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题名: Theoretical Determination of the Rate Coefficient for the HO2 + HO2 -> H2O2+O-2 Reaction: Adiabatic Treatment of Anharmonic Torsional Effects
作者: Zhou, Dingyu D. Y.1, 3;  Han, Keli2;  Zhang, Peiyu2;  Harding, Lawrence B.3;  Davis, Michael J.3;  Skodje, Rex T.1, 2, 3
刊名: JOURNAL OF PHYSICAL CHEMISTRY A
发表日期: 2012-03-08
DOI: 10.1021/jp209684s
卷: 116, 期:9, 页:2089-2100
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: The HO2 + HO2 -> H2O2 + O-2 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.
关键词[WOS]: MULTIREFERENCE PERTURBATION-THEORY ;  NEGATIVE ACTIVATION-ENERGIES ;  REFERENCE WAVE-FUNCTIONS ;  TRANSITION-STATE-THEORY ;  SELF-REACTION ;  GAS-PHASE ;  SHOCK-WAVE ;  TEMPERATURE-DEPENDENCE ;  ATMOSPHERIC CHEMISTRY ;  MOLECULAR-HYDROGEN
语种: 英语
WOS记录号: WOS:000301169700015
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/138007
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
2.Acad Sinica, Dalian Inst Chem Phys, Key State Lab React Dynam, Dalian, Peoples R China
3.Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA

Recommended Citation:
Zhou, Dingyu D. Y.,Han, Keli,Zhang, Peiyu,et al. Theoretical Determination of the Rate Coefficient for the HO2 + HO2 -> H2O2+O-2 Reaction: Adiabatic Treatment of Anharmonic Torsional Effects[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2012,116(9):2089-2100.
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