Valence bond Modeling of barriers in the nonidentity hydrogen abstraction reactions, X′•+H-X→X′-H+X• (X′ ≠ X = CH3, SiH3, GeH3, SnH3, PbH3)

被引：30

作者：

Song, LC

Wu, W ^{[1
]}

Dong, KM

Hiberty, PC

Shaik, S

机构：

[1] Xiamen Univ, Dept Chem, Xiamen 361005, Peoples R China

[2] Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China

[3] Univ Paris 11, Grp Chim Theor, Lab Chim Phys, F-91405 Orsay, France

[4] Hebrew Univ Jerusalem, Dept Organ Chem, IL-91904 Jerusalem, Israel

[5] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2002年 / 106卷 / 46期

关键词：

D O I：

10.1021/jp026438y

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Breathing orbital valence bond (BOVB) computations (Hiberty, P. C.; Humbel, S.; Byrman, C. P.; van Lenthe, J. H. J. Chem. Phys. 1994, 101, 5969) are used to obtain nonidentity barriers for hydrogen transfer reactions between X and X' groups, X not equal X' = CH3, SiH3, GeH3, SnH3, PbH3. Modeling of these barriers by means of VB state correlation diagrams (Shaik, S.; Shurki, A. Angew. Chem., Int. Ed. Engl. 1999, 38, 586) leads to a simple expression for the barrier (eq 29) as an interplay of an intrinsic term and the reaction driving force. The equation predicts barrier heights that are compatible with the BOVB computed barrier heights. Its comparison with the Marcus equation shows similarities and differences.

引用

页码：11361 / 11370

页数：10

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