  series       = {Chemical Physics Letters},
  title        = {Relative rate study of the kinetic isotope effect in the (CH3D)-C-13 + Cl reaction},
  url          = {http://dx.doi.org/10.1016/j.cplett.2014.05.022},
  volume       = {605},
  year         = {2014},
}