Discovering chemistry with natural bond orbitals / Frank Weinhold, Clark R. Landis.

Format:

Book

Author/Creator:

Weinhold, Frank, 1941-

Contributor:

Landis, Clark R., 1956-

Isaac Norris Library Fund.

Language:

English

Subjects (All):

Chemical bonds.

Molecular orbitals.

Physical Description:

xii, 319 pages, 16 unnumbered pages of plates : illustrations (some color) ; 24 cm

Place of Publication:

Hoboken, N.J. : Wiley, [2012]

Summary:

"This book is about chemical bonds, their intrinsic energies and the corresponding dissociation energies which are relevant in reactivity problems; it is the first book to detail relatively uncomplicated but physically meaningful approaches to molecular properties, an area important to help understand chemical principles and predict chemical properties. The primary goal of this book is to enable students to gain proficiency in using the NBO program to re-express complex many-electron wavefunctions in terms of intuitive chemical concepts and orbital imagery, with minimal distractions from underlying mathematical or programming details"--Provided by publisher.

Contents:

1 Getting Started 1

1.1 Talking to your electronic structure system 1

1.2 Helpful tools 3

1.3 General $NBO keylist usage 4

1.4 Producing orbital imagery 6

Problems and exercises 8

2 Electrons in Atoms 10

2.1 Finding the electrons in atomic wavefunctions 10

2.2 Atomic orbitals and their graphical representation 13

2.3 Atomic electron configurations 18

2.4 How to find electronic orbitals and configurations in NBO output 23

2.5 Natural atomic orbitals and the natural minimal basis 29

Problems and exercises 31

3 Atoms in Molecules 34

3.1 Atomic orbitals in molecules 35

3.2 Atomic configurations and atomic charges in molecules 39

3.3 Atoms in open-shell molecules 44

Problems and exercises 49

4 Hybrids and Bonds in Molecules 51

4.1 Bonds and lone pairs in molecules 52

4.2 Atomic hybrids and bonding geometry 60

4.3 Bond polarity, electronegativity, and Bent's rule 71

4.4 Hypovalent three-center bonds 78

4.5 Open-shell Lewis structures and spin hybrids 82

4.6 Lewis-like structures in transition metal bonding 86

Problems and exercises 89

5 Resonance Delocalization Corrections 92

5.1 The natural Lewis structure perturbative model 93

5.2 Second-order perturbative analysis of donor-acceptor interactions 96

5.3 $Del energetic analysis [integrated ESS/NBO only] 105

5.4 Delocalization tails of natural localized molecular orbitals 113

5.5 How to $CHOOSE alternative Lewis structures 117

5.6 Natural resonance theory 123

Problems and exercises 133

6 Steric and Electrostatic Effects 135

6.1 Nature and evaluation of steric interactions 136

6.2 Electrostatic and dipolar analysis 145

Problems and exercises 153

7 Nuclear and Electronic Spin Effects 155

7.1 NMR chemical shielding analysis 156

7.2 NMR J-coupling analysis 162

7.3 ESR spin density distribution 168

Problems and exercises 173

8 Coordination and Hyperbonding 176

8.1 Lewis acid-base complexes 178

8.2 Transition metal coordinate bonding 193

8.3 Three-center, four-electron hyperbonding 204

Problems and exercises 206

9 Intermolecular Interactions 209

9.1 Hydrogen-bonded complexes 210

9.2 Other donor-acceptor complexes 217

9.3 Natural energy decomposition analysis 223

Problems and exercises 227

10 Transition State Species and Chemical Reactions 231

10.1 Ambivalent Lewis structures: the transition-state limit 232

10.2 Example: bimolecular formation of formaldehyde 236

10.3 Example: unimolecular isomerization of formaldehyde 243

10.4 Example: S_N₂ halide exchange reaction 246

Problems and exercises 249

11 Excited State Chemistry 252

11.1 Getting to the "root" of the problem 252

11.2 Illustrative applications to NO excitations 256

11.3 Finding common ground: NBO versus MO state-to-state transferability 269

11.4 NBO/NRT description of excited-state structure and reactivity 277

11.5 Conical intersections and intersystem crossings 282

Problems and exercises 289.

Notes:

Includes index.

Machine generated contents note: Preface 1 Getting Started1.1 Talking to your electronic structure system1.2 Helpful tools1.3 General $NBO keylist usage1.4 Producing orbital imageryProblems and Exercises2 Electrons in Atoms2.1 Finding the electrons in atomic wavefunctions2.2 Atomic orbitals and their graphical representation2.3 Atomic electron configurations2.4 How to find electronic orbitals and configurations in NBO output2.5 Natural Atomic Orbitals and the Natural Minimal BasisProblems and Exercises3 Atoms in Molecules3.1 Atomic orbitals in molecules3.2 Atomic configurations and atomic charges in molecules3.3 Atoms in open-shell moleculesProblems and Exercises4 Hybrids and Bonds in Molecules4.1 Bonds and lone pairs in molecules4.2 Atomic hybrids and bonding geometry4.3 Bond polarity, electronegativity, and Bent's rule4.4 Electron-deficient 3-center bonds4.5 Open-shell Lewis structures4.6 Lewis-like structures in transition metal bondingProblems and Exercises5 Resonance Delocalization Corrections5.1 The Natural Lewis Structure perturbative model5.2 2nd-order perturbative analysis of donor-acceptor interactions5.3 $DEL energetic analysis5.4 Delocalization tails of Natural Localized Molecular Orbitals5.5 How to $CHOOSE alternative Lewis structures5.6 Natural Resonance TheoryProblems and Exercises6 Steric and Electrostatic Effects6.1 Nature and evaluation of steric interactions6.2 Electrostatic and dipolar analysisProblems and Exercises7 Nuclear and Electronic Spin Effects7.1 NMR chemical shielding analysis7.2 NMR J-coupling analysis7.3 ESR spin-density distributionProblems and Exercises8 Coordination and Hyperbonding8.1 Lewis acid-base complexes8.2 Transition metal coordinate bonding8.3 Three-center, four-electron hyperbondingProblems and Exercises9 Intermolecular Interactions9.1 Hydrogen-bonded complexes9.2 Other donor-acceptor complexes9.3 Natural energy decomposition analysisProblems and Exercises10 Transition State Species and Chemical Reactions10.1 Ambivalent Lewis structures: the transition-state limit10.2 Example: bimolecular formation of formaldehyde10.3 Example: unimolecular isomerization of formaldehyde10.4 Example: SN2 halide exchange reactionProblems and Exercises11 Excited State Chemistry11.1 Getting to the "root" of the problem11.2 Illustrative applications to NO excitations11.3 Finding common ground: state-to-state NBO transferability11.4 NBO/NRT description of excited state structure and reactivity11.5 Conical intersections and intersystem crossingsProblems and ExercisesAppendix A: What's Under the Hood?Appendix B: Orbital Graphics: The NBOView Orbital PlotterAppendix C: Digging at the DetailsAppendix D: What if Something Goes Wrong?Appendix E: Atomic Units and Conversion Factors.

Local Notes:

Acquired for the Penn Libraries with assistance from the Isaac Norris Library Fund.

ISBN:

1118119967

9781118119969

OCLC:

767564568

Publisher Number:

99953678691