《Spectroscopy and Molecular Srtucture》

CHAPTER 1.THE TECHNIQUES OF SPECTRO-SCOPY1

The Historical Background1

The Electromagnetic Spectrum2

Spectro-scopic Instruments3

Prism Spectrometers6

Diffraction Gratings7

RADIATION SOURCES9

Emission Sources9

Absorption Spectroscopy11

Line and Band Spectra13

Radicals and Polyatomic Ions14

CHAPTER 2.WAVE MECHANICS AND THE HYDROGEN ATOM17

THE QUANTIZATION OF ENERGY17

Black-body Radiation17

The Photoelectric Effect19

The Heat Capacities of Solids20

The Spectrum of Atomic Hydrogen21

THE BOHR-SOMMERFELD ATOMIC THEORY23

Bohr’s Atomic Model for Hydrogen23

Sommerfeld’s Extension of the Bohr Atomic Model27

Excitation Potentials29

Shortcomings of the Bohr-Sommerfeld Theory30

ELECTRONS AND WAVE MOTIONS30

De Broglie’s Wave Equation for Electrons30

Electron Diffraction31

Standing and Progressive Waves32

The Uncertainty Principle33

Wave Equations34

HYDROGEN AND HYDROGENLIKE ATOMS37

The Wave Equation for Hydrogenlike Atoms37

The Angular Eigenfunctions38

The Radial Eigenfunctions40

The Atomic Wave Functions42

QUANTUM MECHANICS45

Fundamental Postulates45

The Vector Model for Atoms49

The Variation Principle51

The Perturbation Method53

Degenerate States55

Basis Functions and Mean Energies56

Electron Spin57

TransitionProbabilities58

Fluorescence and Phosphorescence60

CHAPTER 3.POLYELECTRONIC ATOMS63

THE ELEMENTS OF ATOMIC STRUCTURE63

One-Electron Wave Functions63

The Pauli Exclusion Principle66

The Electronic Configurations of the Elements67

The Angular Momenta of Atoms70

Spin-Orbit Interaction74

THE ALKALI METALS77

Spectral Terms of the Alkali Metals77

Multiplet Structure80

THE HELIUM ATOM81

Spectral Terms of the Helium Atom81

Wave Mechanics of the Helium Atom82

Fine Structure in the Spectra of Heliumlike Atoms86

THE SPECTRA OF COMPLEX ATOMS AND IONS87

Terms of Complex Atoms87

Selection Rules and Transitions90

Auto-ionization(Auger Process)92

Calculation of the Energies of Complex Atoms93

ATOMS IN EXTERNAL FIELDS94

The Normal Zeeman Effect94

Larmor Precession97

The Anomalous Zeeman Effect99

The Paschen-Back Effect101

The Stark Effect103

NUCLEAR EFFECTS IN ATOMIC SPECTRA104

Hyperfme Structure104

Isotope Effects104

Nuclear Magnetic Moments105

The Nuclear Zeeman Effect107

CHAPTER 4.THE STRUCTURES OF DIATOMIC MOLECULES113

The Born-Oppenheimer Approximation113

THE VECTOR MODEL FOR DIATOMIC MOLECULES116

Classification of Electronic States116

Electron Spin119

The Separated-Atom Approximation121

The United-Atom Approximation125

Correlation of Electron Orbitals128

Electron Configurations of Diatomic Molecules130

THE METHOD OF MOLECULAR ORBITALS132

The LCAO/MO Approximation132

The Hydrogen Molecule-Ion133

Bonding in the H2+ Ion136

Molecular Orbital Wave Functions for the Hydrogen Molecule140

Valence Bond Wave Functions for the Hydrogen Molecule143

Improved Trial Wave Functions for the Hydrogen Mole-cule144

Configuration Interaction145

WAVE FUNCTIONS FOR COMPLEX DIATOMIC MOLECULES146

LCAO/MO Wave Functions146

CHAPTER 5.THE ROTATION AND VIBRATION OF DIATOMIC MOLECULES151

Nuclear Motion151

The Rigid Rotator153

The Harmonic Oscillator155

The Spectrum of the Harmonic Oscillator159

The Anharmonic Oscillator160

Potentional Energy Functions164

The Spectrum of the Anharmonic Oscillator168

THE VIBRATING ROTATOR170

Rotational States170

Rotation-Vibration Spectra173

THE SYMMETRY OF MOLECULAR WAVE FUNCTIONS175

Symmetry Transformations175

Homonuclear Molecules178

Intensity Distribution in Rotational Structure179

Nuclear Statistical Weights182

Ortho and Para States186

THE RAMAN EFFECT187

The Scattering of Light187

Experimental Raman Spectroscopy188

Classical Theory190

Quantum Theory192

CHAPTER 6.ELECTRONIC TRANSITIONS IN DIATOMIC MOLECULES197

Electronic Band Spectra197

Rotational and Electro？ic Interactions199

Case(a)Coupling201

Case(b)Coupling203

Case(c)Coupling205

Case(d)Coupling206

A-Type Doubling208

Spin Uncoupling211

The Symmetry Classifications of Rotational Levels214

Statistical Weights216

Selection Rules220

Singlet-Singlet Transitions223

Multiplet-Multiplet Transitions226

THE VIBRATIONAL STRUCTURE OF ELECTRONIC TRANSITIONS227

Band Progressions and Sequences227

Transition Moments and Intensity Distributions232

The Franck-Condon Principle233

Electronic Band Spectra in Absorption237

Perturbation Theory of Interactions239

Spectroscopic Perturbations241

Continuous Spectra and Predissociation245

CHAPTER 7.THE SYMMETRIES OF POLYATOMIC MOLECULES249

INTRODUCTORY GROUP THEORY249

Symmetry Operations249

Symmetry Elements252

Groups255

Point Groups258

REPRESENTATIONS OF GROUPS263

Group Algebra263

The C3 Point Group265

The C3v Point Group268

Character Tables270

APPLICATION OF GROUP THEORY272

Nuclear Coordinate Transformations272

Translations,Rotations,and Vibrations274

Electronic States of Molecules275

Direct Product Representations278

Integrals over Configuration Space279

CHAPTER 8.THE ROTATIONS OF POLYATOMIC MOLECULES283

Nuclear Motion283

Principal Axes285

Rotational Energy Levels287

LINEAR MOLECULES289

Rotational States289

Rotational Spectra292

SYMMETRIC TOP MOLECULES294

Rotational States294

Symmetry and Statistical Weights296

Rotational Spectra302

SPHERICAL TOP MOLECULES303

Rotational States303

ASYMMETRIC TOP MOLECULES304

Rotational States304

Symmetry and Statistical Weights309

Rotational Spectra312

CHAPTER 9.THE VIBRATIONS OF POLYATOMIC MOLECULES315

Vibrational Motion315

Motion in Cartesian Coordinates316

Example;Vibrations of a Linear Molecule AB2322

Matrix Formulation324

Motion in Generalized Coordinates326

Motion in Normal Coordinates327

Motion in Internal Coordinates329

GROUP THEORY AND MOLECULAR VIBRATIONS332

Symmetry Operations on Displacement Coordinates332

The Symmetries of Normal Vibrations333

Representations in Cartesian Coordinates335

Motion in Symmetry Coordinates338

QUANTIZED VIBRATIONAL MOTION339

Vibrational Eigenstates and Eigenfunctions339

The Symmetry of VibrationalWave Functions341

Vibrational Angular Momentum346

Perturbations348

Vibrational Spectra and Selection Rules352

Inversion Doubling357

VIBRATIONAL RAMAN SPECTRA361

Polarizability361

Selection Rules362

The Mutual Exclusion Rule366

THE ROTATIONAL STRUCTURE OF INFRARED BANDS367

Rotation-Vibration Spectra367

CHAPTER 10.THE ELECTRONIC SPECTROSCOPY OF POLYATOMIC MOLECULES377

Electronic States of Polyatomie Molecules377

LCAO/MO’s for Polyatomic Molecules380

Orbital and Ionization Energies383

Equivalent Molecular Orbitals387

Localized Molecular Orbitals390

Hybrid Atomic Orbitals392

Aromatic Molecules396

ELECTRONIC BAND SPECTRA402

Electronic and Vibrational Terms402

Electronic and Vibronic Transitions402

Electronic and Vibronic Selection Rules404

Vibrational-Electronic Interactions405

The Jahn-Teller Effect410

The Renner Effect412

MO Correlation Diagrams418

Walsh’s Rules420

Chromo-phores and Group Absorption424

n→π* Transitions424

π→π* Transitions431

Crystal Field Theory437

APPENDIX Ⅰ.OPERATORS452

EIGENFUNCTIONS OF COMMUTING OPERATORS453

APPENDIX Ⅱ.SELECTION RULES454

APPENDIX Ⅲ.CHARACTER TABLES FOR SELECTED POINT GROUPS461

APPENDIX Ⅳ.PHYSICAL CONSTANTS AND CONVERSION FACTORS465

AUTHOR INDEX466

SUBJECT INDEX468