A chemist's guide to valence bond theory:
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| Main Authors: | , |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
Hoboken, NJ
Wiley
2008
|
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XIV, 316 S. graph. Darst. |
| ISBN: | 9780470037355 |
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MARC
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| 245 | 1 | 0 | |a A chemist's guide to valence bond theory |c Sason Shaik ; Philippe C. Hiberty |
| 246 | 1 | 3 | |a Valence bond theory |
| 264 | 1 | |a Hoboken, NJ |b Wiley |c 2008 | |
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| _version_ | 1804137293903036416 |
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| adam_text | A CHEMIST S GUIDE TO VALENCE BOND THEORY SASON SHAIK THE HEBREW
UNIVERSITY JERUSALEM, ISRAEL PHILIPPE C. HIBERTY UNIVERSITE DE PARIS-SUD
ORSAY, FRANCE BICENTENNIAL 3ICCNTENNIAL WILEY-INTERSCIENCE A JOHN WILEY
& SONS, INC., PUBLICATION CONTENTS PREFACE XIII 1 A BRIEF STORY OF
VALENCE BOND THEORY, ITS RIVALRY WITH MOLECULAR ORBITAL THEORY, ITS
DEMISE, AND RESURGENCE 1 1.1 ROOTSOFVB THEORY 2 1.2 ORIGINS OF MO THEORY
AND THE ROOTS OF VB-MO RIVALRY 5 1.3 ONE THEORY IS UP THE OTHER IS DOWN
7 1.4 MYTHICAL FAILURES OF VB THEORY: MORE GROUND IS GAINED BY MO THEORY
8 1.5 ARE THE FAILURES OF VB THEORY REAL? 12 1.5.1 THE0 2 FAILURE 12
1.5.2 THE C 4 H 4 FAILURE 13 1.5.3 THE C 5 H 5+ FAILURE 13 1.5.4 THE
FAILURE ASSOCIATED WITH THE PHOTOELECTRON SPECTROSCOPY OF CH 4 13 1.6
VALENCE BOND IS A LEGITIMATE THEORY ALONGSIDE MOLECULAR ORBITAL THEORY
14 1.7 MODERN VB THEORY: VALENCE BOND THEORY IS COMING OF AGE 14 2 A
BRIEF TOUR THROUGH SOME VALENCE BOND OUTPUTS AND TERMINOLOGY 26 2.1
VALENCE BOND OUTPUT FOR THE H 2 MOLECULE 26 2.2 VALENCE BOND MIXING
DIAGRAMS 32 2.3 VALENCE BOND OUTPUT FOR THE HF MOLECULE 33 3 BASIC
VALENCE BOND THEORY 40 3.1 WRITING AND REPRESENTING VALENCE BOND WAVE
FUNCTIONS 40 3.1.1 VB WAVE FUNCTIONS WITH LOCALIZED ATOMIC ORBITALS 40
3.1.2 VALENCE BOND WAVE FUNCTIONS WITH SEMILOCALIZED AOS 41 3.1.3
VALENCE BOND WAVE FUNCTIONS WITH FRAGMENT ORBITALS 42 3.1.4 WRITING
VALENCE BOND WAVE FUNCTIONS BEYOND THE 2E/2C CASE 43 3.1.5 PICTORIAL
REPRESENTATION OF VALENCE BOND WAVE FUNCTIONS BY BOND DIAGRAMS 45 VIII
CONTENTS 3.2 OVERLAPS BETWEEN DETERMINANTS 45 3.3 VALENCE BOND FORMALISM
USING THE EXACT HAMILTONIAN 46 3.3.1 PURELY COVALENT SINGLET AND TRIPLET
REPULSIVE STATES 47 3.3.2 CONFIGURATION INTERACTION INVOLVING IONIC
TERMS 49 3.4 VALENCE BOND FORMALISM USING AN EFFECTIVE HAMILTONIAN 49
3.5 SOME SIMPLE FORMULAS FOR ELEMENTARY INTERACTIONS 51 3.5.1 THE
TWO-ELECTRON BOND 51 3.5.2 REPULSIVE INTERACTIONS IN VALENCE BOND THEORY
52 3.5.3 MIXING OF DEGENERATE VALENCE BOND STRUCTURES 53 3.5.4
NONBONDING INTERACTIONS IN VALENCE BOND THEORY 54 3.6 STRUCTURAL
COEFFICIENTS AND WEIGHTS OF VALENCE BOND WAVE FUNCTIONS 56 3.7 BRIDGES
BETWEEN MOLECULAR ORBITAL AND VALENCE BOND THEORIES 56 3.7.1 COMPARISON
OF QUALITATIVE VALENCE BOND AND MOLECULAR ORBITAL THEORIES 57 3.7.2 THE
RELATIONSHIP BETWEEN MOLECULAR ORBITAL AND VALENCE BOND WAVE FUNCTIONS
58 3.7.3 LOCALIZED BOND ORBITALS: A PICTORIAL BRIDGE BETWEEN MOLECULAR
ORBITAL AND VALENCE BOND WAVE FUNCTIONS 60 APPENDIX 65 3.A.1
NORMALIZATION CONSTANTS, ENERGIES, OVERLAPS, AND MATRIX ELEMENTS OF
VALENCE BOND WAVE FUNCTIONS 65 3.A. 1.1 ENERGY AND SELF-OVERLAP OF AN
ATOMIC ORBITAL - BASED DETERMINANT 66 3.A. 1.2 HAMILTONIAN MATRIX
ELEMENTS AND OVERLAPS BETWEEN ATOMIC ORBITAL-BASED DETERMINANTS 68 3.A.2
SIMPLE GUIDELINES FOR VALENCE BOND MIXING 68 EXERCISES 70 ANSWERS 74
MAPPING MOLECULAR ORBITAL*CONFIGURATION INTERACTION TO VALENCE BOND WAVE
FUNCTIONS 81 4.1 GENERATING A SET OF VALENCE BOND STRUCTURES 81 4.2
MAPPING A MOLECULAR ORBITAL-CONFIGURATION INTERACTION WAVE FUNCTION INTO
A VALENCE BOND WAVE FUNCTION 83 4.2.1 EXPANSION OF MOLECULAR ORBITAL
DETERMINANTS IN TERMS OF ATOMIC ORBITAL DETERMINANTS 83 4.2.2 PROJECTING
THE MOLECULAR ORBITAL-CONFIGURATION INTERACTION WAVE FUNCTION ONTO THE
RUMER BASIS OF VALENCE BOND STRUCTURES 85 4.2.3 AN EXAMPLE: THE
HARTREE-FOCK WAVE FUNCTION OFBUTADIENE 86 CONTENTS IX 4.3 USING
HALF-DETERMINANTS TO CALCULATE OVERLAPS BETWEEN VALENCE BOND STRUCTURES
88 EXERCISES 89 ANSWERS 90 5 ARE THE FAILURES OF VALENCE BOND THEORY
REAL? 94 5.1 INTRODUCTION 94 5.2 THE TRIPLET GROUND STATE OF DIOXYGEN 94
5.3 AROMATICITY-ANTIAROMATICITY IN IONIC RINGS C N H N+/ 97 5.4
AROMATICITY/ANTIAROMATICITY IN NEUTRAL RINGS 100 5.5 THE VALENCE
IONIZATION SPECTRUM OF CH 4 104 5.6 THE VALENCE IONIZATION SPECTRUM OF H
2 0 AND THE RABBIT-EAR LONE PAIRS 106 5.7 A SUMMARY 109 EXERCISES 111
ANSWERS 112 6 VALENCE BOND DIAGRAMS FOR CHEMICAL REACTIVITY 116 6.1
INTRODUCTION 116 6.2 TWO ARCHETYPAL VALENCE BOND DIAGRAMS 116 6.3 THE
VALENCE BOND STATE CORRELATION DIAGRAM MODEL AND ITS GENERAL OUTLOOK ON
REACTIVITY 117 6.4 CONSTRUCTION OF VALENCE BOND STATE CORRELATION
DIAGRAMS FOR ELEMENTARY PROCESSES 119 6.4.1 VALENCE BOND STATE
CORRELATION DIAGRAMS FOR RADICAL EXCHANGE REACTIONS 119 6.4.2 VALENCE
BOND STATE CORRELATION DIAGRAMS FOR REACTIONS BETWEEN NUCLEOPHILES AND
ELECTROPHILES 122 6.4.3 GENERALIZATION OF VALENCE BOND STATE CORRELATION
DIAGRAMS FOR REACTIONS INVOLVING REORGANIZATION OF COVALENT BONDS 124
6.5 BARRIER EXPRESSIONS BASED ON THE VALENCE BOND STATE CORRELATION
DIAGRAM MODEL 126 6.5.1 SOME GUIDELINES FOR QUANTITATIVE APPLICATIONS OF
THE VALENCE BOND STATE CORRELATION DIAGRAM MODEL 128 6.6 MAKING
QUALITATIVE REACTIVITY PREDICTIONS WITH THE VALENCE BOND STATE
CORRELATION DIAGRAM 128 6.6.1 REACTIVITY TRENDS IN RADICAL EXCHANGE
REACTIONS 130 6.6.2 REACTIVITY TRENDS IN ALLOWED AND FORBIDDEN REACTIONS
132 6.6.3 REACTIVITY TRENDS IN OXIDATIVE-ADDITION REACTIONS 133 6.6.4
REACTIVITY TRENDS IN REACTIONS BETWEEN NUCLEOPHILES AND ELECTROPHILES
136 X CONTENTS 6.6.5 CHEMICAL SIGNIFICANCE OF THE F FACTOR 138 6.6.6
MAKING STEREOCHEMICAL PREDICTIONS WITH THE VBSCD MODEL 138 6.6.7
PREDICTING TRANSITION STATE STRUCTURES WITH THE VALENCE BOND STATE
CORRELATION DIAGRAM MODEL 140 6.6.8 TRENDS IN TRANSITION STATE RESONANCE
ENERGIES 141 6.7 VALENCE BOND CONFIGURATION MIXING DIAGRAMS: GENERAL
FEATURES 144 6.8 VALENCE BOND CONFIGURATION MIXING DIAGRAM WITH IONIC
INTERMEDIATE CURVES 144 6.8.1 VALENCE BOND CONFIGURATION MIXING DIAGRAMS
FOR PROTON-TRANSFER PROCESSES 145 6.8.2 INSIGHTS FROM VALENCE BOND
CONFIGURATION MIXING DIAGRAMS: ONE ELECTRON LESS-ONE ELECTRON MORE 146
6.8.3 NUCLEOPHILIC SUBSTITUTION ON SILICON: STABLE HYPERCOORDINATED
SPECIES 147 6.9 VALENCE BOND CONFIGURATION MIXING DIAGRAM WITH
INTERMEDIATES NASCENT FROM FOREIGN STATES 149 6.9.1 THE MECHANISM OF
NUCLEOPHILIC SUBSTITUTION OF ESTERS 149 6.9.2 THE SRN2 AND SRN2 C
MECHANISMS 150 6.10 VALENCE BOND STATE CORRELATION DIAGRAM: A GENERAL
MODEL FOR ELECTRONIC DELOCALIZATION IN CLUSTERS 153 6.10.1 WHAT IS THE
DRIVING FORCE FOR THE D 6H GEOMETRY OF BENZENE, CT OR TT? 154 6.11
VALENCE BOND STATE CORRELATION DIAGRAM: APPLICATION TO PHOTOCHEMICAL
REACTIVITY 157 6.11.1 PHOTOREACTIVITY IN 3E/3C REACTIONS 158 6.11.2
PHOTOREACTIVITY IN 4E/3C REACTIONS 159 6.12 A SUMMARY 163 EXERCISES 171
ANSWERS 1 76 USING VALENCE BOND THEORY TO COMPUTE AND CONCEPTUALIZE
EXCITED STATES 193 7.1 EXCITED STATES OF A SINGLE BOND 194 7.2 EXCITED
STATES OF MOLECULES WITH CONJUGATED BONDS 196 7.2.1 USE OF MOLECULAR
SYMMETRY TO GENERATE COVALENT EXCITED STATES BASED ON VALENCE BOND
THEORY 197 7.2.2 COVALENT EXCITED STATES OF POLYENES 209 7.3 A SUMMARY
212 EXERCISES 215 ANSWERS 216 CONTENTS XI SPIN HAMILTONIAN VALENCE BOND
THEORY AND ITS APPLICATIONS TO ORGANIC RADICALS, DIRADICALS, AND
POLYRADICALS 222 8.1 A TOPOLOGICAL SEMIEMPIRICAL HAMILTONIAN 223 8.2
APPLICATIONS 225 8.2.1 GROUND STATES OF POLYENES AND HUND S RULE
VIOLATIONS 225 8.2.2 SPIN DISTRIBUTION IN ALTERNANT RADICALS 227 8.2.3
RELATIVE STABILITIES OF POLYENES 228 8.2.4 EXTENDING OVCHINNIKOV S RULE
TO SEARCH FOR BISTABLE HYDROCARBONS 230 8.3 ASUMMARY 231 EXERCISES 232
ANSWERS 234 CURRENTLY AVAILABLE AB INITIO VALENC E BOND COMPUTATIONAL
METHODS AND THEIR PRINCIPLES 238 9.1 INTRODUCTION 238 9.2 VALENCE BOND
METHODS BASED ON SEMILOCALIZED ORBITALS 239 9.2.1 THE GENERALIZED
VALENCE BOND METHOD 240 9.2.2 THE SPIN-COUPLED VALENCE BOND METHOD 242
9.2.3 THE CASVB METHOD 243 9.2.4 THE GENERALIZED RESONATING VALENCE BOND
METHOD 245 9.2.5 MULTICONFIGURATION VALENCE BOND METHODS WITH OPTIMIZED
ORBITALS 246 9.3 VALENCE BOND METHODS BASED ON LOCALIZED ORBITALS 247
9.3.1 VALENCE BOND SELF-CONSISTENT FIELD METHOD WITH LOCALIZED ORBITALS
247 9.3.2 THE BREATHING-ORBITAL VALENCE BOND METHOD 249 9.3.3 THE
VALENCE BOND CONFIGURATION INTERACTION METHOD 252 9.4 METHODS FOR
GETTING VALENCE BOND QUANTITIES FROM MOLECULAR ORBITAL-BASED PROCEDURES
253 9.4.1 USING STANDARD MOLECULAR ORBITAL SOFTWARE TO COMPUTE SINGLE
VALENCE BOND STRUCTURES OR DETERMINANTS 253 9.4.2 THE BLOCK-LOCALIZED
WAVE FUNCTION AND RELATED METHODS 254 9.5 A VALENCE BOND METHOD WITH
POLANZABLE CONTINUUM MODEL 255 APPENDIX 257 9.A. 1 SOME AVAILABLE
VALENCE BOND PROGRAMS 257 9. A. 1.1 THE TURTLE SOFTWARE 257 9.A.1.2 THE
XMVB PROGRAM 257 XII CONTENTS 9.A.1.3 THE CRUNCH SOFTWARE 257 9.A.1.4
THE VB2000 SOFTWARE 258 9.A.2 IMPLEMENTATIONS OF VALENCE BOND METHODS IN
STANDARD AB INITIO PACKAGE S 258 10 DO YOUR OWN VALENCE BOND
CALCULATIONS*A PRACTICAL GUIDE 271 10.1 INTRODUCTION 271 10.2 WAVE
FUNCTIONS AND ENERGIES FOR THE GROUND STATE OF F 2 271 10.2.1 GVB, SC,
AND VBSCF METHODS 272 10.2.2 THE BOVB METHOD 276 10.2.3 THE VBCI METHOD
280 10.3 VALENCE BOND CALCULATIONS OF DIABATIC STATES AND RESONANCE
ENERGIES 281 10.3.1 DEFINITION OF DIABATIC STATES 282 10.3.2
CALCULATIONS OF MEANINGFUL DIABETIC STATES 282 10.3.3 RESONANCE ENERGIES
284 10.4 COMMENTS ON CALCULATIONS OF VBSCDS AND VBCMDS 287 APPENDIX 290
LO.A.L CALCULATING AT THE SD-BOVB LEVEL IN LOW SYMMETRY CASES 290
EPILOGUE 304 GLOSSARY 306 INDEX 311
|
| adam_txt |
A CHEMIST'S GUIDE TO VALENCE BOND THEORY SASON SHAIK THE HEBREW
UNIVERSITY JERUSALEM, ISRAEL PHILIPPE C. HIBERTY UNIVERSITE DE PARIS-SUD
ORSAY, FRANCE BICENTENNIAL 3ICCNTENNIAL WILEY-INTERSCIENCE A JOHN WILEY
& SONS, INC., PUBLICATION CONTENTS PREFACE XIII 1 A BRIEF STORY OF
VALENCE BOND THEORY, ITS RIVALRY WITH MOLECULAR ORBITAL THEORY, ITS
DEMISE, AND RESURGENCE 1 1.1 ROOTSOFVB THEORY 2 1.2 ORIGINS OF MO THEORY
AND THE ROOTS OF VB-MO RIVALRY 5 1.3 ONE THEORY IS UP THE OTHER IS DOWN
7 1.4 MYTHICAL FAILURES OF VB THEORY: MORE GROUND IS GAINED BY MO THEORY
8 1.5 ARE THE FAILURES OF VB THEORY REAL? 12 1.5.1 THE0 2 FAILURE 12
1.5.2 THE C 4 H 4 FAILURE 13 1.5.3 THE C 5 H 5+ FAILURE 13 1.5.4 THE
FAILURE ASSOCIATED WITH THE PHOTOELECTRON SPECTROSCOPY OF CH 4 13 1.6
VALENCE BOND IS A LEGITIMATE THEORY ALONGSIDE MOLECULAR ORBITAL THEORY
14 1.7 MODERN VB THEORY: VALENCE BOND THEORY IS COMING OF AGE 14 2 A
BRIEF TOUR THROUGH SOME VALENCE BOND OUTPUTS AND TERMINOLOGY 26 2.1
VALENCE BOND OUTPUT FOR THE H 2 MOLECULE 26 2.2 VALENCE BOND MIXING
DIAGRAMS 32 2.3 VALENCE BOND OUTPUT FOR THE HF MOLECULE 33 3 BASIC
VALENCE BOND THEORY 40 3.1 WRITING AND REPRESENTING VALENCE BOND WAVE
FUNCTIONS 40 3.1.1 VB WAVE FUNCTIONS WITH LOCALIZED ATOMIC ORBITALS 40
3.1.2 VALENCE BOND WAVE FUNCTIONS WITH SEMILOCALIZED AOS 41 3.1.3
VALENCE BOND WAVE FUNCTIONS WITH FRAGMENT ORBITALS 42 3.1.4 WRITING
VALENCE BOND WAVE FUNCTIONS BEYOND THE 2E/2C CASE 43 3.1.5 PICTORIAL
REPRESENTATION OF VALENCE BOND WAVE FUNCTIONS BY BOND DIAGRAMS 45 VIII
CONTENTS 3.2 OVERLAPS BETWEEN DETERMINANTS 45 3.3 VALENCE BOND FORMALISM
USING THE EXACT HAMILTONIAN 46 3.3.1 PURELY COVALENT SINGLET AND TRIPLET
REPULSIVE STATES 47 3.3.2 CONFIGURATION INTERACTION INVOLVING IONIC
TERMS 49 3.4 VALENCE BOND FORMALISM USING AN EFFECTIVE HAMILTONIAN 49
3.5 SOME SIMPLE FORMULAS FOR ELEMENTARY INTERACTIONS 51 3.5.1 THE
TWO-ELECTRON BOND 51 3.5.2 REPULSIVE INTERACTIONS IN VALENCE BOND THEORY
52 3.5.3 MIXING OF DEGENERATE VALENCE BOND STRUCTURES 53 3.5.4
NONBONDING INTERACTIONS IN VALENCE BOND THEORY 54 3.6 STRUCTURAL
COEFFICIENTS AND WEIGHTS OF VALENCE BOND WAVE FUNCTIONS 56 3.7 BRIDGES
BETWEEN MOLECULAR ORBITAL AND VALENCE BOND THEORIES 56 3.7.1 COMPARISON
OF QUALITATIVE VALENCE BOND AND MOLECULAR ORBITAL THEORIES 57 3.7.2 THE
RELATIONSHIP BETWEEN MOLECULAR ORBITAL AND VALENCE BOND WAVE FUNCTIONS
58 3.7.3 LOCALIZED BOND ORBITALS: A PICTORIAL BRIDGE BETWEEN MOLECULAR
ORBITAL AND VALENCE BOND WAVE FUNCTIONS 60 APPENDIX 65 3.A.1
NORMALIZATION CONSTANTS, ENERGIES, OVERLAPS, AND MATRIX ELEMENTS OF
VALENCE BOND WAVE FUNCTIONS 65 3.A. 1.1 ENERGY AND SELF-OVERLAP OF AN
ATOMIC ORBITAL - BASED DETERMINANT 66 3.A. 1.2 HAMILTONIAN MATRIX
ELEMENTS AND OVERLAPS BETWEEN ATOMIC ORBITAL-BASED DETERMINANTS 68 3.A.2
SIMPLE GUIDELINES FOR VALENCE BOND MIXING 68 EXERCISES 70 ANSWERS 74
MAPPING MOLECULAR ORBITAL*CONFIGURATION INTERACTION TO VALENCE BOND WAVE
FUNCTIONS 81 4.1 GENERATING A SET OF VALENCE BOND STRUCTURES 81 4.2
MAPPING A MOLECULAR ORBITAL-CONFIGURATION INTERACTION WAVE FUNCTION INTO
A VALENCE BOND WAVE FUNCTION 83 4.2.1 EXPANSION OF MOLECULAR ORBITAL
DETERMINANTS IN TERMS OF ATOMIC ORBITAL DETERMINANTS 83 4.2.2 PROJECTING
THE MOLECULAR ORBITAL-CONFIGURATION INTERACTION WAVE FUNCTION ONTO THE
RUMER BASIS OF VALENCE BOND STRUCTURES 85 4.2.3 AN EXAMPLE: THE
HARTREE-FOCK WAVE FUNCTION OFBUTADIENE 86 CONTENTS IX 4.3 USING
HALF-DETERMINANTS TO CALCULATE OVERLAPS BETWEEN VALENCE BOND STRUCTURES
88 EXERCISES 89 ANSWERS 90 5 ARE THE "FAILURES" OF VALENCE BOND THEORY
REAL? 94 5.1 INTRODUCTION 94 5.2 THE TRIPLET GROUND STATE OF DIOXYGEN 94
5.3 AROMATICITY-ANTIAROMATICITY IN IONIC RINGS C N H N+/ 97 5.4
AROMATICITY/ANTIAROMATICITY IN NEUTRAL RINGS 100 5.5 THE VALENCE
IONIZATION SPECTRUM OF CH 4 104 5.6 THE VALENCE IONIZATION SPECTRUM OF H
2 0 AND THE "RABBIT-EAR" LONE PAIRS 106 5.7 A SUMMARY 109 EXERCISES 111
ANSWERS 112 6 VALENCE BOND DIAGRAMS FOR CHEMICAL REACTIVITY 116 6.1
INTRODUCTION 116 6.2 TWO ARCHETYPAL VALENCE BOND DIAGRAMS 116 6.3 THE
VALENCE BOND STATE CORRELATION DIAGRAM MODEL AND ITS GENERAL OUTLOOK ON
REACTIVITY 117 6.4 CONSTRUCTION OF VALENCE BOND STATE CORRELATION
DIAGRAMS FOR ELEMENTARY PROCESSES 119 6.4.1 VALENCE BOND STATE
CORRELATION DIAGRAMS FOR RADICAL EXCHANGE REACTIONS 119 6.4.2 VALENCE
BOND STATE CORRELATION DIAGRAMS FOR REACTIONS BETWEEN NUCLEOPHILES AND
ELECTROPHILES 122 6.4.3 GENERALIZATION OF VALENCE BOND STATE CORRELATION
DIAGRAMS FOR REACTIONS INVOLVING REORGANIZATION OF COVALENT BONDS 124
6.5 BARRIER EXPRESSIONS BASED ON THE VALENCE BOND STATE CORRELATION
DIAGRAM MODEL 126 6.5.1 SOME GUIDELINES FOR QUANTITATIVE APPLICATIONS OF
THE VALENCE BOND STATE CORRELATION DIAGRAM MODEL 128 6.6 MAKING
QUALITATIVE REACTIVITY PREDICTIONS WITH THE VALENCE BOND STATE
CORRELATION DIAGRAM 128 6.6.1 REACTIVITY TRENDS IN RADICAL EXCHANGE
REACTIONS 130 6.6.2 REACTIVITY TRENDS IN ALLOWED AND FORBIDDEN REACTIONS
132 6.6.3 REACTIVITY TRENDS IN OXIDATIVE-ADDITION REACTIONS 133 6.6.4
REACTIVITY TRENDS IN REACTIONS BETWEEN NUCLEOPHILES AND ELECTROPHILES
136 X CONTENTS 6.6.5 CHEMICAL SIGNIFICANCE OF THE F FACTOR 138 6.6.6
MAKING STEREOCHEMICAL PREDICTIONS WITH THE VBSCD MODEL 138 6.6.7
PREDICTING TRANSITION STATE STRUCTURES WITH THE VALENCE BOND STATE
CORRELATION DIAGRAM MODEL 140 6.6.8 TRENDS IN TRANSITION STATE RESONANCE
ENERGIES 141 6.7 VALENCE BOND CONFIGURATION MIXING DIAGRAMS: GENERAL
FEATURES 144 6.8 VALENCE BOND CONFIGURATION MIXING DIAGRAM WITH IONIC
INTERMEDIATE CURVES 144 6.8.1 VALENCE BOND CONFIGURATION MIXING DIAGRAMS
FOR PROTON-TRANSFER PROCESSES 145 6.8.2 INSIGHTS FROM VALENCE BOND
CONFIGURATION MIXING DIAGRAMS: ONE ELECTRON LESS-ONE ELECTRON MORE 146
6.8.3 NUCLEOPHILIC SUBSTITUTION ON SILICON: STABLE HYPERCOORDINATED
SPECIES 147 6.9 VALENCE BOND CONFIGURATION MIXING DIAGRAM WITH
INTERMEDIATES NASCENT FROM "FOREIGN STATES" 149 6.9.1 THE MECHANISM OF
NUCLEOPHILIC SUBSTITUTION OF ESTERS 149 6.9.2 THE SRN2 AND SRN2 C
MECHANISMS 150 6.10 VALENCE BOND STATE CORRELATION DIAGRAM: A GENERAL
MODEL FOR ELECTRONIC DELOCALIZATION IN CLUSTERS 153 6.10.1 WHAT IS THE
DRIVING FORCE FOR THE D 6H GEOMETRY OF BENZENE, CT OR TT? 154 6.11
VALENCE BOND STATE CORRELATION DIAGRAM: APPLICATION TO PHOTOCHEMICAL
REACTIVITY 157 6.11.1 PHOTOREACTIVITY IN 3E/3C REACTIONS 158 6.11.2
PHOTOREACTIVITY IN 4E/3C REACTIONS 159 6.12 A SUMMARY 163 EXERCISES 171
ANSWERS 1 76 USING VALENCE BOND THEORY TO COMPUTE AND CONCEPTUALIZE
EXCITED STATES 193 7.1 EXCITED STATES OF A SINGLE BOND 194 7.2 EXCITED
STATES OF MOLECULES WITH CONJUGATED BONDS 196 7.2.1 USE OF MOLECULAR
SYMMETRY TO GENERATE COVALENT EXCITED STATES BASED ON VALENCE BOND
THEORY 197 7.2.2 COVALENT EXCITED STATES OF POLYENES 209 7.3 A SUMMARY
212 EXERCISES 215 ANSWERS 216 CONTENTS XI SPIN HAMILTONIAN VALENCE BOND
THEORY AND ITS APPLICATIONS TO ORGANIC RADICALS, DIRADICALS, AND
POLYRADICALS 222 8.1 A TOPOLOGICAL SEMIEMPIRICAL HAMILTONIAN 223 8.2
APPLICATIONS 225 8.2.1 GROUND STATES OF POLYENES AND HUND'S RULE
VIOLATIONS 225 8.2.2 SPIN DISTRIBUTION IN ALTERNANT RADICALS 227 8.2.3
RELATIVE STABILITIES OF POLYENES 228 8.2.4 EXTENDING OVCHINNIKOV'S RULE
TO SEARCH FOR BISTABLE HYDROCARBONS 230 8.3 ASUMMARY 231 EXERCISES 232
ANSWERS 234 CURRENTLY AVAILABLE AB INITIO VALENC E BOND COMPUTATIONAL
METHODS AND THEIR PRINCIPLES 238 9.1 INTRODUCTION 238 9.2 VALENCE BOND
METHODS BASED ON SEMILOCALIZED ORBITALS 239 9.2.1 THE GENERALIZED
VALENCE BOND METHOD 240 9.2.2 THE SPIN-COUPLED VALENCE BOND METHOD 242
9.2.3 THE CASVB METHOD 243 9.2.4 THE GENERALIZED RESONATING VALENCE BOND
METHOD 245 9.2.5 MULTICONFIGURATION VALENCE BOND METHODS WITH OPTIMIZED
ORBITALS 246 9.3 VALENCE BOND METHODS BASED ON LOCALIZED ORBITALS 247
9.3.1 VALENCE BOND SELF-CONSISTENT FIELD METHOD WITH LOCALIZED ORBITALS
247 9.3.2 THE BREATHING-ORBITAL VALENCE BOND METHOD 249 9.3.3 THE
VALENCE BOND CONFIGURATION INTERACTION METHOD 252 9.4 METHODS FOR
GETTING VALENCE BOND QUANTITIES FROM MOLECULAR ORBITAL-BASED PROCEDURES
253 9.4.1 USING STANDARD MOLECULAR ORBITAL SOFTWARE TO COMPUTE SINGLE
VALENCE BOND STRUCTURES OR DETERMINANTS 253 9.4.2 THE BLOCK-LOCALIZED
WAVE FUNCTION AND RELATED METHODS 254 9.5 A VALENCE BOND METHOD WITH
POLANZABLE CONTINUUM MODEL 255 APPENDIX 257 9.A. 1 SOME AVAILABLE
VALENCE BOND PROGRAMS 257 9. A. 1.1 THE TURTLE SOFTWARE 257 9.A.1.2 THE
XMVB PROGRAM 257 XII CONTENTS 9.A.1.3 THE CRUNCH SOFTWARE 257 9.A.1.4
THE VB2000 SOFTWARE 258 9.A.2 IMPLEMENTATIONS OF VALENCE BOND METHODS IN
STANDARD AB INITIO PACKAGE S 258 10 DO YOUR OWN VALENCE BOND
CALCULATIONS*A PRACTICAL GUIDE 271 10.1 INTRODUCTION 271 10.2 WAVE
FUNCTIONS AND ENERGIES FOR THE GROUND STATE OF F 2 271 10.2.1 GVB, SC,
AND VBSCF METHODS 272 10.2.2 THE BOVB METHOD 276 10.2.3 THE VBCI METHOD
280 10.3 VALENCE BOND CALCULATIONS OF DIABATIC STATES AND RESONANCE
ENERGIES 281 10.3.1 DEFINITION OF DIABATIC STATES 282 10.3.2
CALCULATIONS OF MEANINGFUL DIABETIC STATES 282 10.3.3 RESONANCE ENERGIES
284 10.4 COMMENTS ON CALCULATIONS OF VBSCDS AND VBCMDS 287 APPENDIX 290
LO.A.L CALCULATING AT THE SD-BOVB LEVEL IN LOW SYMMETRY CASES 290
EPILOGUE 304 GLOSSARY 306 INDEX 311 |
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| id | DE-604.BV023057979 |
| illustrated | Illustrated |
| index_date | 2024-07-02T19:27:32Z |
| indexdate | 2024-07-09T21:10:00Z |
| institution | BVB |
| isbn | 9780470037355 |
| language | English |
| lccn | 2007040432 |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-016261242 |
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| physical | XIV, 316 S. graph. Darst. |
| publishDate | 2008 |
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| publisher | Wiley |
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| spelling | Shaik, Sason S. Verfasser aut A chemist's guide to valence bond theory Sason Shaik ; Philippe C. Hiberty Valence bond theory Hoboken, NJ Wiley 2008 XIV, 316 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Química teórica larpcal Valence (Theoretical chemistry) Valenz Chemie (DE-588)4187347-6 gnd rswk-swf Valenztheorie Chemie (DE-588)4187351-8 gnd rswk-swf Valenztheorie Chemie (DE-588)4187351-8 s DE-604 Valenz Chemie (DE-588)4187347-6 s Hiberty, Philippe C. Verfasser aut GBV Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016261242&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Shaik, Sason S. Hiberty, Philippe C. A chemist's guide to valence bond theory Química teórica larpcal Valence (Theoretical chemistry) Valenz Chemie (DE-588)4187347-6 gnd Valenztheorie Chemie (DE-588)4187351-8 gnd |
| subject_GND | (DE-588)4187347-6 (DE-588)4187351-8 |
| title | A chemist's guide to valence bond theory |
| title_alt | Valence bond theory |
| title_auth | A chemist's guide to valence bond theory |
| title_exact_search | A chemist's guide to valence bond theory |
| title_exact_search_txtP | A chemist's guide to valence bond theory |
| title_full | A chemist's guide to valence bond theory Sason Shaik ; Philippe C. Hiberty |
| title_fullStr | A chemist's guide to valence bond theory Sason Shaik ; Philippe C. Hiberty |
| title_full_unstemmed | A chemist's guide to valence bond theory Sason Shaik ; Philippe C. Hiberty |
| title_short | A chemist's guide to valence bond theory |
| title_sort | a chemist s guide to valence bond theory |
| topic | Química teórica larpcal Valence (Theoretical chemistry) Valenz Chemie (DE-588)4187347-6 gnd Valenztheorie Chemie (DE-588)4187351-8 gnd |
| topic_facet | Química teórica Valence (Theoretical chemistry) Valenz Chemie Valenztheorie Chemie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016261242&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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