HIGH RESOLUTIO N LASE R PHOTOIONIZATIO N AN D PHOTOELECTRO N STUDIE S Wiley Series in Ion Chemistr y and Physic s Edited b y Ivan Powis Department of Chemistry, University of Nottingham, Nottingham, England, U K Tomas Baer Department of Chemistry, The University of North Carolina at Chapel Hill , Chapel Hill, North Carolina, USA Cheuk-Yiu N g Ames Laboratory, USDOE, and Department of Chemistry, Iowa State University, Ames , Iowa, USA
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HIGH RESOLUTION LASER PHOTOIONIZATION AND …9.3 .7 Bond Energies from Adiabatic Ionization Potentials 347 9.3 .8 Ab Initio Equilibrium Geometries and Torsional Barriers 348 9.3 .9
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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
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