Excited-state dynamics of organic intermediates [Elektronische Ressource] / Bastian M. Noller

© Bastian Noller, Universität Würzburg/Université Orsay, Physical Chemistry

Informations

• Publié par: julius-maximilians-universitat_wurzburg
• Publié le: 01 janvier 2009
• Nombre de lectures: 36
• Poids de l'ouvrage: 66 Mo

Extrait

dipl.-chem. bastian m. noller
D I S S E RTAT I O NG E R M A N C O M M I T T E E :
Eingereicht am: 19.03.2009
bei der Fakultät für Chemie und Pharmazie
1. Gutachter: Prof. Dr. I. Fischer
2. Prof. Dr. M. Mostafavi
der Dissertation
1. Prüfer: Prof. Dr. T. Brixner
2. Prüfer: Prof. Dr. B. Engels
3. Prüfer: Prof. Dr. C. Meier
des öffentlichen Promotionskolloquiums
Tag des öffentlichen Promotionskolloquiums: 11.05.2009
Doktorurkunde ausgehändigt am: ..........................................
F R E N C H C O M M I T T E E :
Soutenue: 11.05.2009
devant la commission d’examen:
1. Rapporteur: Prof. Dr. M. Mostafavi
2. Prof. Dr. C. Meier
de thèse de doctorat
1. Directeur de thèse: Dr. J.-M. Mestdagh
No. d’ordre: 9420No. d’ordre: 9420
U N I V E R S I T É PA R I S - S U D 1 1
THÈSE
présentée pour obtenir le grade de
D O C T E U R E N S C I E N C E S D E L’ U N I V E R S I T É
PA R I S - S U D 1 1
par
D I P L . - C H E M . B A S T I A N M . N O L L E R
Sujet:
Excited-State Dynamics of Organic Intermediates
Soutenue le lundi 11 mai 2009 devant la commission d’examen:
Prof. Dr. Mehran Mostafavi Président
Prof. Dr. Christoph Meier Rapporteur
Prof. Dr. Bernd Engels
Prof. Dr. Tobias Brixner Rapporteur
Prof. Dr. Ingo Fischer Directeur de thèse
Dr. Jean-Michel Mestdagh Directeur de thèseTruly to want something means to do an experiment in order to find
out what we can do. —Friedrich NietzscheC O N T E N T S
1 introduction 1
2 spectroscopic techniques 5
2.1 REMPI Spectroscopy 5
2.2 Photofragment & Doppler Spectroscopy 6
2.3 Velocity Map Imaging 8
2.3.1 Inversion Methods 9
2.4 Femtosecond Time-Resolved Pump-Probe Spectroscopy 11
2.5 Synchrotron Light Sources & Reactive Intermediates 14
2.5.1 TPEPICO Spectroscopy 15
3 experimental setup 17
3.1 Carbene and Radical Sources 17
3.1.1 Water Cooled Pyrolysis Source 17
3.2 Seeding Pyrophorus Compounds into a Molecular Beam 18
3.3 Nanosecond Setup in Würzburg 19
3.3.1 Laser System & Molecular Beam Apparatus 19
3.4 Femtosecond Setup at the CEA in Saclay 21
3.4.1 Laser System 21
3.4.2 Molecular Beam Apparatus 22
3.4.3 Velocity Map Imaging Spectrometer 22
3.5 Synchrotron Light Source with TPEPICO: Soleil 23
4 computational tools for experimentalists 25
4.1 Restricted and Unrestricted Calculations 25
4.2 Calculating Ground State Equilibrium Properties 26
4.3 Transition States and Dissociation Energies 27
4.3.1 Methods and Transition States 27
4.3.2 How to Find Precise Transition States 28
4.4 Excited-State Calculations 28
4.5 Selecting Senseful Basis Sets 29
4.6 RRKM Theory for Predicting Unimolecular Reaction Rates 30
5 convolution in femtosecond spectroscopy 33
5.1 The Convolution of Signals 33
5.2 The Two-State Model 35
5.3 The Three-State 36
6 photodissociation dynamcis of 2-propyl 39
6.1 Introduction and State of Knowledge 39
6.2 Mass Spectra and Experimental Details 40
6.3 Doppler Profiles 41
6.4 Unimolecular Rate Constants 44
6.5 RRKM Calculations 45
6.6 Calculations on Dissociation Barriers 47
6.7 Experiments with 1-Propyl 49
6.8 Discussion and Conclusions 50
IX7 photoionization studies of diazirines and their
cations 53
7.1 Introduction and Goals 53
7.2 Deriving Thermochemical Properties 53
7.3 Experimental Results 55
7.4 Computational 59
7.5 Discussion 61
8 photoionization studies of phenylcarbenes 67
8.1 Experimental Details 67
8.2 Results 67
8.3 Computational for Interpretation 72
8.4 Conclusions on the Photoionization of Phenylcarbenes 74
9 ultrafast excited-state dynamics of phenylcar-
benes 75
9.1 Introduction and State of Knowledge 75
9.2 Experimental Details 76
9.3 Results 76
9.3.1 Clean Phenylcarbene Generation 76
9.3.2 Time-Resolved Measurements 82
9.4 Computations 88
9.4.1 Procedures, Goals and Methods 88
9.4.2 Computational Results 89
9.5 Discussion 91
9.5.1 Pyrolysis of Diazirines 91
9.5.2 Excited-State Dynamics of CPC 93
9.5.3 of TFPC 95
9.5.4 Conclusions 96
10 excited-state dynamics of propadienylidene 99
10.1 Introduction and State of Knowledge 99
10.2 Dissociation of the Precursor 101
10.3 Femtosecond Time-Resolved Excited-State Dynamics 104
10.3.1 Specific Experimental Details 104
10.3.2 Experimental Results 104
10.3.3 1-Iodopropyne and3-Bromopropyne Radicals 105
10.3.4 Excited-State Dynamics of Propadienylidene 106
11 photodissociation dynamcis of propadienylidene 109
11.1 Experimental Details and Mass Spectra 110
11.2 H-Atom Photofragment Spectroscopy 113
11.3 Rate Constants for the Loss of Hydrogen 115
12 excited-state dynamics of the 2,3-dimethylbut-2-
yl radical 119
12.1 Introduction 119
12.2 Radical Generation 121
12.3 Time-Resolved Experimental Results 123
12.4 Conclusions and Discussion 124
13 synthesis 127
13.1 1,3-Dibromopropyne 127
13.2 3-Bromo-1-iodopropyne 127
X