Anharmonic effect of the unimolecular dissociation of CH3COOH |
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Authors: | Liwei Zhang Qian Li Guiqiu Wang SH Lin |
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Institution: | 1. Department of Physics, Dalian Maritime University, Dalian, China;2. Department of Applied Chemistry, National Chiao-Tung University, Hsin-chu, Taiwan |
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Abstract: | Anharmonic and harmonic rate constants of the reactions have been calculated with the Rice–Ramsperger–Kassel–Marcus theory, and the anharmonic results are higher than the harmonic ones. The anharmonic effect and isotopic effect on the decomposition reactions have also been examined. The anharmonic effect in all the four reactions is obvious, especially at the high temperatures or energies. Relatively, the anharmonic effect on the reaction trans-acetic acid → TS2 radical is the least obvious among the four reactions. In the microcanonical system, the difference of the rate constants between the deuterated results and the non-deuterated results is not negligible; in other words, the isotopic effect is obvious in all the four reactions. Among these reactions, three of the deuterated results (d, d3 and d4) have a big difference. |
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Keywords: | anharmonic effect unimolecular reaction rate constant RRKM method isotopic effect |
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