Chemical Spectroscopy and Photochemistry in the Vacuum-Ultraviolet

Vacuum Ultraviolet and Photoelectron Spectroscopy — Historical Background and Survey.- V.U.V. Spectra of Polyatomic Molecules.- Photoionization.- Photoelectron Spectroscopy.- References.- Aspects of Molecular Rydberg States.- References.- Photoelectron Spectroscopy.- - Electrons and Photons.- Some Experimental Aspects of Electron Energy Analysis.- Light Sources.- Photoelectron Bands Designated According to the Ionic States.- Vibrational Fine Structure.- Vibrational Fine Structure in the Third Band of Formaldehyde.- Vibrational Fine Structure in the Ketene Photoelectron Spectrum.- Vertical Ionization.- Interpretative Methods Involving Molecular Orbital Calculations.- Correlations between P.E. Spectral Data and Other Physical Parameters.- Photoelectron Spectra of Transient Species.- Photoelectron Spectra from Solids.- References.- Absolute Intensities and Classification of Transitions in Electron Impact Spectroscopy.- Generalized Oscillator Strengths.- Determination of Oscillator Strengths.- Oscillator Strengths Obtained by Extrapolation.- Optical Oscillator Strengths from Forward Scattering.- Classification of Transitions. Dipole-Quadrupole Behavior.- Franck-Condon Principle. Invariance in Relative Intensities.- Singlet-Triplet Transitions.- Strongly Forbidden Transitions at Low Kinetic Energies.- Identification of Triplets by Positive Ion Scattering.- Recent Results.- Deviations from Born Approximation at Small Scattering Angles. Selection Rules.- Singlet-Triplet Excitation at High Kinetic Energy. 11S?23S Transition in Helium.- Theoretical Study of Singlet-Triplet Selection Rules.- Other Singlet-Triplet Transitions.- Calculation of Singlet-Triplet Energy Differences.- Excited Triplet of H2O.- Other Recent Researches.- Addendum on Benzene.- References.- Photoionization of Free Radicals.- Methods of Production.- Available Data.- Hydrocarbon and Fluorocarbon Radicals.- Atmospheric Radicals.- O(3P).- N(4S).- OH.- O3 and HNO3.- References.- Photoelectron Spectroscopy of Molecular Beams.- and Chemical Studies.- Physical Studies.- Comparison of Photoelectron Intensities and Franck-Condon Factors in the Photoionization of H2, HD and D2.- Rotational Band Shapes in the Photoelectron Spectra of HF and DF.- Spin-Orbit Coupling and the Ratio of Photoionization Cross Sections in Some Atoms.- Summary and Conclusions.- References.- High Resolution Vacuum Ultraviolet Spectroscopy of Diatomic Molecules.- Instrumentation.- Spectrographs.- Sources.- Spectra.- Spectra of Valence States.- Spectra of Rydberg States.- BH.- Nitric Oxide.- Nitrogen.- Fluorine.- Hydrogen Fluoride.- Conclusions.- References.- Optical Properties of Liquids in the Vacuum UV.- Experimental Background.- Theory.- Carbon Ring Liquids.- Water.- Other Liquids.- Discussion.- References.- The Far Ultraviolet Absorption Spectra of Organic Molecules: Lone Pairs and Double Bonds.- Halogen Derivatives of Methane.- Halogen Derivatives of Ethane.- Ethylene Derivatives.- Benzene Derivatives.- Molecules Containing Divalent Sulfur.- References.- The Ethane Problem.- The Ground State.- The Ion.- The Ultraviolet Spectra.- Possible Weak Transitions.- The Primary Steps.- References.- A Pot-Pourri of Ultraviolet and Photoelectron Spectra of Iodides.- PE Spectrum of Vinyl Iodide.- UV Spectra of Alkyl Iodides.- PE Spectra of Fluoroiodoethanes.- References.- Beyond the Orbital Approximation.- The Need for a Language Adapted to Very Elaborate Wave-Functions.- The Loge Theory.- Change in the Localizability of Electrons during Ionization.- The Localizability of the Electron as a Starting Point to Calculate an Elaborate Wave-Function.- Loge Theory and Exciton Localizability.- References.- Natural and Magnetic Circular Dichroism Spectroscopy in the Vacuum Ultraviolet.- General.- Natural Circular Dichroism.- Magnetic Circular Dichroism.- Instrumentation.- The Natural CD Spectra of Benzene Chromophores.- The Natural CD Spectra of Ethylene Chromophores.- MCD Spectra of Benzene and Toluene.- References.- (H3C)2C=C(CH3)2, (H3C)2BN(CH3)2, (H3C)BF and (H3C)3B. Further Evidence for a ? ? ?* Assignment of the OLEFIN UV “Mystery” Band.- Helium (I) PE Spectra.- Far UV Spectra.- Concluding Remarks.- References.- Photoelectron Spectra of Moderate Sized Molecules.- The Interpretation of the PE Spectra of Structurally Similar Molecules.- A Comparison of the Bonding of First and Second Row p-Block Elements.- Photoelectron Studies of the Bonding of Particular Elements.- The Investigation of “Through Space” and “Through Bond” Interactions.- The Correlation of PES with UV Spectra and Other Techniques.- Theoretical Studies.- References.- HAM — a Semi-Empirical MO Theory.- The HAM Method.- Shielding (preliminary form).- Electrostatic Interaction (preliminary form).- Results.- References.- Ab Initio Calculations for Excited States of Molecules.- Geometrical Aspects..- Use of Ab Initio Walsh-Type Diagrams.- Some Examples.- Calculation of Vertical Transition Energies.- Consideration of the Vibrational Structure of Electronic Transitions.- References and Footnotes.- Threshold Electron-Impact Spectroscopy.- Interaction of Electrons and Molecules.- Experimental Techniques.- Applications of Threshold Methods.- Saturated Hydrocarbons.- Olefins.- Other Unsaturated Hydrocarbons.- Molecules Containing a Carbonyl Group.- Molecules Containing a Nitrogen Atom.- Other Molecules.- Conclusions.- References.- Spectra of Free Radicals and Molecular Ions Produced by Vacuum Ultraviolet Photolysis in Low-Temperature Matrices.- General Principles.- Stabilization and Spectra of Free Radicals.- Stabilization and Spectra of Molecular Ions.- References.- Rydberg States of Diatomic and Polyatomic Molecules.- Atomic Calibration.- Results.- Conclusions.- References.- Theory of Intravalency and Rydberg Transitions in Molecules.- Questions.- Theory of Excited States, Non-Closed Shell States.- Semi-Internal Orbitals.- The “Charge Wave Function, ?c” of a Non-Closed Shell State.- Energy of a Non-Closed Shell State.- Relation of the Intravalency and Rydberg States of Spectra.- Classification of Transitions into Intravalency, Pre-Rydberg and Rydberg Types.- Spectral Form of the Charge Wave Function of an Intravalency State.- The Charge Wave Function of a Pre-Rydberg State.- Electric Dipole Oscillator Strengths of Intravalency$$
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$$ and Pre-Rydberg(pR) Transitions.- Inner Ionization Potentials; Excited Core Rydberg Series Limits.- Theory of Excited States of Molecules.- Many Center Aspects.- Intravalency and Pre-Rydberg States of Molecules with RHF-MO(SCF)/NCMET.- The Intravalency AO Pool.- Molecular Semi-Internal Orbitals from the $$
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$$ Problems of the United Atom.- The Spectral Charge Wave Function of a Molecular Intravalency State $$
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$$ and of a Pre-Rydberg State(pR).- What is a Rydberg Orbital ?.- References and Footnotes.- On the Assignment of Molecular Rydberg Series.- The Rydberg Equation.- Series Identification.- Conclusion.- References.- On Molecular Rydberg Term Values.- Results.- Conclusions.- References.- Correlation of Molecular and Rare Gas Term Values.- References.- On the Possibilities of Studying the Electronic Structure of Organic Molecules through the Analysis of the Wave Function.- References.- The Early Years of Photochemistry in the Vacuum Ultraviolet.- Oxygen.- Nitrogen.- Hydrogen.- Carbon Dioxide.- Carbon Monoxide.- Water Vapour.- Organic Compounds.- Photoionization and Fragmentation of Polyatomic Molecules.- Experimental.- General Considerations.- Photoionization and Energy Deposition.- Dissociation Processes and the Determination of Thermochemical Quantities.- Diatomic Molecules.- Small Polyatomic Molecules.- Large Polyatomic Molecules.- Statistical Theory of Mass Spectra.- Radiationless Transitions.- Recent Tests of QET.- Benzene and Some Derivatives.- Kinetic Energy Release in Fragmentation.- Conclusion.- References.- Far Ultraviolet Photochemistry of Organic Compounds.- Direct Methods of Determining Photofragments.- Indirect Methods of Determining Photofragments.- Alkanes and Cycloalkanes.- Alkenes.- Carbonyl Compounds.- References.- Energy Partioning in the Photochemistry of Alkanes.- Photophysical and Photochemical Description.- Physical Methods for Determining Energy Partioning.- Chemical Methods.- Experimental Results and Discussion.- Conclusion.- References.- Recent Studies of the Fluorescence from Some Hydrocarbon Molecules.- Experimental.- Saturated Hydrocarbons.- Aromatic Molecules.- Simple Olefins.- References and Footnotes.- Production of Electronically Excited Species in Photodissociation of Simple Molecules in the Vacuum Ultraviolet.- Apparatus.- Application of Threshold Measurements.- Nature of the Primary Process.- The Spin Conservation Rule.- Predissociation.- Configuration of an Excited State.- References.- Energy Partitioning in the Photofragments.- Internal Energy of Photofragments.- Translational Energy.- Hot Photofragments.- Other Methods of Excitation.- References.- Generation of Coherent Light in the Vacuum Ultraviolet.- References.- Synchrotron Radiation as a Light Source.- Machines for the Production of Light.- Basic Equations Relating to Photon Energy and Intensity.- The Polarization of Synchrotron Radiation.- Possible Machine Improvements.- Some Experiments Utilizing the Pulse and Polarization Characteristics of Synchrotron Radiation.- References.- Optical Studies of Molecular Crystals in the Vacuum Ultraviolet Using Synchrotron Radiation.- Experimental Aspects.- Excitonic Excitations in Solid Rare Gases.- Atmospheric Molecules.- Organic Molecular Crystals.- References.- Photochemistry of Planetary Atmospheres and Interstellar Molecules.- Planetary Atmospheres.- The HO2 Mechanisms.- Ozone Mechanism.- Ionic Mechanism.- Interstellar Molecules.- The Interstellar Medium.- The Lifetime of Interstellar Molecules.- References.