Chemical Bonding and Molecular Geometry From Lewis to Electron Densities

by Gillespie, Ronald J.; Popelier, Paul L. A.

• ISBN13: 9780195104950
• ISBN10: 0195104951
• Format: Hardcover
• Copyright: 2001-03-08
• Publisher: Oxford University Press

Summary

Ideal for undergraduate and first-year graduate courses in chemical bonding, Chemical Bonding and Molecular Geometry: From Lewis to Electron Densities can also be used in inorganic chemistry courses. Authored by Ronald Gillespie, a world-class chemist and expert on chemical bonding, and Paul Popelier of the University of Manchester Institute of Science and Technology, this text provides students with a comprehensive and detailed introduction to the principal models and theories of chemical bonding and geometry. It also serves as a useful resource and an up-to-date introduction to modern developments in the field for instructors teaching chemical bonding at any level. Features: * Shows students how the concept of the chemical bond has developed from its earliest days, through Lewis's brilliant concept of the electron pair bond and up to the present day * Presents a novel, non-traditional approach that emphasizes the importance of the Pauli principle as a basis for understanding bonding * Begins with the fundamental classical concepts and proceeds through orbital models to recent ideas based on the analysis of electron densities, which help to clarify and emphasize many of the limitations of earlier models * Provides a thorough and up-to-date treatment of the well-known valence-shell electron pair (VSEPR) model (which was first formulated and developed by author Ronald Gillespie) and the more recent ligand close-packing (LCP) model * Presents a unique pictorial and nonmathematical discussion of the analysis of electron density distributions using the atoms in molecules (AIM) theory * Emphasizes the relationships between these various models, giving examples of their uses, limitations, and comparative advantages and disadvantages

Author Biography

Ronald J. Gillespie is Emeritus Professor of Chemistry at McMaster University in Ontario, Canada, where he has taught inorganic chemistry and general chemistry for over thirty years Paul L.A. Popelier is Lecturer of Physical Chemistry at the University of Manchester Institute of Science and Technology, UK

Table of Contents

Preface	xi
Acknowledgments	xiii
The Chemical Bond: Classical Concepts and Theories	1	(24)
Introduction	1	(1)
Valence	1	(1)
The Periodic Table of the Elements	2	(1)
Structural Formulas	3	(2)
Stereochemistry	5	(1)
The Shell Model	6	(2)
The Ionic Model of the Chemical Bond	8	(1)
The Covalent Bond and Lewis Structures	9	(5)
Polar Bonds and Electronegativity	14	(3)
Polyatomic Anions and Formal Charges	17	(1)
Oxidation Number (Oxidation State)	18	(1)
Donor-Acceptor Bonds	19	(1)
Exceptions to the Octet Rule: Hypervalent and Hypovalent Molecules	20	(3)
Limitations of the Lewis Model	23	(2)
Bond Properties	25	(24)
Introduction	25	(2)
Bond Lengths and Covalent Radii	27	(3)
Multiple Bonds and Bond Order	30	(3)
Ionic Radii	33	(4)
The Lengths of Polar Bonds	37	(1)
Back-Bonding	38	(1)
Bond Dissociation Energies and Bond Enthalpies	39	(3)
Force Constants	42	(1)
Dipole Moments	43	(6)
Some Basic Concepts of Quantum Mechanics	49	(35)
Introduction	49	(1)
Light, Quantization, and Probability	50	(1)
The Early Quantum Model of the Atom	51	(2)
The Wave Nature of Matter and the Uncertainty Principle	53	(1)
The Schrodinger equation and the Wave Function	53	(4)
The Meaning of the Wave Function: Probability and Electron Density	57	(1)
The Hydrogen Atom and Atomic Orbitals	58	(6)
Electron Spin	64	(1)
The Pauli Principle	64	(5)
Multielectron Atoms and Electron Configurations	69	(2)
Bonding Models	71	(8)
Ab Initio Calculations	79	(2)
Postscript	81	(3)
Molecular Geometry and the VSEPR Model	84	(29)
Introduction	84	(1)
The Distribution of Electrons in Valence Shells	85	(3)
Electron Pair Domains	88	(7)
Two, Three, Four, and Six Electron Pair Valence Shells	95	(4)
Multiple Bonds	99	(7)
Five Electron Pair Valence Shells	106	(4)
Limitations and Exceptions	110	(3)
Ligand-Ligand Interactions and the Ligand Close-Packing (LCP) Model	113	(21)
Introduction	113	(3)
Ligand-Ligand Interactions	116	(3)
The Ligand Close-Packing (LCP) Model	119	(3)
Bond Lengths and Coordination Number	122	(2)
Molecules with Two or More Different Ligands	124	(2)
Bond Angles in Molecules with Lone Pairs	126	(2)
Weakly Electronegative Ligands	128	(2)
Ligand-Ligand Interactions in Molecules of the Elements in Periods 3-6	130	(1)
Polyatomic Ligands	130	(2)
Comparison of the LCP and VSEPR Models	132	(2)
The AIM Theory and the Analysis of the Electron Density	134	(29)
Introduction	134	(1)
The Hellmann-Feynman Theorem	134	(2)
Representing the Electron Density	136	(3)
The Density Difference or Deformation Function	139	(4)
The Electron Density from Experiment	143	(1)
The Topology of the Electron Density	144	(9)
Atomic Properties	153	(2)
Bond Properties	155	(2)
The Diatomic Hydrides of Periods 2 and 3	157	(4)
Summary	161	(2)
The Laplacian of the Electron Density	163	(17)
Introduction	163	(1)
The Laplacian of the Electron Density	164	(1)
The Valence Shell Charge Concentration	165	(5)
The Laplacian and the VSEPR Model	170	(8)
Electron Pair Localization and the Lewis and VSEPR Models	178	(1)
Summary	179	(1)
Molecules of the Elements of Period 2	180	(43)
Introduction	180	(1)
The Relationship Between Bond Properties and the AIM Theory	180	(4)
The Nature of the Bonding in the Fluorides, Chlorides, and Hydrides of Li, Be, B, and C	184	(13)
The Geometry of the Molecules of Be, B, and C	197	(1)
Hydroxo and Related Molecules of Be, B, and C	198	(4)
The Nature of the CO and Other Polar Multiple Bonds	202	(7)
Bonding and Geometry of the Molecules of Nitrogen	209	(7)
The Geometry of the Molecules of Oxygen	216	(4)
The Geometry of the Molecules of Fluorine	220	(3)
Molecules of the Elements of Periods 3-6	223	(36)
Introduction	223	(1)
Hypervalence	224	(7)
Bonding in the Fluorides, Chlorides, and Hydrides with and LLP Coordination Number Up to Four	231	(8)
Geometry of the Fluorides, Chlorides, and Hydrides with and LLP Coordination Number Up to Four	239	(3)
Molecules with an LLP Coordination Number of Five	242	(8)
Molecules with an LLP Coordination Number of Six	250	(1)
Molecules with an LLP Coordination Number of Seven or Higher	251	(7)
Molecules of the Transition Metals	258	(1)
Index	259	(6)
Formula Index	265