Note: Front Cover -- The Spectra and Dynamics of Diatomic Molecules -- Copyright Page -- Table of Contents -- List of Tables -- List of Figures -- Preface -- From the Preface to "Perturbations in the Spectra of Diatomic Molecules -- Chapter 1. Simple Spectra and Standard Experimental Techniques -- 1.1 Rotation-Vibration-Electronic Spectra of Diatomic Molecules -- 1.2 Experimental Techniques of Diatomic Molecule Spectroscopy -- 1.3 References -- Chapter 2. Basic Models -- 2.1 What Is a Perturbation? -- 2.2 Structural Models -- 2.3 Elementary Properties of Angular Momenta in Diatomic Molecules -- 2.4 Estimation of Parameters in a Model Hamiltonian -- 2.5 Data Compilations -- 2.6 References -- Chapter 3. Terms Neglected in the Born-Oppenheimer Approximation -- 3.1 The Born-Oppenheimer Approximation -- 3.2 Basis Functions -- 3.3 Electrostatic Perturbations -- 3.4 Spin Part of the Hamiltonian -- 3.5 Rotational Perturbations -- 3.6 References -- Chapter 4. Methods of Deperturbation -- 4.1 Variational Calculations -- 4.2 The Van Vleck Transformation and Effective Hamiltonians -- 4.3 Approximate Solutions -- 4.4 Exact Solutions -- 4.5 Typical Examples of Fitted Perturbations -- 4.6 References -- Chapter 5. Interpretation of the Perturbation Matrix Elements -- 5.1 Calculation of the Vibrational Factor -- 5.2 Order of Magnitude of Electrostatic Perturbation Parameters: Interactions Between Valence and Rydberg States of the Same Symmetry -- 5.3 Order of Magnitude of Spin Parameters -- 5.4 Magnitudes of Rotational Perturbation Parameters -- 5.5 Pure Precession Approximation -- 5.6 R-Dependence of the Spin Interaction Parameters -- 5.7 Beyond the Single-Configuration Approximation -- 5.8 Identification and Location of Metastable States by Perturbation Effects -- 5.9 References -- Chapter 6. Transition Intensities and Special Effects -- 6.1 Intensity Factors. , 6.2 Intensity Borrowing -- 6.3 Interference Effects -- 6.4 Forbidden Transitions -- Intensity Borrowing by Mixing with a Remote Perturber -- 6.5 Special Effects -- 6.6 References -- Chapter 7. Photodissociation Dynamics -- 7.1 Photofragmentation -- 7.2 Direct Dissociation -- 7.3 Introduction to Predissociation -- 7.4 Experimental Aspects of Predissociation -- 7.5 Theoretical Expressions for Widths and Level Shifts -- 7.6 The Vibrational Factor -- 7.7 Mulliken's Classification of Predissociations -- 7.8 The Electronic Interaction Strength -- 7.9 Fano Lineshape -- 7.10 Isotope Effects -- 7.11 Examples of Predissociation -- 7.12 Case of Intermediate Coupling Strength -- 7.13 Indirect (Accidental) Predissociation and Interference Effects -- 7.14 Some Recipes for Interpretation -- 7.15 References -- Chapter 8. Photoionization Dynamics -- 8.1 Direct Ionization -- 8.2 Experimental Aspects of Autoionization -- 8.3 The Nature of Autoionized States -- 8.4 Autoionization Widths -- 8.5 Rotational Autoionization -- 8.6 Vibrational Autoionization -- 8.7 Spin-Orbit Autoionization -- 8.8 Electronic (or Electrostatic) Autoionization -- 8.9 Validity of the Approximations -- 8.10 Influence of Autoionization on ZEKE Peak Intensities -- 8.11 Photoelectron Angular Distribution, Photoion Alignment, and Spin Polarization -- 8.12 Competition between Autoionization and Predissociation -- 8.13 Coherent Control of Photofragmentation Product Branching Ratios -- 8.14 References -- Chapter 9. Dynamics -- 9.1 Dynamical Concepts, Tools, and Terminology -- 9.2 From Quantum Beats to Wavepackets -- 9.3 Relaxation into a Quasi-Continuum: A Tool for Dimensionality Reduction -- 9.4 Beyond the Spectra and Dynamics of Diatomic Molecules -- 9.5 References -- Index.

Note: Intro -- Preface -- References -- Contents -- List of Figures -- 1 Introduction -- 1.1 Rotation: The Rigid Rotor -- 1.2 Vibration: The Harmonic Oscillator -- 1.3 Electronic Structure: The Particle in a Box and the Hydrogen Atom -- 1.4 Transition Selection and Propensity Rules: J, Franck-Condon, and S -- 1.5 Rotational Branches, Vibrational Bands, and ElectronicTransitions -- 1.6 Some Sum Rules -- 1.7 Eigenstates are Stationary -- References -- 2 Hierarchy of Terms in the Effective Hamiltonian -- 2.1 Adiabatic and Diabatic Representations -- 2.1.1 Introduction -- 2.1.2 Adiabatic vs. Diabatic Representations -- 2.2 Hspin-orbit -- 2.3 HROT, the Rotational Operator -- 2.4 Hund's Cases -- 2.4.1 H(0) vs. H(1) -- 2.5 Two Basis Sets for the 22 ``Two-Level'' Problem -- 2.6 Some Reasons for Patterns -- 2.7 Straight Line Plots -- 2.8 Stacked Plots -- 2.9 Angular Momenta: A Brief Summary -- 2.10 Where Have We Been and Where are We Going? -- References -- 3 Spectroscopic Perturbations: Homogeneous and Heterogeneous -- 3.1 What Is a Perturbation? -- 3.2 Level Shifts and Intensity Borrowing -- 3.3 Two Qualitatively Distinct Classes of Perturbation: Homogeneous and Heterogeneous -- 3.4 Franck-Condon Factors -- 3.5 Which Franck-Condon Factors Should I Use? -- 3.6 Intensity Borrowed from a Nearby Bright State -- 3.7 Intensity Borrowed from an Energetically Remote Bright State -- 3.8 Intensity Interference Effects -- References -- 4 The Effective Hamiltonian for Diatomic Molecules -- 4.1 Introduction -- 4.2 Main Topics of This Lecture -- 4.2.1 R-Dependence -- 4.2.2 How Do We Account for Interactions with Energetically Remote States? -- 4.2.3 Van Vleck Transformation -- 4.3 R-Dependence Is Encoded in v,J Dependence -- 4.3.1 Transition Moments: μ (R) →Mv,v -- 4.3.2 Centrifugal Distortion, De -- 4.3.3 Vibration-Rotation Interaction, αe: A Small Surprise. , 4.4 Van Vleck Transformation for Non-1+ States -- 4.4.1 Centrifugal Distortion -- 4.4.2 The Van Vleck Transformation -- 4.4.2.1 List of Initial and Final States -- 4.4.2.2 List of Relevant Intermediate States -- 4.4.2.3 Railroad Diagrams -- 4.4.2.4 Harvest the Information in Each Railroad Diagram -- 4.4.3 Example of Centrifugal Distortion in a 3 State -- 4.4.4 -Doubling -- 4.4.4.1 Elimination of Nonsense -- 4.4.4.2 Relationship Between Parity and e/f-Symmetry -- 4.4.4.3 The Central Role of -States -- 4.4.4.4 General -Doubling Hamiltonian, HLD -- 4.4.4.5 Worked Examples -- < -- 31 ef|H|31 ef> -- , a Diagonal Contribution -- < -- 31 ef|H|30 ef> -- , an Off-Diagonal Contribution -- -Doubling in a 1 State Due to an Energetically Remote 3+ State -- 4.5 Summary -- References -- 5 Rotation of Polyatomic Molecules -- 5.1 Introduction -- 5.2 Rotational Energy Levels of Rigid Polyatomic Rotors -- 5.2.1 Symmetric Top -- 5.2.2 Asymmetric Top -- 5.3 Correlation Diagrams: WHY? -- 5.3.1 Prolate-Oblate Top Correlation Diagram -- 5.3.2 Assignments of Rotational Transitions -- 5.4 Vibrational Dependence of Rotational Constants -- References -- 6 Quantum Beats -- 6.1 Introduction -- 6.2 Time-Dependent Schrödinger Equation (TDSE) -- 6.3 ``Bright'' and ``Dark'' States -- 6.4 Dynamics -- 6.5 Quantum Beats -- 6.5.1 Simple Two-Level Quantum Beats -- 6.5.2 Two-Level Treatment of QB with Complex Energies -- 6.5.3 What Does a Quantum Beat Signal Look Like? -- 6.5.4 Population Quantum Beats -- 6.5.4.1 Polarization Quantum Beats -- 6.5.4.2 Direction Cosine Matrix Element Based Picture of Polarization Quantum Beats -- 6.5.4.3 Zeeman vs. Stark Polarization Quantum Beats -- 6.5.5 Level-Crossing vs. Anticrossing -- References -- 7 The Effective Hamiltonian for Polyatomic Molecule Vibration -- 7.1 The Effective Vibrational Hamiltonian for PolyatomicMolecules. , 7.2 Harmonic Oscillator -- 7.2.1 Matrix Elements of P and Q -- 7.2.2 Dimensionless Forms: , , -- 7.2.2.1 Matrix Elements and Selection Rules -- 7.2.2.2 Use of Commutation Rules -- 7.2.2.3 We Use this Result to Evaluate Matrix Elements of (0) -- 7.2.2.4 Matrix Elements of Anharmonic V(Q) -- 7.3 Polyatomic Molecules -- 7.3.1 Basis Set as Product of 3N-6 Harmonic Oscillator Eigenstates -- 7.3.2 Matrix Elements of V(1,2,…3N-6) in the ψ(0)v1,v2,…,3N-6 Basis Set -- 7.3.3 Breakdown of Non-Degenerate Perturbation Theory -- 7.3.4 Polyads -- 7.3.5 Patterns for Spectral Assignment and Mechanisms of Intramolecular Vibrational Redistribution (IVR) and Unimolecular Isomerization -- 7.4 Polyads in the Acetylene Electronic Ground State (S0) -- References -- 8 Intramolecular Dynamics: Representations, Visualizations, and Mechanisms -- 8.1 From the ``Pluck'' at t=0 to the Time-Evolving State -- 8.2 Perturbation Theory -- 8.3 Toluene: A Hindered Rotor. A Fully Worked Out Example -- 8.4 The Pluck: (Q,t=0) -- 8.5 (Q,t) Contains too Much Information -- 8.5.1 Motion in Real Space -- 8.5.2 Motion in State Space -- 8.6 Mechanism -- References.