Discovering Chemistry With Natural Bond Orbitals

by Weinhold, Frank

• ISBN13: 9781118119969
• ISBN10: 1118119967
• Edition: 1st
• Format: Paperback
• Copyright: 2012-07-10
• Publisher: Wiley

Summary

This book explores chemical bonds, their intrinsic energies, and the corresponding dissociation energies which are relevant in reactivity problems. It offers the first book on conceptual quantum chemistry, a key area for understanding chemical principles and predicting chemical properties. It presents NBO mathematical algorithms embedded in a well-tested and widely used computer program (currently, NBO 5.9). While encouraging a "look under the hood" (Appendix A), this book mainly enables students to gain proficiency in using the NBO program to re-express complex wavefunctions in terms of intuitive chemical concepts and orbital imagery.

Author Biography

Frank Weinhold, PhD, is Emeritus Professor of Physical and Theoretical Chemistry at the University of Wisconsin-Madison. Professor Weinhold has served on the editorial advisory boards of the International Journal or Quantum Chemistry and Russian Journal of Physical Chemistry. He is the author of more than 170 technical publications and software packages, including the natural bond orbital program. Clark R. Landis, PhD, is Professor of Inorganic Chemistry at the University of Wisconsin-Madison. He has received teaching and lectureship awards for his contributions to chemical education. Dr. Landis's research focuses on catalysis in transition metal complexes.

Table of Contents

Preface	p. xi
Getting Started	p. 1
Talking to your electronic structure system	p. 1
Helpful tools	p. 3
General $NBO keylist usage	p. 4
Producing orbital imagery	p. 6
Problems and exercises	p. 8
Electrons in Atoms	p. 10
Finding the electrons in atomic wavefunctions	p. 10
Atomic orbitals and their graphical representation	p. 13
Atomic electron configurations	p. 18
How to find electronic orbitals and configurations in NBO output	p. 23
Natural atomic orbitals and the natural minimal basis	p. 29
Problems and exercises	p. 31
Atoms in Molecules	p. 34
Atomic orbitals in molecules	p. 35
Atomic configurations and atomic charges in molecules	p. 39
Atoms in open-shell molecules	p. 44
Problems and exercises	p. 49
Hybrids and Bonds in Molecules	p. 51
Bonds and lone pairs in molecules	p. 52
Atomic hybrids and bonding geometry	p. 60
Bond polarity, electronegativity, and Bent's rule	p. 71
Hypovalent three-center bonds	p. 78
Open-shell Lewis structures and spin hybrids	p. 82
Lewis-like structures in transition metal bonding	p. 86
Problems and exercises	p. 89
Resonance Delocalization Corrections	p. 92
The natural Lewis structure perturbative model	p. 93
Second-order perturbative analysis of donor-acceptor interactions	p. 96
$Del energetic analysis [integrated ESS/NBO only]	p. 105
Delocalization tails of natural localized molecular orbitals	p. 113
How to $CHOOSE alternative Lewis structures	p. 117
Natural resonance theory	p. 123
Problems and exercises	p. 133
Steric and Electrostatic Effects	p. 135
Nature and evaluation of steric interactions	p. 136
Electrostatic and dipolar analysis	p. 145
Problems and exercises	p. 153
Nuclear and Electronic Spin Effects	p. 155
NMR chemical shielding analysis	p. 156
NMR J-coupling analysis	p. 162
ESR spin density distribution	p. 168
Problems and exercises	p. 173
Coordination and Hyperbonding	p. 176
Lewis acid-base complexes	p. 178
Transition metal coordinate bonding	p. 193
Three-center, four-electron hyperbonding	p. 204
Problems and exercises	p. 206
Intermolecular Interactions	p. 209
Hydrogen-bonded complexes	p. 210
Other donor-acceptor complexes	p. 217
Natural energy decomposition analysis	p. 223
Problems and exercises	p. 227
Transition State Species and Chemical Reactions	p. 231
Ambivalent Lewis structures: the transition-state limit	p. 232
Example: bimolecular formation of formaldehyde	p. 236
Example: unimolecular isomerization of formaldehyde	p. 243
Example: SN2 halide exchange reaction	p. 246
Problems and exercises	p. 249
Excited State Chemistry	p. 252
Getting to the "root" of the problem	p. 252
Illustrative applications to NO excitations	p. 256
Finding common ground: NBO versus MO state-to-state transferability	p. 269
NBO/NRT description of excited-state structure and reactivity	p. 277
Conical intersections and intersystem crossings	p. 282
Problems and exercises	p. 289
What's Under the Hood?	p. 297
Orbital Graphics: The NBO View Orbital Plotter	p. 300
Digging at the Details	p. 302
What If Something Goes Wrong?	p. 304
Atomic Units (a.u.) and Conversion Factors	p. 307
Index	p. 309
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