MOLECULAR SPECTROSCOPY - GBV

1 MOLECULAR SPECTROSCOPYF irst EditionJeanne L. McHaleUniversity of IdahoPRENTICE HALL, Upper Saddle River, New Jersey 07458 CONTENTSPREFACE xiii1 INTRODUCTION AND REVIEW Historical Perspective Definitions, Derivations, and Discovery Review of Quantum Mechanics The Particle in a Box: A Model for Translational Energies The Rigid Rotor: A Model for Rotational Motion of Diatomics The Harmonic Oscillator: Vibrational Motion . Approximate Solutions to the Schrodinger Equation Variation Method.

2 Perturbation Theory Statistical Mechanics Summary \ Problems 30 BIBLIOGRAPHY 312 THE NATURE OF ELECTROMAGNETIC RADIATION Introduction The Classical Description of Electromagnetic Radiation Maxwell's Equations

3 Polarization Properties of Light Electric Dipole Radiation Propagation of Light in Matter Refraction Absorption and Emission of Light 44vi Effect of an Electromagnetic Field on Charged Particles Quantum Mechanical Aspects of Light Quantization of the Radiation Field Blackbody Radiation and the Planck Distribution Law The Photoelectric Effect and the Discovery of Photons Summary Problems 53 BIBLIOGRAPHY 553 ELECTRIC AND MAGNETIC PROPERTIES OF MOLECULESAND BULK MATTER Introduction Electric Properties of Molecules

4 Review of Electrostatics Electric Moments Quantum Mechanical Calculation of Multipole Moments Interaction of Electric Moments with the Electric Field Polarizability and Induced Moments Frequency Dependence of Polarizability Quantum Mechanical Expression for the Polarizability Electric Properties of Bulk Matter Dielectric Permittivity Frequency Dependence of Permittivity Relationships between Macroscopic and Microscopic Properties The Local Field Problem.

5 The Onsager and Kirkwood Models Magnetic Properties of Matter Basic Principles of Magnetism Magnetic Properties of Bulk Matter Magnetic Moments and Intrinsic Angular Momenta Summary Problems 89 BIBLIOGRAPHY 914 TIME-DEPENDENT PERTURBATION THEORY OFSPECTROSCOPY Introduction: Time Dependence in Quantum Mechanics Time-Dependent Perturbation Theory 94 Contents First-order Solution to the Time-Dependent Schrodinger Equa-tion Perturbation due to Electromagnetic Radiation.

6 Momentumversus Dipole Operator " Fermi's Golden Rule and the Time-Energy Uncertainty Prin-ciple Rate Expression for Emission Photon Density of States Fermi's Golden Rule for Stimulated and SpontaneousEmission Perturbation Theory Calculation of Polarizability Derivation of the Kramers-Heisenberg-Dirac Equation Finite State Lifetimes and Imaginary Component of Polariz-ability Oscillator Strength Quantum Mechanical Expression for Emission Rate Time Dependence of the Density Matrix Summary Problems 116 BIBLIOGRAPHY 1185 THE TIME-DEPENDENT APPROACH TO SPECTROSCOPY Introduction Time-Correlation Functions and

7 Spectra as Fourier Transform Pairs Properties of Time-Correlation Functions and Spectral Lineshapes The Fluctuation-Dissipation Theorem Rotational Correlation Functions and Pure Rotational Spectra Correlation Functions for Absorption and Light Scattering Classical Free-Rotor Correlation Function and Spectrum Reorientational SPECTROSCOPY of Liquids Dielectric Relaxation Far-Infrared Absorption Depolarized Rayleigh Scattering Vibration-Rotation Spectra Spectral Moments Summary Problems 149 Vlil ContentsBIBLIOGRAPHY 1516 EXPERIMENTAL CONSIDERATIONS.

8 ABSORPTION, EMIS-SION, AND SCATTERING Introduction Einstein A and B Coefficients for Absorption and Emission Absorption and Stimulated Emission Absorption and Emission SPECTROSCOPY Atomic Spectra MOLECULAR Electronic Spectra Measurement of Light Scattering: The Raman and Rayleigh Effects Spectral Lineshapes Summary Problems 171 BIBLIOGRAPHY 1737 ATOMIC SPECTROSCOPY Introduction Good Quantum Numbers and Not So Good Quantum Numbers The Hydrogen Atom.

9 Energy Levels and Selection Rules Many-Electron Atoms The Clebsch-Gordan Series Spin-Orbit Coupling Selection Rules for Atomic Absorption and Emission El, Ml, and E2 Allowed Transitions Hyperfine Structure I The Effect of External Fields The Zeeman Effect The Stark Effect Atomic Lasers and the Principles of Laser Emission Summary Problems 206 BIBLIOGRAPHY 2088

10 ROTATIONAL SPECTROSCOPY Introduction Energy Levels of Free Rigid Rotors 209 Contents Diatomics Polyatomic Rotations Angular Momentum Coupling in Non-1!] Electronic States Nuclear Statistics and J States of Homonuclear Diatomics Rotational Absorption and Emission SPECTROSCOPY Rotational Raman SPECTROSCOPY Corrections to the Rigid-Rotor Approximation Internal Rotation