DFTStudyontheOs+-catalyticReductionReactionofN2OwithH2intheGasPhase

被引：2

作者：

李涛洪 ^{[1
]}

王传铭 ^{[2
]}

余仕问 ^{[3
]}

谢小光 ^{[4
]}

机构：

[1] The Key Laboratory of Forest Resources Conservation and Use in the Southwest Mountains of China,Southwest Forestry University

[2] Department of Biology,Honghe University

[3] Department of Chemistry,Qujing Normal University

[4] Department of Chemistry,Yunnan University

来源：

结构化学 | 2011年 / 30卷 / 04期

关键词：

DFT; gas phase; catalytic reduction; mechanism;

D O I：

10.14102/j.cnki.0254-5861.2011.04.019

中图分类号：

O643.32 [催化反应];

学科分类号：

081705 ;

摘要：

The Os+-catalytic reduction of N2O by H2 in gas phase has been theoretically investigated with B3LYP method.The reaction mechanisms on the sextet and quartet surfaces were found to be similar.The calculated sextet potential energy profiles show that the two reactions involved in the catalytic cycle,Os+ + N2O → OsO+ + N2 and OsO+ + H2 → Os+ + H2O,have barriers of 28.3 and 123.3 kJ/mol,respectively.In contrast,the reactions on the quartet surfaces are energetically much more favorable.These results rationalize the experimentally observed low catalytic reactivity of sextet(ground-state) Os+.Further,the crossing between the sextet and quartet surfaces are also suggested and qualitatively discussed.

引用

页码：580 / 586

页数：7

共 26 条

[1]

Baranov,V.,Javahery,G.,Hopkinson,A.C.,Bohme,D.K. Journal of the American Chemical Society . 1995

[2]

Li,T.H.,Wang,C.M.,Shi,W.Y.,Liu,X.Y.,Fu,H.,Xie,X.G. Chinese Chemical Letters . 2009

[3]

Rondinelli,F.,Russo,N.,Toscano,M. Inorganic Chemistry . 2007

[4]

Koyanagi,G.K.,Bohme,D.K. J.Phys.Chem.A . 2001

[5]

Becke,A.D. The Journal of Chemical Physics . 1993

[6]

Lavrov,V.V.,Blagojevic,V.,Koyanagi,G.K.,Orlova,G.,Bohme,D.K. J.Phys.Chem.A . 2004

[7]

Dai,G.L.,Fan,K.N. J.Mol.Struct.(Theochem.) . 2007

[8]

Kappes,M.M.,Staley,R.H. Journal of the American Chemical Society . 1981

[9]

Li,T.H.,Wang,C.M.,Xie,X.G. Chinese Physics Letter . 2008

[10]

Contracted Gaussian basis sets for molecular calculations I. Second row atoms, Z=11-18. McLean AD,Chandler GS. Journal of Chemical Physics,The . 1980

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