Rotational Spectra and Molecular Structure

PrefaceChapter 1 Rotational Spectra 1-1. Energy Levels and Rotational Transitions 1-2. Information Contained in Rotational SpectraChapter 2 Rigid Rotor 2-1. Introduction 2-2. Molecular Parameters 2-3. Classes of Molecules 2-4a. Rigid Linear Molecules 2-4b. Spectrum and Selection Rules 2-5a. Rigid Symmetric Top Molecules 2-5b. Spectrum and Selection Rules 2-6a. Rigid Asymmetric Top Molecules 2-6b. Matrix Elements of E(¿) 2-6c. Asymmetric Rotor Functions 2-6d. Selection Rules 2-6e. K Doubling in an Asymmetric Rotor 2-6f. Graphical Methods for Determining ¿ and (A - C)/2 2-7. Rotational Transition Intensities 2-8. Statistical Weights 2-9. Nuclear Spin Statistics for Linear Molecules 2-10a. Nuclear Spin Statistics for Symmetric Tops 2-10b. Rotational Wave Functions 2-10c. Spin Wave Functions 2-1la. Nuclear Spin Statistics for Asymmetric Tops 2-11b. Rotational Wave Functions 2-11c. Spin Wave Functions 2-12a. Dipole Matrix Elements 2-12b. Dipole Matrix Elements for a Linear Molecule 2-12c. Dipole Matrix Elements for a Symmetric Rotor 2-12d. Dipole Matrix Elements for an Asymmetric Rotor 2-13. Transition Strengths and Approximate Wave Functions for Near Symmetric Tops Chapter 3 Centrifugal Distortion, Coriolis Coupling, and Fermi Resonance 3-1. Introduction 3-2. Classical Appearance of Centrifugal and Coriolis Forces 3-3. Centrifugal Distortion in a Linear Molecule 3-4. Centrifugal Distortion in Symmetric Top Molecules 3-5. The Coriolis Coupling Constant 3-6a. l-Type Doubling in Linear Molecules 3-6b. Direct l-Type Transitions 3-7a. Degenerate Coriolis Splitting 3-7b. l-Type Doubling in Symmetric Top Molecules 3-7c. Energy Levels and Effects of Centrifugal Distortion 3-8. Dipole Matrix Elements and Selection Rules for l-Doubling 3-9. Fermi Resonance in Linear Molecules 3-10a. Nonrigid Effects in Asymmetric Rotors 3-10b. Perturbation Treatment of Vibration-Rotation Hamiltonian 3-10c. Interactions for Near Degeneracies 3-11. Coriolis Coupling Effects on Rotational Constants 3-12. Centrifugal Distortion in Asymmetric Tops 3-13. Fermi Resonance in Nonlinear Molecules Chapter 4 Molecular Structure 4-1. Internuclear Distances and Moments of Inertia 4-2. r0 Structure 4-3. rs Structure 4-4a. Linear Molecules 4-4b. Comparison of r0 and rs Structures for Linear Molecules 4-5. Off-Axis Substitution in a Symmetric Top 4-6a. Planar Asymmetric Tops 4-6b. Nonplanar Asymmetric Tops 4-7. Structure Determinations When All Atoms are Not Isotopically Substituted 4-8a. Determination of Coordinates near Principal Axes:Linear Molecules 4-8b. Near Axis Coordinates in Asymmetric Tops 4-8c. Coordinates of Atoms near the COM in an Asymmetric Top with a Plane of Symmetry 4-9a. The Inertia Defect 4-9b. Planar Molecules 4-9c. Inertia Defect and Molecular Structure of Planar Molecules 4-9d. Inertia Defect in Nonplanar Molecules 4-10. Variation of Bond Length with Isotopic Substitution 4-11. Values and Limitations of the Average Structure Chapter 5 Nuclear Quadrupole Coupling 5-1. Quadrupole Nuclei in Molecules 5-2. Origin of the Quadrupole Interaction 5-3. Matrix Elements of HQ 5-4. First-Order Quadrupole Energy 5-5. Second-Order Quadrupole Energy 5-6. Molecules with Two Quadrupole Nuclei 5-7. Molecules with Three Quadrupole Nuclei 5-8. Quadrupole Hyperfine Structure in Excited Vibrational States 5-9. Relative Intensities of Quadrupole Components Chapter 6 Internal Rotation 6-1a. Introduction 6-1b. Physical Models 6-1c. Potential Energy and Hindered Rotation 6-2. High Potential Barriers 6-3a. Energy Levels, Selection Rules, and Intensities for a High Barrier 6-3b.