Theoretical Determination of the Rate Coefficient for the HO2聽+ HO2 鈫?H2O2+O2 Reaction: Adiabatic Treatment of Anharmonic Torsional Effect

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• 作者：Dingyu D. Y. Zhou ; Keli Han ; Peiyu Zhang ; Lawrence B. Harding ; Michael J. Davis ; Rex T. Skodje
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：March 8, 2012
• 年：2012
• 卷：116
• 期：9
• 页码：2089-2100
• 全文大小：504K
• 年卷期：v.116,no.9(March 8, 2012)
• ISSN：1520-5215

文摘

The HO₂ + HO₂ 鈫?H₂O₂ + O₂ chemical reaction is studied using statistical rate theory in conjunction with high level ab initio electronic structure calculations. A new theoretical rate coefficient is generated that is appropriate for both high and low temperature regimes. The transition state region for the ground triplet potential energy surface is characterized using the CASPT2/CBS/aug-cc-pVTZ method with 14 active electrons and 10 active orbitals. The reaction is found to proceed through an intermediate complex bound by approximately 9.79 kcal/mol. There is no potential barrier in the entrance channel, although the free energy barrier was determined using a large Monte Carlo sampling of the HO₂ orientations. The inner (tight) transition state lies below the entrance threshold. It is found that this inner transition state exhibits two saddle points corresponding to torsional conformations of the complex. A unified treatment based on vibrational adiabatic theory is presented that permits the reaction to occur on an equal footing for any value of the torsional angle. The quantum tunneling is also reformulated based on this new approach. The rate coefficient obtained is in good agreement with low temperature experimental results but is significantly lower than the results of shock tube experiments for high temperatures.