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INTRODUCTION1

CHAPTER 1.ROTATIONAL SPECTRA OF DIATOMIC MOLECULES3

1-1.The Rigid Rotor3

1-2.Energy Levels of the Diatomic Molecule5

1-3.Mass Measurements14

1-4.Absorption Intensities and Selection Rules18

CHAPTER 2.LINEAR POLYATOMIC MOLECULES25

2-1.Pure Rotational Spectra-General Considerations25

2-2.l-Type Doubling31

2-3.Perturbations between Vibrational States-Fermi Resonanee35

2-4.Moments of Inertia and Internuclear Distances40

2-5.Determination of Nuclear Masses42

CHAPTER 3.SYMMETRIC-TOP MOLECULES48

3-1.Introduction and General Features of Rotational Spectra48

3-2.Symmetric-top Wave Functions60

3-3.Symmetry and Inversion62

3-4.Effects of Nuclear Spins and Statistics69

3-5.Intensities of Symmetric-top Transitions73

3-6.Centrifugal Stretching in Symmetric Tops77

3-7.Rotation-Vibration Interactions and l-Type Doubling in Symmetric Tops79

3-8.Dipole Moment Due to Degenerate Vibrations82

CHAPTER 4.ASYMMETRIC-TOP MOLECULES83

4-1.Energy Levels of Asymmetric and Slightly Asymmetric Rotors83

4-2.Symmetry Considerations and Intensities92

4-3.Centrifugal Distortion105

4-4.Structures of Asymmetric Rotors109

CHAPTER 5.ATOMIC SPECTRA115

5-1.The Hydrogen Atom115

5-2.Atoms with More Than One Electron118

5-3.Fine Structure,Electron Spin,and the Vector Model120

5-4.Atoms with More Than One Valence Electron123

5-5.Selection Rules and Intensities124

5-6.Fine Structure-More Exact Treatment126

5-7.Hyperfine Structure130

5-8.Penetrating Orbits143

5-9.Zeeman Effects for Atoms143

5-10.Microwave Studies of Atomic Hyperfine Structure145

5-11.Microwave Spectra from Atronomical Sources146

CHAPTER 6.QUADRUPOLE HYPERFINE STRUCTURE IN MOLECULES149

6-1.Introduction149

6-2.Quadrupole Hyperfine Structure in Linear Molecules150

6-3.Quadrupole Hyperfine Structure in Symmetric Tops154

6-4.Second-order Quadrupole Effects155

6-5.Asymmetric Tops159

6-6.Hyperfine Structure from Two or More Nuclei in the Same Molecule164

CHAPTER 7.MOLECULES WITH ELECTRONIC ANGULAR MOMENTUM174

7-1.Introduction174

7-2.Hund’s Coupling Cases177

7-3.Rotational Energies180

7-4.Spin Uncoupling185

7-5.A-Type Doubling188

7-6.Nonlinear Molecules192

CHAPTER 8.MAGNETIC HYPERFINE STRUCTURE IN MOLECULAR SPECTRA194

8-1.Introduction194

8-2.Coupling Schemes for Magnetic Hyperfine Structure196

8-3.Examples of Magnetic Hyperfine Structure in Molecules with Electronic Angular Momentum199

8-4.Nonlinear Molecules200

8-5.Spin-spin Interaction between Nuclei202

8-6.Effect of Hyperfine Structure on Doubling-Hyperfine Doubling203

8-7.Electronic Angular Momentum in 1∑ Molecules and Its Contributions to Molecular Energy207

8-8.Effect of Electronic Motion on Rotational Energy212

8-9.Magnetic Hyperfine Interaction(I·J)in 1∑ Molecules215

8-10.Magnetic Hyperfine Structure of Nonlinear Molecules in 1∑ States219

CHAPTER 9.INTERPRETATION OF HYPERFINE COUPLING CONSTANTS IN TERMS OF MOLECULAR STRUCTURE AND NUCLEAR MOMENTS225

9-1.Inroductory Remarks on Quadrupole Coupling225

9-2.Quadrupole Coupling in Atoms226

9-3.Quadrupole Coupling in Molecules-General Considerations228

9-4.Procedure for Caleulating q in a Molecule234

9-5.Quadrupole Coupling in Asymmetric Molecules241

9-6.Interpretation of Magnetic Hyperfine Coupling Constants245

CHAPTER 10.STARK EFFECTS IN MOLECULAR SPECTRA248

10-1.Introduction248

10-2.Quantum-mechanical Calculation of Stark Energy for Static Fields250

10-3.Relative Intensities of Stark Components and Identification of Transitions from Their Stark Patterns255

10-4.Stark Effect When Hyperfine Structure Is Present258

10-5.Determination of Molecular Dipole Moments264

10-6.Forbidden Lines and Change of Intensity Due to Stark Effect269

10-7.Polarization of Molecules by Electric Fields270

10-8.Stark Effects in Rapidly Varying Fields-Nonresonant Case273

10-9.Stark Effects in Rapidly Varying Fields-Resonant Modulation279

CHAPTER 11.ZEEMAN EFFECTS IN MOLECULAR SPECTRA284

11-1.Introduction284

11-2.Zeeman Effect in Weak Fields for Molecules Having Electronic Angular Momentum284

11-3.Characteristics of Zeeman Splitting of Spectral Lines286

11-4.Intermediate Coupling and Intermediate Fields289

11-5.Zeeman Effect with Hyperfine Structure289

11-6.Zeeman Effects in Ordinary Molecules(1∑ States)290

11-7.Combined Zeeman-Stark Effects296

11-8.Transitions between Zeeman Components296

CHAPTER 12.THE AMMONIA SPECTRUM AND HINDERED MOTIONS300

12-1.Introduction300

12-2.Inversion Frequency of NH8302

12-3.Inversion of Other Symmetric Hydrides307

12-4.Fine Structure of the Ammonia Inversion Spectrum-Rotation-Vibration Interactions307

12-5.Asymmetric Forms of Ammonia314

12-6.Hindered Torsional Motions in Symmetric Rotors315

12-7.Heights of Hindering Barriers322

12-8.Hindered Torsional Motions in Asymmetric Rotors324

12-9.Selection Rules331

12-10.Examples of Hindered Torsional Motion in Asymmetric Rotors333

CHAPTER 13.SHAPES AND WIDTHS OF SPECTRAL LINES336

13-1.Natural Line Breadth336

13-2.Doppler Effect337

13-3.Pressure Broadening338

13-4.Absolute or Integrated Line Intensity343

13-5.Comparison of the Van Vleck-Weisskopf Line Shape with Experiment344

13-6.Pressure Broadening and Intermolecular Forces347

13-7.Comparison of Methods of Treating Pressure Broadening348

13-8.Impact Theory-Anderson’s Treatment355

13-9.Comparison of Theories with Experiment361

13-10.Self-broadening of Linear Molecules366

13-11.Oxygen Line Breadths368

13-12.Temperature Dependence of Line Widths368

13-13.Effect of Temperature on Intensities369

13-14.High Pressures370

13-15.Saturation Effects371

13-16.Broadening by Collisions with Walls374

13-17.Microwave Absorption in Nonpolar Gases375

CHAPTER 14.MICROWAVE CIRCUIT ELEMENTS AND TECHNIQUES376

14-1.Introduction.Electromagnetic Fields and Waves376

14-2.Waveguides379

14-3.Attenuation383

14-4.Reflections in Waveguides386

14-5.Cavity Resonators390

14-6.Coupling of Cavities to Waveguide392

14-7.Directional Couplers394

14-8.Attenuators397

14-9.Joints in Waveguide Systems397

14-10.Waveguide Windows398

14-11.Plungers399

14-12.Other Types of Guided Waves399

14-13.Microwave Applications of Ferrites400

14-14.Microwave Generators401

14-15.Klystrons402

14-16.Magnetrons405

14-17.Traveling-wave and Backward-wave Tubes405

14-18.Detectors407

CHAPTER 15.MICROWAVE SPECTROGRAPHS411

15-1.General Principles and Ultimate Sensitivity411

15-2.Source Modulation416

15-3.Stark Modulation418

15-4.Modulation-frequency Signal Amplifiers420

15-5.Zeeman Modulation Spectrographs424

15-6.Choice of Modulation Frequency for Spectrographs425

15-7.Superheterodyne Detection425

15-8.Bridge Spectrographs425

15-9.High-resolution Spectrometers427

15-10.Some High-resolution Spectrometers428

15-11.Cavity Spectrographs435

15-12.Large Untuned Cavity439

15-13.Spectrographs for Measurements of Zeeman Effect441

15-14.Spectrometers for High and Low Temperatures443

15-15.Spectrographs for Intensity and Line-Shape Measurements445

15-16.Gas Handling for Microwave Spectrographs446

15-17.Spectrometers for Free Radicals447

15-18.Microwave Radiometers448

CHAPTER 16.MILLIMETER WAVES451

16-1.Introduction451

16-2.Spark Oscillators for Millimeter Waves451

16-3.Vacuum-tube Generators452

16-4.Harmonics from Vacuum Tubes454

16-5.Detection of Millimeter Waves455

16-6.Semi-conducting Crystal Harmonic Generators458

16-7.Propagation of Millimeter Waves462

16-8.Frequency Measurement463

16-9.Absorption Spectrographs for the Millimeter Region464

CHAPTER 17.FREQUENCY MEASUREMENT AND CONTROL466

17-1.Wavemeters466

17-2.Quartz-crystal-controlled Frequency Standards468

17-3.Measurement of Frequency Differences473

17-4.Frequency Stabilization of Microwave Oscillators474

17-5.Control of Frequency by a Resonant Cavity475

17-6.Stabilization of Microwave Oscillators by Absorption Lines477

17-7.The Molecular-beam Maser482

17-8.Realization of Atomic Frequency and Time Standards483

CHAPTER 18.THE USE OF MICROWAVE SPECTROSCOPY FOR CHEMICAL ANALYSIS486

18-1.Microwave Spectroscopy for Analysis486

18-2.Qualitative Analysis488

18-3.Quantitative Analysis492

18-4.Special Equipment and Techniques for Spectroscopic Analysis497

APPENDIX Ⅰ.Intensities of Hyperfine Structure Components and Energies Due to Nuclear Quadrupole Interactions499

Ⅱ.Second-order Energies Due to Nuclear Quadrupole Interactions in Linear Molecules and Symmetric Tops517

Ⅲ.Coefficients for Energy Levels of a Slightly Asymmetric Top522

Ⅳ.Energy Levels of a Rigid Rotor527

Ⅴ.Transition Strengths for Rotational Transitions557

Ⅵ.Molecular Constants Involved in Microwave Spectra613

Ⅶ.Properties of the Stable Nuclei(Abundance,Mass,and Moments)643

BIBLIOGRAPHY649

AUTHOR INDEX683

SUBJECT INDEX689