Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

Lars Magnus Torvald Joelsson; Roslyn Forecast; Johan Albrecht Schmidt; Carl Meusinger; E.J.K. Nilsson; S. Ono; Matthew Stanley Johnson

doi:10.1016/j.cplett.2014.05.022

Relative rate study of the kinetic isotope effect in the ¹³CH₃D + Cl reaction

Lars Magnus Torvald Joelsson, Roslyn Forecast, Johan Albrecht Schmidt, Carl Meusinger, E.J.K. Nilsson, S. Ono, Matthew Stanley Johnson^*

^*Corresponding author af dette arbejde

9 Citationer (Scopus)

Abstract

The ¹³CH₃D/¹²CH₄kinetic isotope effect, α¹³CH₃D, of CH₄ + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α¹³CH₃D 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 α¹³CH₃D 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.

Originalsprog	Engelsk
Tidsskrift	Chemical Physics Letters
Vol/bind	605-606
Sider (fra-til)	152-157
Antal sider	6
ISSN	0009-2614
DOI	https://doi.org/10.1016/j.cplett.2014.05.022
Status	Udgivet - 2014

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10.1016/j.cplett.2014.05.022

Citationsformater

@article{286160836d5644d095472702e4233221,

title = "Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction",

abstract = "The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D 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 α13CH3D 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.",

author = "Joelsson, {Lars Magnus Torvald} and Roslyn Forecast and Schmidt, {Johan Albrecht} and Carl Meusinger and E.J.K. Nilsson and S. Ono and Johnson, {Matthew Stanley}",

year = "2014",

doi = "10.1016/j.cplett.2014.05.022",

language = "English",

volume = "605-606",

pages = "152--157",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

}

TY - JOUR

T1 - Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

AU - Joelsson, Lars Magnus Torvald

AU - Forecast, Roslyn

AU - Schmidt, Johan Albrecht

AU - Meusinger, Carl

AU - Nilsson, E.J.K.

AU - Ono, S.

AU - Johnson, Matthew Stanley

PY - 2014

Y1 - 2014

N2 - The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D 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 α13CH3D 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.

AB - The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D 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 α13CH3D 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.

U2 - 10.1016/j.cplett.2014.05.022

DO - 10.1016/j.cplett.2014.05.022

M3 - Journal article

AN - SCOPUS:84901930732

SN - 0009-2614

VL - 605-606

SP - 152

EP - 157

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

Abstract

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Relative rate study of the kinetic isotope effect in the ¹³CH₃D + Cl reaction