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HIGH RESOLUTIONLASERPHOTOIONIZATIONANDPHOTOELECTRONSTUDIESWiley Series in Ion Chemistryand Physics
Edited by
Ivan PowisDepartment of Chemistry, University of Nottingham, Nottingham, England, UK
Tomas BaerDepartment of Chemistry, The University of North Carolina at Chapel Hill,Chapel Hill, North Carolina, USA
Cheuk-Yiu NgAmes Laboratory, USDOE, and Department of Chemistry, Iowa State University, Ames ,Iowa, USA
List of Contributors
xi i i
Preface
xv
CHAPTER 1 An Historical Introduction to Threshold Photoionization
1T. Baer and P-M Guyon
1 .1
Introduction
11 .2 Threshold Photoelectron Spectroscopy (TPES)
3
1 .2 .1 The Suppression of Energetic Electrons by TOF
8
1 .2 .2 The Role of Autoionization in TPES
91 .2 .3 The Mechanism for Threshold Electron Production
1 1
1 .3 Threshold Ionization with Pulsed Laser Sources
1 31 .3 .1
The Third Surprise
1 51 .3 .2 A Comparison of PFI-TPES and TPES
1 6
1 .4 Conclusions
1 7
CHAPTER 2 High Resolution Spectroscopy with Photoelectrons :ZEKE Spectroscopy of Molecular Systems
2 1K. Müller-Dethlefs
2 .1 Introduction
2 22 .1 .1 Development of Photoionization Experiments
2 82 .2 From Photoelectron to ZEKE Spectroscopy
3 12 .2 .1 Principle of ZEKE Detection
3 12 .2 .2 The Delayed Pulsed Field Ionization of Rydberg States
3 42 .3 Details of the ZEKE Experiment : Toward Highest Resolution
3 72 .4 Rotationally Resolved ZEKE Spectroscopy of Molecules
4 32 .4.1 NO
4 32 .4.2 Benzene
4 72 .4.3 H2O and H2 S
5 82 .5 Vibrationally Resolved ZEKE Spectroscopy of Molecular Clusters
602 .5 .1 Ar-NO
602 .5 .2 The NO Dimer
602 .5 .3 Hydrogen-bonded Complexes
6 1
2 .5 .4 Comparison between the Different Hydrogen-bondedPhenol-X Complexes
692 .6 Perspectives and Conclusions
70
CHAPTER 3 State-resolved Photoionization Dynamics of SmallMolecules Using Coherent VUV Radiation
7 9R.T. Redman and MG. White
3 .1 Introduction
80
3 .2 Photoionization Dynamics
84
3 .3 Experiment
87
3 .3 .1 Coherent VUV Harmonic Generation
893 .3 .2 ZEKE-PFI Techniques
9 23 .4 Rotationally Resolved Photoionization of Molecules: Selected
Examples
9 6
3 .4.1 Diatomic Molecules
9 6
3 .4 .2 Nonlinear Polyatomic Molecules
10 4
3 .5 Summary
11 2
CHAPTER 4 VUV-ZEKE Photoelectron Spectroscopy : Final-stateInteractions in Small Molecular Systems
119F. Merkt and T.P. Sofiley
4.1 Experimental Techniques
1204 .1 .1 Introduction : The Advantages of Single-photon Ionization
12 04 .1 .2 Vacuum Ultraviolet and Extreme Ultraviolet Radiation Sources 12 14 .1 .3 Experimental ZEKE Photoelectron Spectroscopy
12 64.2 Intensity Perturbations in Rotationally Resolved Spectra
12 84 .2 .1 Intensities in Conventional, Threshold and ZEKE
Photoelectron Spectroscopy
12 84 .2 .2 The Hydrogen Molecule
13 14 .2 .3 The Nitrogen Molecule
13 44.2 .4 The Oxygen Molecule
13 64 .2 .5 The Carbon Dioxide Molecule
13 84 .2 .6 Other Examples of Final-state Interactions
14 0
4 .2 .7 Conclusions
14 1
4 .3 Review of Factors Affecting High Rydberg State Lifetimes
14 34 .3 .1 Lifetimes of the States Detected in ZEKE-PFI Experiments
14 34 .3 .2 The Nature and the Formation of the ZEKE States
14 5
4 .3 .3 Effects of Electric Fields
1474.4 Theoretical Models
1494 .4 .1 Rotational Autoionization
1494 .4 .2 Electric Field Effects
15 54 .4 .3 Complex Resonances in Vibrational and Electronic
Autoionization
164
CHAPTER 5 Rotationally Resolved Autoionization of MolecularRydberg States
17 1H. Lefebvre-Brion
5 .1
Introduction
17 25 .2 Theoretical Treatment of High Rydberg States
17 25 .2 .1 Generalities on Different Hund's Coupling Cases
17 25 .2 .2 Rydberg States Having a E Ion Core
17 35 .2 .3 Rydberg States Having a 2n Ion Core
17 45 .2 .4 Examples of Rydberg Complexes
17 55 .3 Rotational Autoionization
18 45 .3 .1 Rotational Autoionization for a E Ion Core
18 45 .3 .2 Rotational Autoionization for a 2II Ion Core
18 85 .4 Conclusion
19 0
CHAPTER 6 Rotationally Resolved Resonance-enhanced MultiphotonIonization Photoelectron Spectroscopy of Diatomi cHydrides
19 5C.A. de Lange
6 .1 Introduction
19 66 .2 Experimental Techniques
19 96.2 .1
`Magnetic Bottle' Electron Spectrometer
19 96.2 .2 Time-of-flight to Energy Conversion and Calibration
2026 .2 .3 Wavelength Spectra and Photoelectron Spectra
2046 .2 .4 Mass-resolved Ion Detection
20 56 .2.5 ZEKE-PFI
20 56 .2 .6 Nanosecond Laser System
20 66.3 Theory
2076.4 Diatomic Hydrides
21 16 .4.1 The OH Radical
21 16 .4.2 The NH Radical
2206 .4.3 The HC1 Molecule
2326.5 Conclusions
242
CHAPTER 7 Exploiting Polarization in the Study of Molecula rPhotoionization Dynamics
247K.L. Reid and D.J. Leahy
7 .1 Introduction
2487.2 Two-photon Ionization
2547 .2.1 Advantages
2547 .2.2 Formalism
2597.3 Applications
265
7 .3 .1 The First `Complete' Molecular PhotoionizationExperiment : NO(A ZE+)
26 57 .3 .2 Further Experiments
2747 .3 .3 Determination of Alignment
27 57 .3 .4 Extension to Other Systems
2767.4 Conclusions
277
CHAPTER 8 Rotationally Resolved Photoelectron Spectra a tNear-threshold Kinetic Energies
28 1K. Wang and V. McKoy
8 .1 Introduction
2828 .2 Theory and Formulation
2848 .2 .1 (n + 1') REMPI for Linear Molecules
2848 .2 .2 (n + 1') REMPI for Asymmetric Tops
29 18 .2 .3 (n + 1') REMPI for Symmetric Tops
29 58 .2 .4 Computational Procedures
2968.3 Results and Discussion
2978 .3 .1 REMPI via Rydberg States of Linear Molecules
2978 .3 .2 ZEKE-PFI of Linear Molecules
31 28 .3 .3 ZEKE-PFI of Nonlinear Molecules
31 9
CHAPTER 9 Low-frequency Torsional and Vibrational Motions i nToluene +, Phenylsilane+, and Benzyl +: Experimentsand Ab Initio Calculations
33 1K.-T. Lu, G.C Eiden, J.K. Badenhoop, F.A . Weinhold,and JC Weisshaar
9 .1
Introduction
33 29.2 Experimental Technique
33 39 .3 , Internal Rotation in Toluene and Phenylsilane Neutral s
and Cations
3349 .3 .1 Introduction to Internal Rotation Barriers
3349 .3 .2 Rotor States
33 69 .3 .3
S 1 -So Selection Rules
3379 .3 .4 PFI Selection Rules
33 89 .3.5 S1 -So Spectra and Assignments
3409 .3 .6 Cation Rotor States : PFI Spectra of Toluene+ and
Phenylsilane +
34 19 .3 .7 Bond Energies from Adiabatic Ionization Potentials
3479 .3 .8 Ab Initio Equilibrium Geometries and Torsional Barriers
3489 .3 .9 Vibronic Coupling in Phenylsilane + and Toluene+
35 19 .3 .10 Donor-Acceptor Model of CH3 and SiH3 Torsional
Potentials
354
9 .4 R2PI-PFI Studies of the Benzyl Radical
3599 .4 .1 R2PI and PFI Spectra
3599 .4 .2 Assignment of Benzyl+ Vibrational Bands
3609 .4 .3 Vibronic Coupling Mechanism
3649 .4 .4 Nature of Exocyclic C-C Bond in Benzyl and Benzyl+
364
CHAPTER 10 ZEKE Studies with Picosecond Lasers
369J.L. Knee
10 .1
Introduction
37010 .2 Background
37 110 .2 .1 Formulation of the Molecular Problem
37 110 .2 .2 Available Experimental Techniques
37 510 .3 Photoelectron Probing of Molecular Dynamics
37 910 .3 .1 Laser Time-of-flight Photoelectron Spectroscopy
38010 .3 .2 Methodology for Dynamics Studies Using ZEKE PES
38310 .4 Applications of Time-resolved ZEKE
38 910 .4 .1 ZEKE Studies of IVR
38910 .4 .2 Van der Waals Molecule IVR and Vibrational
Predissociation
39 310 .4 .3 Electronic State Nonradiative Transitions
39 810 .5 Future Directions
400
CHAPTER 11 On the Control of Molecular Photoionization : Effectsof Mode Specificity in Discrete-Continuum Couplingon the Dynamics of Near-threshold Electron Ejectio nin NO2
407E.R. Gran t
11 .1
Introduction
40811 .1 .1
Vibrational Autoionization
40811 .1 .2 Normal Coordinate Dependence of Vibrationa l
Autoionization
40911 .1 .3 Electronic Structure of the Higher Excited States of NO 2
41011 .2 Photoselection and the Preparation of Excited States of NO 2
41 111 .3 Triple Resonance and the Mode-selected Vibrational
Autoionization of NO 2
41 311 .4 Triple-resonant Threshold Photoionization of NO 2 : The Effect
of Mode Selectivity in Discrete-Continuum Interactions onThreshold Photoionization Intensities
41911 .4 .1 Method for High-resolution Threshold Photoionizatio n
Spectroscopy
41911 .4.2 Vibrational Structure
420
11 .4 .3 Rotational Structure in the Vibrational Ground State o fNO2+
42 311 .4 .4 Rotational Intensities for Threshold Photoionization to
Form Vibrationally Excited States of NO 2 +
42 911 .5 Conclusions
43 2
CHAPTER 12 Physics of Near-threshold States in Molecula rHydrogen
437E.E. Eyler
12 .1
Introduction
43 812 .2 General Behavior of Near-threshold Levels
43912 .2 .1 Long-range Potentials : Rydberg States in the Coulomb
Potential
43 912 .2 .2 Short-range Potentials
44 1
12 .3 Atom-like Molecules: Nonpenetrating Rydberg States
44 512 .3 .1 Overall Structure of Rydberg States with High n and 1
44 512 .3 .2 Autoionization and Predissociation
44812 .3 .3 Effects of External Electric Fields
44812 .4 Rydberg np States of Molecular Hydrogen
45 012 .4 .1
Understanding Strong Interchannel Perturbations :Two-channel Quantum-defect Theory
45 112 .4 .2 High-precision Energy Level Measurements
45 312 .4 .3 Determination of the Ionization Potential
45 512 .4 .4 Dynamics of the np States
45912 .5 High Vibrational Levels near the Second Dissociation Limit
46 112 .5 .1
General Structure
46 112 .5 .2 Perturbations, Including Gerade-Ungerade Mixing
46412 .5 .3 Relation to Long-range Atomic Collisions and Trap
Physics
46 712 .6 Near-threshold Dissociation to H(ls) + H(2s or 2p)
46 912 .6 .1 General Observations and Calculated Cross-sections
46 912 .6 .2 High-resolution Measurements of Continuum Structure ,
Including Atomic 2s : 2p Branching Ratios
47 012 .6 .3 Determination of the Dissociation Limit
47412 .6 .4 Shape Resonances above the Threshold
47 512 .6 .5 Prospects for Observing Vibrational Rydberg States of a n
Ion Pair
47712 .7 Summary and Conclusions
47 8
Author Index
48 3
Subject Index
503
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