Femtochemistry : with the Nobel lecture of A. Zewail / edited by Frans C. De Schryver, Steven De Feyter, and Gerd Schweitzer.

Format:

Book

Contributor:

Zewail, Ahmed H.

Schryver, Frans C. de.

Feyter, Steven De.

Schweitzer, Gerd.

Language:

English

Subjects (All):

Chemical bonds--Congresses.

Chemical bonds.

Chemical kinetics--Congresses.

Chemical kinetics.

Genre:

Conference papers and proceedings.

Physical Description:

xxii, 438 pages : illustrations (some color) ; 25 cm

Place of Publication:

Weinheim ; New York : Wiley-VCH, [2001]

Contents:

1 Femtochemistry: Atomic-Scale Dynamics of the Chemical Bond Using Ultrafast Lasers (Nobel Lecture) / Ahmed H. Zewail 1

1.2 Dynamics and Arrow of Time 10

1.2.1 Origins

From Kinetics To Dynamics 10

1.2.2 The Arrow of Time 14

1.3 Femtochemistry: Development of the Field 17

1.3.1 The Early Years of Coherence 17

1.3.2 The Marriage with Molecular Beams 22

1.3.3 The Transition to the Sub-Picosecond Regime 29

1.3.4 The Femtosecond Dream 32

1.3.5 Femtocopia

Examples from Caltech 50

1.3.6 Opportunities for the Future 57

1.4 Impact and Concepts

A Retrospective 65

1.4.1 Time Resolution

Reaching the Transition-State Limit 65

1.4.2 Atomic-Scale Resolution 66

1.4.3 Generality of the Approach 66

1.6.1 A Primer for Femtoscopy, Coherence and Atoms in Motion 72

2 Transition State Theory and Reaction Dynamics - An Overview / Ward H. Thompson, Philip M. Kiefer, James T. Hynes 87

2.2 Crossing the Transition State in Solution 88

2.3 Acid-Base Proton-Transfer Reactions in Solution 89

2.4 Wave-Packet Evolution for Proton-Transfer Reactions 92

3 Organic Femtochemistry: Diradicals, Theory and Experiments / Steven De Feyter, Eric W.-G. Diau, Ahmed H. Zewail 97

3.2 Experimental 97

3.3 Tetramethylene, Trimethylene, and the Constrained Diradical[6] 99

3.3.1 Theoretical: PES and Reaction Pathways 99

3.3.2 Tetramethylene: Dynamical Time Scales and Stereochemistry 101

3.3.3 The Constrained Diradical and Trimethylene 104

3.3.4 PES, IVR, and Entropy Effects 104

3.4 Diradicals as Intermediates in Norrish Type-II Reactions 106

4 The Coulomb Explosion Imaging Method and Excited-State Proton-Transfer Reactions / Eric S. Wisniewski, Jason R. Stairs, Daniel E. Folmer, A. Welford Castleman, Jr. 113

4.2 Experimental Techniques 116

4.2.1 Femtosecond Laser System and Amplification 116

4.2.2 Pump-Probe and Coulomb Explosion Imaging 116

4.3.1 Coulomb Explosion Imaging Method 117

4.3.2 Hydration of 7-Azaindole 125

5 Femtosecond Dynamics at Conical Intersections / Wolfgang Domcke 133

5.2 Modeling of Conical Intersections 135

5.3 Time-Dependent Quantum Wave-Packet and Reduced-Density-Matrix Dynamics 138

5.4 Aspects of Ultrafast Dynamics at Conical Intersections 139

6 Femtosecond Spectroscopy of Molecular Caging: Quantum and Classical Approaches / Vladimir A. Ermoshin, Volker Engel, Christoph Meier 147

6.2 Quantum Treatment 148

6.3 Classical Treatment 150

6.4 I[subscript 2]/Ar Caging 150

7 Ultrafast Geometrical Relaxation in Polydiacetylene Induced by Sub-5-fs Pulses / Takayoshi Kobayashi 155

7.2 Experimental 156

8 Ultrafast Probing and Control of Molecular Dynamics: Beyond the Pump-Probe Method / Marcos Dantus 169

8.2 Four-Wave Mixing Techniques 170

8.2.1 Differences Between the Pump-Probe Method and Four-Wave Mixing 170

8.2.2 Off-Resonance FWM 171

8.2.3 On-Resonance FWM 172

8.3 Experimental Methods 175

8.4.1 Off-Resonance Measurements 178

8.4.2 Resonance Measurements 179

8.4.3 Coherent Control with FWM 182

8.5.1 Off-Resonance FWM and Time-Resolved Measurements of Ground-State Dynamics 183

8.5.2 Resonance FWM, Ground and Excited-State Dynamics 184

9 Quantum Control of Ultrafast Laser-Driven Isomerization Reactions: Proton Transfer and Selective Preparation Of Enantiomers / Nadja Doslic, Yuichi Fujimura, Leticia Gonzalez, Kunihito Hoki, Dominik Kroner, Oliver Kuhn, Jorn Manz, Yukiyoshi Ohtsuki|p189

9.2 Laser Preparation of Pure Enantiomers 190

9.3 Proton Transfer 193

10 Controlling the Vibration and Dissociation Dynamics in Small Molecules and Clusters / Stefan Vajda, Ludger Woste 199

10.2 The Choice of the Molecular Systems 200

10.3 Experimental Set-Up 204

10.3.1 Molecular Beam and Laser Systems 204

10.3.2 Pulse Shaping 205

10.4 Experimental Results and Discussion 205

10.4.1 Na[subscript 3] 205

10.4.2 Na[subscript 2]K 206

10.4.3 CpMn(CO)[subscript 3] 212

11 Two-Dimensional Optical Nonlinear Spectroscopy in Liquids / Keisuke Tominaga, Hiroaki Maekawa 217

11.2 Calculation of the Two-Dimensional Spectrum 219

11.3 Two-Dimensional Spectrum 221

12 Femtosecond Diffuse Reflectance Spectroscopy and Photochemistry of Organic Microcrystals / Hiroshi Masuhara, Tsuyoshi Asahi, Akihiro Furube 225

12.2 System and Analysis 226

12.2.1 Femtosecond Diffuse Reflectance Spectroscopic System 226

12.2.2 Time-Dependent Kubelka-Munk Model 227

12.2.3 Temporal Characteristics and Time Resolution 229

12.3 Ultrafast Processes in Some Organic Powders 231

12.3.1 Excited Electronic Structure and Dynamics of Weak CT Microcrystals 231

12.3.2 Charge Recombination Process of Molecules Adsorbed in Zeolites 233

12.3.3 Intersystem Crossing in an Acridine Microcrystal 234

12.4 Future Perspectives 236

12.4.1 Femtosecond Absorption Spectroscopy of a Single Microcrystal 236

12.4.2 Femtosecond Light-Scattering Spectroscopy 236

12.4.3 Femtosecond Cooperative Photochromic Reaction in Organic Crystals 237

13 Impurity Rydberg States as Probes of Local Dynamics in the Condensed Phase / Franco Vigliotti, Majed Chergui 239

13.2 Steady-State Spectroscopy 240

13.3 Time-Resolved Spectroscopy 244

13.3.1 NO in Solid Ar 244

13.3.2 NO in Solid Ne 245

13.3.3 NO in Solid Hydrogen 246

13.4.1 Inertial Response (t < 200 fs) 248

13.4.2 Relaxation Process (200 fs < t < 3 ps) 250

14 Photoelectron Spectroscopy as a Probe for Investigating Chemical Dynamics / Ingo Fischer 253

14.2 The Concept 253

14.3 Molecular Photophysics 256

14.4 Monitoring Wavepacket Dynamics by ZEKE and PE Spectroscopy 259

14.5 Intensity Effects in ZEKE and Photoelectron Spectra 261

14.6 Probing Chemical Dynamics by Photoelectron and ZEKE Spectroscopy in the Frequency Domain 262

14.7 New Directions 263

15 Femtochemistry in Nanocavities / Abderrazzak Douhal 267

15.2 Concept of Femtochemistry in Nanocavities 268

15.3 I-I Bond Breaking and Remaking in a Molecular Nanocavity 269

15.4 Intramolecular H-Bond Breaking and Making and Related Reactions in Nanocavities 273

16 Energy- and Angle-Resolved Femtosecond Photoelectron Spectra from Rotating Molecules / Yasuki Arasaki, Kazuo Takatsuka, Kwanghsi Wang, Vincent McKoy 281

16.2 Pump-Probe Photoelectron Spectroscopy and Molecular Rotation 282

16.2.1 Formulation 282

16.2.2 Molecular Rotation 286

16.3 Photoelectron Distribution from Rotating Molecules 288

16.3.1 Vibrational Wave Packets 288

16.3.2 Photoelectrons from a Rigid Rotor 288

16.3.3 Convolution of Molecular Vibration and Rotation 289

17 Femtosecond Time-Resolved Fluorescence and Anisotropy Decay Spectroscopy of a Dendrimer with Eight Chromophores at the Rim / Gerd Schweitzer, Gino De Belder, Sven Jordens, Marc Lor, Klaus Mullen, Andreas Herrmann, Frans C.

De Schryver 295

17.2 Experimental Section 297

17.3 Results and Discussion 298

17.3.1 Steady-State Spectroscopy 298

17.3.2 Fluorescence Decays 299

17.3.3 Anisotropy Decays 303

18 Excited-State Dynamics of Conjugated Polymers and Oligomers / Jean-Yves Bigot, Thierry Barisien 307

18.2 Femtosecond Dynamics of a Polydiacetylene Backbone 309

18.2.1 Photon Echoes and Wavepacket Dynamics of pDCH 309

18.2.2 Structural Relaxation of a Model Polydiacetylene Chain: Ab initio Calculations of the Potential Surfaces 312

18.3 Femtosecond Gain Dynamics in Phenylene-Vinylene Pentamers 314

18.3.1 Amplified Spontaneous Emission of Phenylene-Vinylene Pentamers 314

18.3.2 The Influence of Structural Disorder on the Femtosecond Gain Dynamics 317

19 Excited-State Intramolecular Proton Transfer (ESIPT) and Energy Relaxation Processes in Hydroxyphenylbenzotriazole Derivatives: A Femtosecond Laser Study / Thierry Fournier, Stanislas Pommeret, Jean-Claude Mialocq, Anre Deflandre 323

19.2 Experimental Section 324

19.2.1 Chemicals 324

19.2.2 Steady-State Spectroscopy 325

19.2.3 Femtosecond Time-Resolved Spectroscopy 325

19.3.1 Steady-State Spectroscopy 327

19.3.2 Femtosecond UV/vis Absorption and Gain Spectra 328

20 Direct Detection of the Charge-Shift Reaction in Aromatic Vinyl Polymers by means of Transient Absorption and Dichroism Measurements / Hiroshi Miyasaka, Takao Moriyama, Sazzadur R. Khan, Akira Itaya 335

20.2 Dynamic Behavior in Solid Amorphous Systems 335

20.3 Direct Detection of Charge-Shift Reactions in Aromatic Vinyl Polymers in the Solution Phase 339

21 Femtosecond Chemical Events of Intramolecular Charge Transfer and Intermolecular Hydrogen Bond Breaking after Electronic Excitation: Structural Dynamics in the Condensed Phase / Erik T. J. Nibbering, Jens Dreyer 345

21.2 Structural Information on Transient States: Comparison of Vibrational Spectra with Ab initio CASSCF Calculations 347

21.3 Structural Information on Hydrogen Bonds after Electronic Excitation: Local Femtosecond Dynamics and Comparison of Vibrational Spectra with Line-Shape Theory 350

21.3.1 Ultrafast Response of Hydrogen-Bonded Complexes after Electronic Excitation of One of the Constituents 350

21.3.2 Transient IR Spectroscopy of the Phenol Dimer after Release from Optically Excited Coumarin-102: Structural Dynamics 352

21.3.3 Theory of Absorption Line Shapes of Vibrational Modes Subject to Hydrogen Bonding 353

21.3.4 Inspection of the O-H Stretch Line Shape of the Phenol Dimer with Line-Shape Theories 357

21.4 Conclusions and Prospects 361

22 Vibrational Coherence in Electron Donor-Acceptor Complexes: Assignment of the Oscillatory Mode / Igor V. Rubtsov, Keitaro Yoshihara 367

22.2 Experimental 369

22.3 Results and Discussion 370

22.3.1 Oscillations in the TCNE-HMB Complex 370

22.3.2 Peak-Shift of the Fluorescence Spectrum 372

22.3.3 Modulation of the Mean Transition Moment by the Vibration 374

22.3.4 Assignment of the Oscillatory Modes 375

23 Femtosecond Studies of the Initial Events in the Photocycle of Photoactive Yellow Protein (PYP) / Matthew A. Horn, Julie A. Gruetzmacher, Jeongho Kim, Seung-Eng Choi, Spencer M. Anderson, Keith Moffat, Norbert F. Scherer 381

23.2 Methods 382

23.2.1 Molecular Dynamics Simulations 382

23.2.2 Femtosecond Spectroscopy 382

23.3 Results 383

23.3.1 Pump-Probe Measurements 383

23.3.2 Anisotropy 384

23.3.3 Molecular Dynamics Simulations 385

23.4.1 Energetics 385

23.4.2 Isomerization 385

23.4.3 Anisotropy 387

24 Elementary Reactions in the Condensed Phase: Bond Breaking, Isomerization, and Electron Transfer / Eva Akesson, Alexander N. Tarnovsky, Gabor Benko, Arkady Yartsev, Villy Sundstrom 391

24.2 Bond Breaking and Isomerization in Solution 391

24.2.1 Photodissociation of Dihalomethanes 391

24.2.2 Barrierless Isomerization in Solution 393

24.3 Electron-Transfer in Dye-Sensitized Titanium Dioxide 395

25 Primary Processes in Photosynthesis Studied by Femtosecond Nonlinear Spectroscopy / Jante M. Salverda, Rienk van Grondelle 399

25.2 The Three-Pulse Echo Peak Shift and Transient Grating Methods 400

25.3 The 3PEPS/TG Experiment 403

25.4 Simulations 404

25.5 The B800 Ring of the Purple Bacterial Antenna LH2 406

25.6 The Bacterial Antenna LH1 and its Dimeric Subunit B820 409

25.7 The Accessory Bacteriochlorophylls of the Bacterial Reaction Center 411

26 Femtosecond Studies of Intramolecular Bond Twisting in Solution / Max Glasbeek, Hong Zhang, Pascale Changenet, Pascal Plaza, Monique M. Martin, Wolfgang Rettig 417

26.2 Experimental 419

26.3.1 Auramine 419

26.3.1 (a) Transient Absorption 420

26.3.1 (b) Fluorescence Up-Conversion 421

26.3.2 Ionic Styryl Dyes 424.

Notes:

Selected proceedings from a conference held in Leuven, Belgium, 18-22 July, 1999.

Includes bibliographical references and index.

ISBN:

352730259X

OCLC:

48162990