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科学通报  2011 

HOSO+X(X=F,Cl,Br)的反应机理及电子密度拓扑分析

DOI: 10.1360/972011-75, PP. 1522-1529

Keywords: HOSO,反应机理,速率常数,电子密度拓扑分析

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Abstract:

在CCSD(T)/6-311++G(d,p)//MP2/6-311++G(d,p)水平上研究了HOSO+X(X=F,Cl,Br)的反应机理.优化得到了反应势能曲线上各驻点的几何构型,通过内禀反应坐标(IRC)确认了反应物、中间体、过渡态和产物的相关性.在CCSD(T)/6-311++G(d,p)水平上对计算得到的构型进行了能量校正.应用经典过渡态理论(TST)与变分过渡态理论(CVT),并结合小曲率隧道效应模型(SCT)校正的方法,计算了该反应在200~3000K温度范围内的速率常数kTST,kCVT和kCVT/SCT.计算结果表明HOSO+X(X=F,Cl,Br)反应在单态和三态条件下均可发生,其中单态为主反应通道,HX+SO2为主产物.并利用电子密度拓扑分析方法研究了主反应通道化学键的变化.

References

[1]  2 Lovejoy E R. Kinetic studies of the reactions of mercaptooxy with nitrogen dioxide, nitric oxide, and oxygen. J Phys Chem, 1987, 91:5749-5755??
[2]  3 Frank A J, Sadílek M, Ferrier J G. Hydroxysulfinyl radical and sulfinic acid are stable species in the gas phase. J Am Chem Soc, 1996,118: 11321-11322??
[3]  4 Frank A J, Sadílek M, Ferrier J G. Sulfur oxyacids and radicals in the gas phase. A variable-time neutralization-photoexcitation-reionizationmassspectrometric and ab initio/RRKM study. J Am Chem Soc, 1997, 119: 12343-12353??
[4]  6 Boyd R J, Gupta A, Langler R F. Sulfonyl radicals, sulfinic acid, and related species: An ab initio molecular orbital study. Can J Chem,1980, 58: 331-338??
[5]  7 Binns D, Marshall P. An ab initio study of the reaction of atomic hydrogen with sulfur dioxide. J Chem Phys, 1991, 95: 4941-4947
[6]  8 Zeist W J, Ren Y, Bickelhaupt F M. 卤素及卤素离子的电子结构.中国化学, 2010, 53: 210-215
[7]  9 葛茂发, 马春平. 活性卤素化学. 化学进展, 2009, 21: 308-334
[8]  12 Ishida G, Morokuma K, Komornicki A. The intrinsic reaction coordinate. An ab initio calculation for HNC→HCN and H-+CH4→CH4+H-.J Chem Phys, 1977, 66: 2153-2156
[9]  13 Purvis G D, Bartlett R J. A full coupled-cluster singles and doubles model: The inclusion of disconnected triples. J Chem Phys, 1982, 76:1910-1918??
[10]  1 Glarborg P, Kubel D, Chiang H M. Impact of SO2 and NO on CO oxidation under post-flame conditions. Int J Chem Kinet, 1996, 28:773-790??
[11]  5 Goumri A, Rocha J D R, Laakso D. Characterization of reaction pathways on the potential energy surfaces for H + SO2 and HS + O2. JPhys Chem A, 1999, 103: 11328-11335??
[12]  10 Frisch M J, Head-Gordon M, Pople J A. A direct MP2 gradient method. Chem Phys Lett, 1990, 166: 275-280??
[13]  11 McLean A D, Chandler G S. Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11-18. J Chem Phys,1980, 72: 5639-5648
[14]  14 Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 03, Revision D.01. Pittsburgh: Gaussian, Inc, 2004
[15]  15 Zhang S W, Truong T N. VKLab, Version 1. 0. Salt Lake City, USA: University of Utah, 2001
[16]  16 Biegler-K?nìng F J, Derdau R, Bayles D, et al. W.AIM2000. Version1.0. Bielefeld, Germany: University of Applied Science, 2000
[17]  17 Zheng S J, Cai X H, Meng L P. General Topological Analysis Program. Bloomington: Quantum Chemistry Program Exchange, 1995

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