ANHARMONIC EFFECT OF UNIMOLECULAR REACTION: HCO2 -> H+CO2 WITH RRKM THEORY

作者：Gu, Lingzheng; Yao, Li^*; Shao, Ying; Zhong, Haiyang; Yang, Kun; Zhong, Jingjun

来源：Journal of Theoretical and Computational Chemistry, 2010, 9(4): 813-823.

DOI：10.1142/S0219633610006006

• Anharmonic effect
• unimolecular reaction
• rate constant
• Rice-Ramsperger-Kassel-Marcus theory

Anharmonic and harmonic rate constants were calculated in the unimolecular reaction HCO2 -> H + CO2 with Yao and Lin (YL) method. In microcanonical case, the total number of states and density of states increase reasonably with the increasing of the total energy and the temperature. Both in microcanonical and canonical cases, the harmonic rate constants are much higher than those for anharmonic cases, especially in the case of high total energy and temperature, which indicates that anharmonic effect of the reaction is so significant that it is not negligible. The results obtained in this research show that the YL method works well for such unimolecular reactions.

• 出版日期2010-8
• 单位大连海事大学