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Contents
3
Ultrafast Dynamics of Hydrogen Atoms in Hydrocarbon
Molecules in Intense Laser Fields: Hydrogen Atom Migration
and Scrambling in Methylacetylene . . . . . . . . . . . . . . . . . .
49
Tomoya Okino and Kaoru Yamanouchi
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49
3.2 Experiment and Data Analysis . . . . . . . . . . . . . . . . . . .
50
3.3 Three-Body Decomposition Pathways of Methylacetylene
and Methyl-d 3 -Acetylene . . . . . . . . . . . . . . . . . . . . .
52
3.3.1 Three-Body Decomposition Pathways with CC Bond
Breaking . . . . . . . . . . . . . . . . . . . . . . . . . .
52
3.3.2 Three-Body Decomposition Pathways with H + and H
+
2
Ejection . . . . . . . . . . . . . . . . . . . . . . . . . .
56
3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
59
4
Femtosecond Photodissociation Dynamics by Velocity Map
Imaging. The Methyl Iodide Case . . . . . . . . . . . . . . . . . . .
61
Rebeca de Nalda, Luis Rubio-Lago, Vincent Loriot, and Luis Bañares
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . .
61
4.2 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . .
64
4.2.1 The Experiment: Femtosecond Velocity Map Imaging . .
64
4.2.2 The Multidimensional Analysis . . . . . . . . . . . . . .
67
4.3 The A Band . . . . . . . . . . . . . . . . . . . . . . . . . . . .
69
4.3.1 Reaction Clocking: The Resonant Experiment . . . . . .
70
4.3.2 Transition-State Imaging: The Non-resonant
Experiment . . . . . . . . . . . . . . . . . . . . . . . . .
76
4.3.3 Observation of Transient Molecular Alignment . . . . . .
81
4.3.4 (CH 3 I) 2 Dimer Photodissociation Dynamics . . . . . . .
82
4.3.5 Resonant Probing: The Role of the Optical Coupling
Window . . . . . . . . . . . . . . . . . . . . . . . . . .
86
4.4 The B Band . . . . . . . . . . . . . . . . . . . . . . . . . . . .
88
4.4.1 Parent Ion Detection . . . . . . . . . . . . . . . . . . . .
89
4.4.2 Fragment Velocity Map Imaging Detection . . . . . . . .
90
4.4.3 Time-Resolved Photoelectron Imaging . . . . . . . . . .
93
4.5 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . .
94
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
96
5
Time-Resolved Photoelectron Spectroscopy for Excited State
Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
99
Roman Spesyvtsev, Jonathan G. Underwood, and Helen H. Fielding
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . .
99
5.2 Probing Non-adiabatic Dynamics Using Time-Resolved
Photoelectron Spectroscopy . . . . . . . . . . . . . . . . . . . . 100
5.2.1 Photoelectron Spectra: Using the Cation to Map Excited
State Dynamics . . . . . . . . . . . . . . . . . . . . . . 101