A primer on qualitative valence bond theory - a theory coming of age

被引：14

作者：

Shaik, Sason ^{[1
,2
]}

Hiberty, Philippe C. ^{[3
]}

机构：

[1] Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel

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

[3] Univ Paris 11, CNRS UMR 8000, Lab Chim Phys, F-19405 Orsay, France

来源：

WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE | 2011年 / 1卷 / 01期

基金：

美国国家科学基金会;

关键词：

ELECTRON SIGMA-BONDS; TRANSITION-STATES; SN2; REACTION; REACTIVITY; MOLECULES; BARRIERS;

D O I：

10.1002/wcms.7

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The use of valence bond (VB) theory as a general and wide-ranging qualitative matrix of ideas and predictions is highlighted. Applications are demonstrated for chemical reactivity, properties of polyradicals, excited states, and chemical bonding. Highlighted subtopics include estimations of reaction barriers from simple properties of reactants and products; predictions of stable intermediates in organic, inorganic, and organometallic reactions; and predictions of reaction stereoselectivity. Additional coverage includes a pictorial model for ground and excited states of polyenes and polyradicals, predictions of Hund's rule violations, spin density polarizations and shifts, and a bonding rule in excited states of conjugated molecules. Discussion of new bonding ideas shows the far-reaching prospects of qualitative VB theory. C (C) 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 18-29 DOI: 10.1002/wcms.7

引用

页码：18 / 29

页数：12

共 56 条

[1]

[Anonymous], 2007, CHEM GUIDE VALENCE B

[2]

[Anonymous], 1960, The Nature of the Chemical Bond, 3rd ed

[3]

Berson J.A., 1999, CHEM CREATIVITY, V1st

[4] Computer modeling of enzyme catalysis and its relationship to concepts in physical organic chemistry [J].

Braun-Sand, S ;

Olsson, MHM ;

Warshel, A .

ADVANCES IN PHYSICAL ORGANIC CHEMISTRY, VOL 40, 2005, 40 :201-245

[5] A THEORETICAL TREATMENT OF NUCLEOPHILIC REACTIVITY IN ADDITIONS TO CARBONYL-COMPOUNDS - ROLE OF THE VERTICAL IONIZATION-ENERGY [J].

BUNCEL, E ;

SHAIK, SS ;

UM, IH ;

WOLFE, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (04) :1275-1279

[6] RELATION BETWEEN SINGLET TRIPLET GAPS AND BOND-ENERGIES [J].

CARTER, EA ;

GODDARD, WA III .

JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (06) :998-1001

[7] Valence Bond Perturbation Theory. A Valence Bond Method That Incorporates Perturbation Theory [J].

Chen, Zhenhua ;

Song, Jinshuai ;

Shaik, Sason ;

Hiberty, Philippe C. ;

Wu, Wei .

JOURNAL OF PHYSICAL CHEMISTRY A, 2009, 113 (43) :11560-11569

[8]

Cooper D., 2002, VALENCE BOND THEORY

[9] STUDY OF THE ELECTRONIC STATES OF THE BENZENE MOLECULE USING SPIN-COUPLED VALENCE-BOND THEORY [J].

DASILVA, EC ;

GERRATT, J ;

COOPER, DL ;

RAIMONDI, M .

JOURNAL OF CHEMICAL PHYSICS, 1994, 101 (05) :3866-3887

[10] Ferromagnetic bonding:: High spin copper clusters (n+1Cun; n) 2-14) devoid of electron pairs but possessing strong bonding [J].

de Visser, Sam P. ;

Kumar, Devesh ;

Danovich, Mark ;

Nevo, Nir ;

Danovich, David ;

Sharma, Pankaz K. ;

Wu, Wei ;

Shaik, Sason .

JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (27) :8510-8518

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