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INTRODUCTION 1

CHAPTER 1.ROTATIONAL SPECTRA OF DIATOMIC MOLECULES 3

1-1.The Rigid Rotor 3

1-2.Energy Levels of the Diatomic Molecule 5

1-3.Mass Measurements 14

1-4.Absorption Intensities and Selection Rules 18

CHAPTER 2.LINEAR POLYATOMIC MOLECULES 25

2-1.Pure Rotational Spectra-General Considerations 25

2-2.l-Type Doubling 31

2-3.Perturbations between Vibrational States-Fermi Resonanee 35

2-4.Moments of Inertia and Internuclear Distances 40

2-5.Determination of Nuclear Masses 42

CHAPTER 3.SYMMETRIC-TOP MOLECULES 48

3-1.Introduction and General Features of Rotational Spectra 48

3-2.Symmetric-top Wave Functions 60

3-3.Symmetry and Inversion 62

3-4.Effects of Nuclear Spins and Statistics 69

3-5.Intensities of Symmetric-top Transitions 73

3-6.Centrifugal Stretching in Symmetric Tops 77

3-7.Rotation-Vibration Interactions and l-Type Doubling in Symmetric Tops 79

3-8.Dipole Moment Due to Degenerate Vibrations 82

CHAPTER 4.ASYMMETRIC-TOP MOLECULES 83

4-1.Energy Levels of Asymmetric and Slightly Asymmetric Rotors 83

4-2.Symmetry Considerations and Intensities 92

4-3.Centrifugal Distortion 105

4-4.Structures of Asymmetric Rotors 109

CHAPTER 5.ATOMIC SPECTRA 115

5-1.The Hydrogen Atom 115

5-2.Atoms with More Than One Electron 118

5-3.Fine Structure,Electron Spin,and the Vector Model 120

5-4.Atoms with More Than One Valence Electron 123

5-5.Selection Rules and Intensities 124

5-6.Fine Structure-More Exact Treatment 126

5-7.Hyperfine Structure 130

5-8.Penetrating Orbits 143

5-9.Zeeman Effects for Atoms 143

5-10.Microwave Studies of Atomic Hyperfine Structure 145

5-11.Microwave Spectra from Atronomical Sources 146

CHAPTER 6.QUADRUPOLE HYPERFINE STRUCTURE IN MOLECULES 149

6-1.Introduction 149

6-2.Quadrupole Hyperfine Structure in Linear Molecules 150

6-3.Quadrupole Hyperfine Structure in Symmetric Tops 154

6-4.Second-order Quadrupole Effects 155

6-5.Asymmetric Tops 159

6-6.Hyperfine Structure from Two or More Nuclei in the Same Molecule 164

CHAPTER 7.MOLECULES WITH ELECTRONIC ANGULAR MOMENTUM 174

7-1.Introduction 174

7-2.Hund’s Coupling Cases 177

7-3.Rotational Energies 180

7-4.Spin Uncoupling 185

7-5.A-Type Doubling 188

7-6.Nonlinear Molecules 192

CHAPTER 8.MAGNETIC HYPERFINE STRUCTURE IN MOLECULAR SPECTRA 194

8-1.Introduction 194

8-2.Coupling Schemes for Magnetic Hyperfine Structure 196

8-3.Examples of Magnetic Hyperfine Structure in Molecules with Electronic Angular Momentum 199

8-4.Nonlinear Molecules 200

8-5.Spin-spin Interaction between Nuclei 202

8-6.Effect of Hyperfine Structure on Doubling-Hyperfine Doubling 203

8-7.Electronic Angular Momentum in 1∑ Molecules and Its Contributions to Molecular Energy 207

8-8.Effect of Electronic Motion on Rotational Energy 212

8-9.Magnetic Hyperfine Interaction(I·J)in 1∑ Molecules 215

8-10.Magnetic Hyperfine Structure of Nonlinear Molecules in 1∑ States 219

CHAPTER 9.INTERPRETATION OF HYPERFINE COUPLING CONSTANTS IN TERMS OF MOLECULAR STRUCTURE AND NUCLEAR MOMENTS 225

9-1.Inroductory Remarks on Quadrupole Coupling 225

9-2.Quadrupole Coupling in Atoms 226

9-3.Quadrupole Coupling in Molecules-General Considerations 228

9-4.Procedure for Caleulating q in a Molecule 234

9-5.Quadrupole Coupling in Asymmetric Molecules 241

9-6.Interpretation of Magnetic Hyperfine Coupling Constants 245

CHAPTER 10.STARK EFFECTS IN MOLECULAR SPECTRA 248

10-1.Introduction 248

10-2.Quantum-mechanical Calculation of Stark Energy for Static Fields 250

10-3.Relative Intensities of Stark Components and Identification of Transitions from Their Stark Patterns 255

10-4.Stark Effect When Hyperfine Structure Is Present 258

10-5.Determination of Molecular Dipole Moments 264

10-6.Forbidden Lines and Change of Intensity Due to Stark Effect 269

10-7.Polarization of Molecules by Electric Fields 270

10-8.Stark Effects in Rapidly Varying Fields-Nonresonant Case 273

10-9.Stark Effects in Rapidly Varying Fields-Resonant Modulation 279

CHAPTER 11.ZEEMAN EFFECTS IN MOLECULAR SPECTRA 284

11-1.Introduction 284

11-2.Zeeman Effect in Weak Fields for Molecules Having Electronic Angular Momentum 284

11-3.Characteristics of Zeeman Splitting of Spectral Lines 286

11-4.Intermediate Coupling and Intermediate Fields 289

11-5.Zeeman Effect with Hyperfine Structure 289

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

11-7.Combined Zeeman-Stark Effects 296

11-8.Transitions between Zeeman Components 296

CHAPTER 12.THE AMMONIA SPECTRUM AND HINDERED MOTIONS 300

12-1.Introduction 300

12-2.Inversion Frequency of NH8 302

12-3.Inversion of Other Symmetric Hydrides 307

12-4.Fine Structure of the Ammonia Inversion Spectrum-Rotation-Vibration Interactions 307

12-5.Asymmetric Forms of Ammonia 314

12-6.Hindered Torsional Motions in Symmetric Rotors 315

12-7.Heights of Hindering Barriers 322

12-8.Hindered Torsional Motions in Asymmetric Rotors 324

12-9.Selection Rules 331

12-10.Examples of Hindered Torsional Motion in Asymmetric Rotors 333

CHAPTER 13.SHAPES AND WIDTHS OF SPECTRAL LINES 336

13-1.Natural Line Breadth 336

13-2.Doppler Effect 337

13-3.Pressure Broadening 338

13-4.Absolute or Integrated Line Intensity 343

13-5.Comparison of the Van Vleck-Weisskopf Line Shape with Experiment 344

13-6.Pressure Broadening and Intermolecular Forces 347

13-7.Comparison of Methods of Treating Pressure Broadening 348

13-8.Impact Theory-Anderson’s Treatment 355

13-9.Comparison of Theories with Experiment 361

13-10.Self-broadening of Linear Molecules 366

13-11.Oxygen Line Breadths 368

13-12.Temperature Dependence of Line Widths 368

13-13.Effect of Temperature on Intensities 369

13-14.High Pressures 370

13-15.Saturation Effects 371

13-16.Broadening by Collisions with Walls 374

13-17.Microwave Absorption in Nonpolar Gases 375

CHAPTER 14.MICROWAVE CIRCUIT ELEMENTS AND TECHNIQUES 376

14-1.Introduction.Electromagnetic Fields and Waves 376

14-2.Waveguides 379

14-3.Attenuation 383

14-4.Reflections in Waveguides 386

14-5.Cavity Resonators 390

14-6.Coupling of Cavities to Waveguide 392

14-7.Directional Couplers 394

14-8.Attenuators 397

14-9.Joints in Waveguide Systems 397

14-10.Waveguide Windows 398

14-11.Plungers 399

14-12.Other Types of Guided Waves 399

14-13.Microwave Applications of Ferrites 400

14-14.Microwave Generators 401

14-15.Klystrons 402

14-16.Magnetrons 405

14-17.Traveling-wave and Backward-wave Tubes 405

14-18.Detectors 407

CHAPTER 15.MICROWAVE SPECTROGRAPHS 411

15-1.General Principles and Ultimate Sensitivity 411

15-2.Source Modulation 416

15-3.Stark Modulation 418

15-4.Modulation-frequency Signal Amplifiers 420

15-5.Zeeman Modulation Spectrographs 424

15-6.Choice of Modulation Frequency for Spectrographs 425

15-7.Superheterodyne Detection 425

15-8.Bridge Spectrographs 425

15-9.High-resolution Spectrometers 427

15-10.Some High-resolution Spectrometers 428

15-11.Cavity Spectrographs 435

15-12.Large Untuned Cavity 439

15-13.Spectrographs for Measurements of Zeeman Effect 441

15-14.Spectrometers for High and Low Temperatures 443

15-15.Spectrographs for Intensity and Line-Shape Measurements 445

15-16.Gas Handling for Microwave Spectrographs 446

15-17.Spectrometers for Free Radicals 447

15-18.Microwave Radiometers 448

CHAPTER 16.MILLIMETER WAVES 451

16-1.Introduction 451

16-2.Spark Oscillators for Millimeter Waves 451

16-3.Vacuum-tube Generators 452

16-4.Harmonics from Vacuum Tubes 454

16-5.Detection of Millimeter Waves 455

16-6.Semi-conducting Crystal Harmonic Generators 458

16-7.Propagation of Millimeter Waves 462

16-8.Frequency Measurement 463

16-9.Absorption Spectrographs for the Millimeter Region 464

CHAPTER 17.FREQUENCY MEASUREMENT AND CONTROL 466

17-1.Wavemeters 466

17-2.Quartz-crystal-controlled Frequency Standards 468

17-3.Measurement of Frequency Differences 473

17-4.Frequency Stabilization of Microwave Oscillators 474

17-5.Control of Frequency by a Resonant Cavity 475

17-6.Stabilization of Microwave Oscillators by Absorption Lines 477

17-7.The Molecular-beam Maser 482

17-8.Realization of Atomic Frequency and Time Standards 483

CHAPTER 18.THE USE OF MICROWAVE SPECTROSCOPY FOR CHEMICAL ANALYSIS 486

18-1.Microwave Spectroscopy for Analysis 486

18-2.Qualitative Analysis 488

18-3.Quantitative Analysis 492

18-4.Special Equipment and Techniques for Spectroscopic Analysis 497

APPENDIX Ⅰ.Intensities of Hyperfine Structure Components and Energies Due to Nuclear Quadrupole Interactions 499

Ⅱ.Second-order Energies Due to Nuclear Quadrupole Interactions in Linear Molecules and Symmetric Tops 517

Ⅲ.Coefficients for Energy Levels of a Slightly Asymmetric Top 522

Ⅳ.Energy Levels of a Rigid Rotor 527

Ⅴ.Transition Strengths for Rotational Transitions 557

Ⅵ.Molecular Constants Involved in Microwave Spectra 613

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

BIBLIOGRAPHY 649

AUTHOR INDEX 683

SUBJECT INDEX 689