Anharmonic Effect of the Unimolecular Dissociation of Ethyl Radical

作者：Li Qian; Yao Li^*; Shao Ying; Yang Kun

来源：Journal of the Chinese Chemical Society, 2014, 61(3): 309-319.

DOI：10.1002/jccs.201300277

• Anharmonic effect
• Unimolecular reaction
• Rate constant
• RRKM theory
• YL method

The anharmonic and harmonic rate constants have been calculated for the unimolecular dissociation of ethyl radical using the method proposed by Yao and Lin (YL method) at both B3LYP/6-311++G** and MP2/6-311++G** levels. The different rate constants indicate that the results obtained from B3LYP and MP2 method are very close. The anharmonic and tunneling effect of the title reaction has also been examined. The comparison shows that, both in microcanonical and canonical systems, the anharmonic rate constants are higher than those for harmonic cases, especially in the case of high total energies and temperatures, which indicates that anharmonic effect of the unimolecular dissociation of ethyl into C2H4 and H is so significant that cannot be neglected. The tunneling effect is very small for the decomposition of C2H5 radical.

• 出版日期2014-3
• 单位大连海事大学