Chandra, AK and Rao, Sreedhara V (1993) Temperature dependence of hydrogen transfer reactions via tunneling at low temperatures. In: International Journal of Quantum Chemistry, 47 (6). pp. 437-448.
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In this paper, we present a symmetrical and adiabatic reaction path for hydrogen transfer from methane by methyl by an ab initio method using the 6-31G** basis set with the MP2 corrections for UHF/6-31G** optimized geometries. The theoretical barrier is fitted with the symmetric Eckart function. We, then, take thermal averages of the rate constant (k) considering the discrete nature of the C-H oscillators and the continuous character of the various low-frequency modes of the composite system. Finally, we present a linear relation between log k and temperature. It is shown that this relation gives a good description of the kinetic results of both thermal and photochemical H-transfer reactions in the region of low temperatures.
|Item Type:||Journal Article|
|Additional Information:||The copyright belongs to John Wiley & Sons, Inc.|
|Department/Centre:||Division of Chemical Sciences > Inorganic & Physical Chemistry|
|Date Deposited:||14 Feb 2007|
|Last Modified:||19 Sep 2010 04:21|
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