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Theoretical Determination of the Rate Coefficient for the HO2 + HO2 -> H2O2+O-2 Reaction: Adiabatic Treatment of Anharmonic Torsional Effects
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
2012-03-08
DOI10.1021/jp209684s
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
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
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.
语种英语
WOS记录号WOS:000301169700015
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文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/138007
专题中国科学院大连化学物理研究所
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
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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.
APA Zhou, Dingyu D. Y.,Han, Keli,Zhang, Peiyu,Harding, Lawrence B.,Davis, Michael J.,&Skodje, Rex T..(2012).Theoretical Determination of the Rate Coefficient for the HO2 + HO2 -> H2O2+O-2 Reaction: Adiabatic Treatment of Anharmonic Torsional Effects.JOURNAL OF PHYSICAL CHEMISTRY A,116(9),2089-2100.
MLA Zhou, Dingyu D. Y.,et al."Theoretical Determination of the Rate Coefficient for the HO2 + HO2 -> H2O2+O-2 Reaction: Adiabatic Treatment of Anharmonic Torsional Effects".JOURNAL OF PHYSICAL CHEMISTRY A 116.9(2012):2089-2100.
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