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Photoabsorption, Photoionization, and Photoelectron Spectroscopy

1st Edition - October 28, 1979

Author: Joseph Berkowitz

eBook ISBN:

9 7 8 - 0 - 3 2 3 - 1 4 8 2 8 - 3

Photoabsorption, Photoionization, and Photoelectron Spectroscopy explores photoabsorption processes involving individual, isolated molecules in the wavelength or photon energy… Read more

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Photoabsorption, Photoionization, and Photoelectron Spectroscopy explores photoabsorption processes involving individual, isolated molecules in the wavelength or photon energy range from the ionization thresholds of molecules (usually in the vacuum ultraviolet region) through the soft and hard X-ray region and beyond the ""K edge."" The interaction between electromagnetic radiation and isolated molecules based on photoabsorption, photoionization, and photoelectron spectroscopy studies is described, along with the techniques for measurement of total and partial cross sections. This book is comprised of eight chapters and examines the decomposition of molecules and molecular ions as well as mildly excited (valence shell excitation) and highly excited (inner shell excitation) molecules. After providing a general theoretical background, it discusses certain classes of atoms and molecules and considers electromagnetic interactions with gases. The following chapters focus on photoabsorption below the first ionization limit; quasi-discrete states above the first ionization potential; and the ionization continuum. Total photoabsorption and photoionization cross sections for selected molecules are also considered, and the angular distribution of photoelectrons is analyzed. The various measurement techniques are described in the last chapter. This monograph will be of interest to radiation chemists, radiation physicists, photochemists, mass spectrometrists, and perhaps radiation biologists.

Preface

Acknowledgments

Units and Conversion Factors

Introduction

Suggested References

Chapter I Survey of Electromagnetic Interactions with Gases

A. The Second-Order Processes

B. The First-Order Process, Photoabsorption

C. The Hierarchy of Photoabsorption Processes

References

Chapter II Photoabsorption below the First Ionization Limit

Appendix

References

Chapter III Quasi-Discrete States above the First Ionization Potential

A. Types of "Discrete" Excitation above the First Ionization Potential

B. Photoelectron Spectroscopy

C. Discrete State-Continuum Interaction: Autoionization and Predissociation

D. The Nature of the Perturbation Matrix Elements in Autoionization

References

Chapter IV The Ionization Continuum

A. The Variation of Cross Section in the Vicinity of the Ionization Threshold

B. The Energy Region for Inner-Shell Excitation

C. "Cooper Minima"

D. Dependence of Absorption Cross Section upon the Type of Orbital (s, p, d, . . .) from Which Ejection Takes Place

E. Molecular "Barriers" to Electron Escape

F. Multiple Electron Excitations and Ionizations

G. Oscillator Strength Distribution in the Continuum

H. Dissociation in the Ionization Continuum

Summary of Useful Sum Rules

Appendix 1. Quantum Mechanical Derivation of Thomas-Reiche-Kuhn Sum Rule

Appendix 2. Relationship of the Electric-Dipole Matrix Elements to the Ground State Wave Function

Appendix 3. Interaction of Fast Charged Particles with Atoms and Molecules—A Digression

References

Chapter V Total Photoabsorption and Photoionization Cross Sections for Selected Molecules

A. Monatomic Gases

B. Diatomic Molecules

C. Triatomic Molecules

D. Polyatomics

References

Chapter VI Partial Cross Sections

A. General Considerations

B. Atoms

C. Diatomic Molecules

D. Triatomic Molecules

E. Polyatomic Molecules

Appendix 1. Table-Photoionization References for Other Molecules

Appendix 2. Derivation of the "Energy Gap Law" Simplified

Appendix 3. Classical Approximation and Dirichlet Integral

Appendix 4. Metastable Ions in Magnetic Mass Spectrometers

References

Chapter VII Angular Distribution of Photoelectrons

A. General Form of the Equation

B. Calculations of Angular Distributions

C. Experimental Considerations

D. Summary of Other Recent Measurements of ß

Appendix

References

Chapter VIII Instruments and Methods

A. Techniques for Measuring Photoabsorption Cross Sections and Ionization Yields

B. Photoionization Mass Spectrometry

C. Photoelectron Spectroscopy

D. Photoelectron-Photoion Coincidence Spectroscopy

References

Index