Thermochemistry and accurate quantum reaction rate calculations for H2/HD/D2 + CH3
SourceThe Journal of Physical Chemistry A, 111, 41, (2007), pp. 10331-10337
Article / Letter to editor
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The Journal of Physical Chemistry A
Accurate quantum-mechanical results for thermodynamic data, cumulative reaction probabilities (for J = 0), thermal rate constants, and kinetic isotope effects for the three isotopic reactions H-2 + CH3 -> CH4 + H, HD + CH3 -> CH4 + D, and D-2 + CH3 -> CH3D + D are presented. The calculations are performed using flux correlation functions and the multiconfigurational time-dependent Hartree (MCTDH) method to propagate wave packets employing a Shephard interpolated potential energy surface based on high-level ab initio calculations. The calculated exothermicity for the H2 + CH3 -> CH4 + H reaction agrees to within 0.2 kcal/ mol with experimentally deduced values. For the H-2 + CH3 -> CH4 + H and D-2 + CH3 -> CH3D + D reactions, experimental rate constants from several groups are available. In comparing to these, we typically find agreement to within a factor of 2 or better. The kinetic isotope effect for the rate of the H-2 + CH3 -> CH4 + H reaction compared to those for the HD + CH3 -> CH4 + D and D-2 + CH3 -> CH3D + D reactions agree with experimental results to within 25% for all data points. Transition state theory is found to predict the kinetic isotope effect accurately when the mass of the transferred atom is unchanged. On the other hand, if the mass of the transferred atom differs between the isotopic reactions, transition state theory fails in the low-temperature regime (T < 400 K), due to the neglect of the tunneling effect.
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