Molecular Physics

Contents

Contributors

Foreword


1. Introduction


1.1. Origins of the Molecular Theory


1.2. Molecular Physics


2. Molecular Spectroscopy


2.1. Microwave Spectroscopy


2.1.1. Introduction


2.1.2. The Spectral Line


2.1.3. Origin of Lines


2.1.4. Stark Effect


2.1.5. Hyperfine Structure


2.1.6. Summary of Procedures


2.1.7. Microwave Components


2.1.8. Frequency Measurements


2.1.9. Spectrometers


2.1.10. Sample Handling


2.1.11. Application of Microwave Spectroscopy


2.2. Infrared


2.2.1. Introduction


2.2.2. General Theory of Infrared Spectra


2.2.3. Experimental Considerations


2.2.4. Infrared Instrumentation


2.2.5. Applications of Infrared Spectroscopy


2.3. Raman Effect


2.3.1. Introduction


2.3.2. Theory of the Raman Effect


2.3.3. Apparatus


2.3.4. Raman Spectra and Their Applications


2.4. Electronic Spectra


2.4.1. Introduction


2.4.2. Apparatus


2.4.3. Simple Free Molecules


2.4.4. External Perturbations


2.4.5. Transition Probabilities in Molecular Electronic Spectra


2.4.6. Conclusions


3. Diffraction Methods of Molecular Structure Determination


3.1. Introduction to Symmetry Groups and Diffraction Theory


3.1.1. Introduction


3.1.2. Crystallography and Symmetry


3.1.3. The Reciprocal Lattice


3.1.4. The Interference Function


3.1.5. The Effect of Thermal Vibration on Laue-Bragg Diffraction


3.1.6. The Crystal Structure Factor


3.1.7. Fourier Representations of a Cell


3.1.8. Procedure of Structure Determination


3.1.9. Computational Methods for Refinement of Parameters


3.2. Techniques of X-Ray Diffraction


3.2.1. Introduction


3.2.2. Interaction of X-Rays with Matter


3.2.3. X-Ray Sources


3.2.4. Methods of Recording Diffraction Patterns


3.2.5. General Expressions for Integrated Intensities


3.2.6. Example of Structure Determination for a Molecule


3.3. Techniques of Electron Diffraction


3.3.1. Introduction


3.3.2. Scattering of Electrons by Atoms


3.3.3. Apparatus and Procedures


3.3.4. Analysis of Results


3.3.5. Accuracy of Results


3.4. Techniques of Neutron Diffraction


3.4.1. Introduction


3.4.2. Scattering of Slow Neutrons by Atoms


3.4.3. Apparatus and Procedure


3.4.4. Analysis of Results


4. Resonance Studies


4.1. Nuclear Magnetic Resonance


4.1.1. Introduction


4.1.2. Elementary Theory


4.1.3. General Experimental Methods


4.1.4. Techniques in High-Resolution Spectroscopy


4.1.5. Methods and Applications of Pulsed rf Systems


4.1.6. The Broadline Continuous rf Spectrometer


4.2. Electron Spin Resonance


4.2.1. Introduction


4.2.2. Basic Principles of Spectrographs


4.2.3. Radio-Frequency and Microwave Components


4.2.4. Amplification and Detection


4.2.5. Magnetic Field


4.2.6. Sensitivity


4.2.7. Electron-Nuclear Double Resonance Techniques


4.3. Nuclear Quadrupole Resonance


4.3.1. Introduction


4.3.2. Nuclear Quadrupole Energy Levels


4.3.3. General Experimental Methods


4.3.4. Applications


5. Mass Spectrometry


5.1. Introduction


5.1.1. Ionization Potentials


5.1.2. Experimental Methods for Determining Appearance Potentials


5.2. Molecular Structural Applications


5.2.1. Molecular Ionization Potentials


5.2.2. The Ionization Potentials of Free Radicals


5.2.3. Bond Dissociation Energies


5.2.4. Electron Affinities by Mass Spectrometric Methods


5.2.5. High-Temperature Chemistry Studies


5.3. Chemical Kinetics


5.3.1. Detection of Free Radicals in Thermal Reactions


5.3.2. Detection of Free Radicals in Photochemical Reactions


5.3.3. Fast Reactions by Mass Spectrometry


5.3.4. Ion-Molecule Reactions


5.3.5. Decomposition of Molecular Ions and Metastable Ion Transitions


6. Molecular Beams


6.1. Introduction


6.2. Beam Formation and Detection


6.2.1. Formation


6.2.2. Sources


6.2.3. Detection


6.3. Gas Kinetics


6.3.1. Velocity Distribution


6.3.2. Diffraction Experiments


6.3.3. Scattering


6.3.4. Chemical Reactions


6.3.5. Vapor Pressures


6.3.6. Surface Physics


6.4. Atoms and Molecules in Magnetic and Electric Fields


6.4.1. Atoms in a Magnetic Field


6.4.2. Molecules in a Magnetic Field


6.4.3. Stark Effect


6.5. Molecular Beam Optics


6.5.1. Optical Analog


6.5.2. Refraction in Various Fields


6.5.3. Molecular Beam Dynamics


6.5.4. Deflection Pattern of a Beam


6.5.5. Spectrometer Deflection Systems


6.6. The Magnetic and Electric Resonance Methods


6.6.1. Introduction


6.6.2. Transition Probabilities and Line Shapes


6.6.3. Design of Oscillating Fields


6.6.4. Separated Oscillating Fields


6.6.5. Special Methods for Obtaining Very Narrow Lines


6.6.6. Double Resonance


6.6.7. The Maser


6.7. Spectroscopy


6.7.1. Atoms


6.7.2. Magnetic Resonance Spectra of Molecules


6.7.3. Electric Resonance Experiments with Molecules


6.7.4. Neutron Beam Magnetic Resonance


6.8. Technology


7. Electric Properties of Molecules


7.1. Electric Polarization


7.1.1. Molar Polarization


7.1.2. Measurement of Dielectric Constant and Molar Polarization


7.2. Refraction of Light


7.2.1. Molar Refraction


7.2.2. Measurement of Index of Refraction and Molar Refraction


7.3. Electric Dipole Moments


7.3.1. Determination of Electric Dipole Moments from Dielectric Properties


7.3.2. Stark Effect in Microwave Spectra


7.3.3. Molecular Beam Method


7.3.4. References to Tables of Dipole Moments


7.4. Molecular Electric Quadrupole Moments


7.4.1. Impact Theory of Spectral Line Widths


7.4.2. Multipole Interactions


7.5. Optical Activity


8. Ultrasonic Studies and Thermodynamic Properties of Fluids


8.1. Velocity and Absorption of Sound in Gases and Vapors


8.1.1. Theory of Sound Transmission in Gases and Vapors


8.1.2. Measurements of Velocity and Absorption in Gases


8.2. Velocity and Absorption of Sound in Liquids


8.2.1. Introduction


8.2.2. The Optical Diffraction Method


8.2.3. The Interferometer Method


8.2.4. The Pulse-Echo Method


9. Appendix


9.1. Evaluation of Measurement


9.1.1. General Rules


9.2. Errors


9.2.1. Systematic Errors, Accuracy


9.2.2. Accidental Errors, Precision


9.3. Statistical Methods


9.3.1. Mean Value and Variance


9.3.2. Statistical Control of Measurements


9.4. Direct Measurements


9.4.1. Errors of Direct Measurements


9.4.2. Rejection of Data


9.4.3. Significance of Results


9.5. Indirect Measurement


9.5.1. Propagation of Errors


9.6. Preliminary Estimation


9.7. Errors of Computation

Author Index

Subject Index