S. P. McGlynn

Photophysics and Photochemistry in the Vacuum Ultraviolet

Photophysics of Highly-Excited States.- 1. Introduction.- 2. Quantum Defect Theory.- 3. Core Effects.- 4. Intermolecular Rydberg Correlations.- 5. Field Effects.- 6. Rydberg States in Condensed Media.- 7. Concluding Remarks.- Methods for Studying Higher Excited States in Molecules and Molecular Crystals by Means of Synchrotron Radiation.- 1. Introduction.- 2. Properties of Synchrotron Radiation Sources: A Short Overview.- 3. Some General Aspects of Synchrotron Radiation Instrumentation.- 4. Absorption and Reflection Spectroscopy.- 5. Time-Resolved and Energy-Resolved VUV Luminescence Spectroscopy.- 6. Photoemission.- 7. Perspectives.- 8. Appendix.- Nonlinear Optics and Laser Spectroscopy in the Vacuum Ultraviolet.- 1. Introduction.- 2. Vacuum Ultraviolet Lasers.- 3. Nonlinear Optical Methods for Producing Tunable VUV Radiation.- 4. Applications to Chemical Physics.- 5. Future Goals.- Multiphoton Ionization and Third-Harmonic Generation in Atoms and Molecules.- 1. Introduction.- 2. Resonantly-Enhanced Multiphoton Ionization.- 3. Multiphoton Ionization and Third-Harmonic Generation in Rare Gases.- Electron-Impact Spectroscopy of Molecules.- 1. Introduction.- 2. General Theory.- 3. Experimental.- 4. Experimental Results.- Elements of Quantum Defect Theory. I. Introduction and Formalism.- 1. Introduction to Quantum Defect Theory.- 2. Multichannel Quantum Defect Theory in Atoms.- Elements of Quantum Defect Theory. II. A Unified Theory of Rydberg and Autoionizing States.- 1. Introduction.- 2. Eigenchannel Quantum Defect Theory.- 3. Ab initio Calculations of Quantum Defect Parameters.- 4. Applications.- Elements of Quantum Defect Theory. III. Diatomic Molecules.- 1. Introduction to Molecular QDT.- 2. Comparison with Experiment.- 3. Inclusion of Molecular Dissociation.- Negative-Ion States.- 1. Introduction.- 2. Negative-Ion Properties.- 3. Unimolecular Electron Attachment.- 4. Multiply-Charged Negative Ions.- 5. Photoabsorption by Negative Ions.- 6. Recent Studies of Long-Lived He Negative Ions.- 7. Production of Negative Ions by Photon Reactions.- 8. Collision of High-Rydberg Atoms with Electron-Attaching Molecules and the Possible Influence of Dipole Bound States.- 9. Negative Ions of Molecular Clusters.- Superexcited nd Ionic State Relaxation Processes in Vacuum Ultraviolet Excited Polyatomic Molecules.- 1. Introduction.- 2. Fundamental Processes.- 3. Competing Decay Channels of Superexcited States.- 4. Methods for Studying Superexcited and Ionic States and Their Relaxation Processes.- 5. Further Remarks on Molecular Autoionization.- 6. Decay of Ion States.- Photoionization Dynamics of Small Molecules.- 1. Introduction.- 2. Shape Resonances in Molecular Photoionization.- 3. Molecular Autoionization.- 4. Concluding Remarks.- Photodissociation Dynamics of Gas-Phase Small Molecules.- 1. Introduction.- 2. ICN Photodissociation in the Near Ultraviolet.- 3. VUV Photodissociation of HCN.- 4. VUV Photodissociation of the Cyanogen Halides.- 5. Conclusions.- VUV Spectroscopy of Rare-Gas Van Der Waals Dimers.- 1. Introduction.- 2. General Background.- 3. Experimental Apparatus.- 4. Dependence of the Cluster Ion Signals on Nozzle Stagnation Pressure.- 5. Appearance Potentials of the Dimer Ions and Dissociation Energies of the Dimer-Ion Ground States.- 6. Molecular Rydberg Structure Between the Atomic Fine-Structure Thresholds: Dissociation Energies of X+2(C 2?1/2u) and XY+(B 2?1/2 and D 2?1/2+).- 7. Molecular Rydberg Structure in the Spectra of NeY Near the Ne 3s Atomic Resonance.- 8. Molecular Rydberg Structure in the Spectra of ArKr and ArXe Near the Ar 5s and 3d Atomic Resonances.- 9. Molecular Rydberg Structure in the Spectra of X2 and XY Near the High-Lying Atomic Rydberg States.- 10. Summary and Conclusions.- Excitons and Energy Transfer in Insulators.- 1. Prologue.- 2. Frenkel Excitons.- 3. Wannier Excitons.- 4. Deep Wannier Atomic Impurity States.- 5. Excitons and Impurity States in Rare-Gas Fluids.- 6. Molecular Wannier Impurity States in Rare-Gas Solids.- 7. Excited-State Dynamics in Rare-Gas Solids.- 8. Self-Trapping of Excitons in Rare-Gas Solids.- 9. Lattice Relaxation Around Impurity States.- 10. Electronic Relaxation of Impurity States.- 11. Electronic Energy Transfer in Rare-Gas Solids.- 12. Perspectives.- Regular and Irregular Motion in Classical and Quantum Systems.- 1. Introduction: Order and Chaos.- 2. Integrable Systems.- 3. Perturbation of Integrable Systems and the KAM-Theorem.- 4. Area-Preserving Mappings.- 5. Chaotic Systems.- 6. A Generic System is Neither Integrable Nor Ergodic, But Shows a Stochastic Transition.- 7. The Birkhoff-Gustavson Normal Form and Invariant Tori Below the Critical Energy.- 8. Do Quantum Systems Exhibit Chaotic Behavior?.- 9. Integrable Systems and Tori Quantization.- 10. Quantization of Chaotic Systems.- 11. Statistics of Energy Levels.- 12. Quantizing a Generic System.- 13. Conclusions and Discussion.- New Trends in Atomic Diamagnetism.- 1. Introduction.- 2. The Coulomb Spectrum.- 3. The Landau Spectrum.- 4. The Atom in a Magnetic Field.- 5. Classical Mechanics of Diamagnetism.- 6. Quantum Mechanical Approach.- 7. Semi-Classical Methods.- 8. Experimental Studies in Atomic Physics.- 9. Prospects and Conclusions.- Evidence for Motional Electric Field Effects in the Absorption Spectrum of Lithium Vapor in a Magnetic Field.- 1. Introduction.- 2. Results and Discussion.- On the Spectrum Of V(?)

Molecular Rydberg states. XI. Quantum defect analogies between molecules and rare gases

Vleft( rho right) = - frac{{qt}}{rho } + frac{{rt}}{{{rho ^2}}} + stp + t{p^2}.

Photoionization of perylene in polar solvents

. Physical Implications for a Variety of Problems.- 1. Introduction.- 2. Solution of the Eigenvalue Problem.- 3. Applications.- 4. Summary.- Perturbation Spectroscopy.- 1. Introduction.- 2. Perturbation Theory and MCD Spectroscopy.- 3. Electric Field-Effect Spectroscopy.- 4. Pressure-Effect Spectroscopy.- Circular Dichroism and Magnetic Circular Dichroism Studies in the Vacuum Ultraviolet.- 1. Introduction.- 2. Instrumentation.- 3. Results.- Electric Field Studies in the Vacuum Ultraviolet.- 1. Introduction.- 2. Experimental.- 3. General Results.- 4. Excited-State Parameters.- 5. Arc-Suppressor Solvent Effects.- 6. Conclusions.- Valence-Shell and Rydberg Transitions in Large Molecules.- 1. Introduction.- 2. The Rydberg Concept.- 3. From Spectra to Photochemistry.- 4. Rydberg States of Transition Metal Complexes.- Multiphoton Spectroscopy and Photochemistry.- 1. Introduction.- 2. Nonlinear Photochemistry.- 3. Two Examples.- 4. Other Systems.- Excess Energy Dependence of Vibrational Relaxation and Photophysical Branching Ratios in Isolated Aromatic Molecules: Relevance to Vacuum Ultraviolet Photochemistry.- 1. Introduction.- 2. Spectral Characteristics of Gas-Phase Fluorescence.- 3. Excess-Energy Dependence of Radiationless Transitions: Theory.- 4. Excess-Energy Dependence of Radiationless Transitions: Experiment.- 5. Intramolecular Vibrational Relaxation.- 6. Photochemical Implications of the Energy Dependence of Electronic Relaxation Processes.- Theoretical Studies of the Electronic Structure and Spectra of NH3+.- 1. Introduction.- 2. Franck-Condon Analysis of the 2A1(NH3+) ? 1A1 (NH3) Spectrum.- 3. Ab initio Calculations on Low-Lying States of NH3+.- Theoretical Correlations of Organic Photochemical Reactions in the VUV.- 1. Introduction.- 2. 1,4-Cyclohexadiene.- 3. Methylene Cyclopropane.- Photochemistry of Saturated Alcohols and Open-Chain Ethers at 185 nm in the Liquid Phase.- 1. Introduction.- 2. Discussion.- Photolysis of Cyclic Ethers and Acetals at 185 nm in the Liquid Phase.- 1. Discussion.- List of Participants.

Photoelectron spectra, electronic structure and long-range electronic interaction in some steroids

Abstract Photoelectron spectroscopic data are reported for a variety of mono-, di-, and tricarbonyls. Band identifications based on correlative arguments are given. Those experimental effects found useful in identifying the nature of the various ionization bands are specified.

Spin uncoupling in the 6s Rydberg states of methyl iodide. Rotational subband structure in one‐photon absorption

The s and d Rydberg series of hydrogen iodide and methyl iodide are reported. These series are assigned using analogies to the corresponding series in xenon. It is shown that a comparison between molecular spectra and pertinent atomic data provides a facile assignment technique for molecular Rydberg spectra. Using the phase amplitude method, the Rydberg data are analyzed in an attempt to provide information on the residual atomic and molecular potentials and to categorize them qualitatively as attractive/repulsive, long range/short range. It is shown that, for l?2, the centrifugal barrier inhibits ingress of the Rydberg electron into the core and that the molecule is effectively spherically symmetric.

Density effects on high‐n molecular Rydberg states: CH3I and C6H6 in H2 and Ar

Abstract The ultraviolet photoelectron spectra of benzoic acid and 20 of its derivatives are presented. The low-energy regions of these spectra are “deconvoluted” and assigned using chemical substitution effects.

Spin uncoupling in the 6s Rydberg states of methyl iodide. Rotational subband structure in two‐photon resonant absorption

The photoionization of perylene in two common polar solvents (acetonitrile and dimethylformamide) is reported. The transient absorption spectra differ significantly from one solvent to the other: Positive and negative ion absorption intensities invert as also do ion decay times. These differences are attributed to solute–solvent interactions in the excited state. The mechanism for the photoionization process is posited to involve electron injection from perylene to the electrophilic solvent (i.e., acetonitrile) and hole injection from perylene to the nucleophilic solvent (i.e., dimethylformamide).

Electronic structure of haloalkanes : a high resolution photoelectron spectroscopic study

Alicyclic molecular frameworks are useful for the study of electronic through-bond (TB) and through space (TS) interactions of functional groups over fixed distances and/or a specified number of C-C bonds. Steroids, being readily available, stable and stereochemically well-defined, are especially suited for such investigations. Indeed, their use in the study of the stereochemical aspects and the long-range effects of groups situated at specified distances from chemically reactive centers has been well documented over the last 20 years. Since steroids are compounds of considerable biological importance, their activity being dramatically dependent on construction, conformation and electronic structure, it is surprising that our knowledge of their electronic structure, whether by quantum chemistry or photoelectron (PE) spectroscopy, is so sparse. Having recorded the first PE spectra of steroids (refs. 1,2) we believe that such studies may resolve many problems concerning long-range intramolecular interaction since (i) PE spectroscopy is a gas phase method and its results pertain to the free molecule and (ii) steroids by virtue of their fixed geometry are unable to form intramolecular (head-to-tail) adducts in which both TB and TS effects might separately propagate. Indeed, one should expect the presence of TB interactions only. We report the PE spectra of several androstane derivatives and derive their electronic structure using empirical arguments and of quantum chemical, MNDO calculations. Emphasis is placed on the long range effects of a carbonyl group located at the biologically important 3-, 11- and 17- positions and the enhancement of these effects by interpolated, localized double bonds.The position and fine structure of the lowest energy PE bands and the shift of the a-onsets are the gauges used to estimate these effects. These long range effects seem to exert considerable influence on conformation, activity and, particularly , on fast intramolecular electron transfer (ET) such as has been observed recently in steroid solutions.