Analysis and Control of Ultrafast Photoinduced Reactions

Springer Series in

chemical physics 87

Springer Series in

chemical physics

Series Editors: A. W. Castleman, Jr. J. P. Toennies K. Yamanouchi W. Zinth

The purpose of this series is to provide comprehensive up-to-date monographs

in both well established disciplines and emerging research areas within the broad

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71 Ultrafast Phenomena XIII

Editors: D. Miller, M.M. Murnane,

N.R. Scherer, and A.M. Weiner

72 Physical Chemistry

of Polymer Rheology

By J. Furukawa

73 Organometallic Conjugation

Structures, Reactions

and Functions of d–d

and d–π Conjugated Systems

Editors: A. Nakamura, N. Ueyama,

and K. Yamaguchi

74 Surface and Interface Analysis

An Electrochmists Toolbox

By R. Holze

75 Basic Principles

in Applied Catalysis

By M. Baerns

76 The Chemical Bond

A Fundamental

Quantum-Mechanical Picture

By T. Shida

77 Heterogeneous Kinetics

Theory of Ziegler-Natta-Kaminsky

Polymerization

By T. Keii

78 Nuclear Fusion Research

Understanding Plasma-Surface

Interactions

Editors: R.E.H. Clark

and D.H. Reiter

79 Ultrafast Phenomena XIV

Editors: T. Kobayashi,

T. Okada, T. Kobayashi,

K.A. Nelson, S. De Silvestri

80 X-Ray Diffraction

by Macromolecules

By N. Kasai and M. Kakudo

81 Advanced Time-Correlated Single

Photon Counting Techniques

By W. Becker

82 Transport Coefficients of Fluids

By B.C. Eu

83 Quantum Dynamics of Complex

Molecular Systems

Editors: D.A. Micha

and I. Burghardt

84 Progress in Ultrafast

Intense Laser Science I

Editors: K. Yamanouchi, S.L. Chin,

P. Agostini, and G. Ferrante

85 Quantum Dynamics

Intense Laser Science II

Editors: K. Yamanouchi, S.L. Chin,

P. Agostini, and G. Ferrante

86 Free Energy Calculations

Theory and Applications

in Chemistry and Biology

Editors: Ch. Chipot

and A. Pohorille

87 Analysis and Control of

Ultrafast Photoinduced Reactions

Editors: O. Kuhn and L. Woste ¨ ¨

O. Kuhn L. W ¨ oste (Eds.) ¨

Analysis and Control

of Ultrafast

Photoinduced Reactions

123

With 374 Figures, 239 in color

Freie Universitat Berlin ¨

Institut f. Chemie und Biochemie

Takustr. 3

D-14195 Berlin, Germany

E-Mail: [email protected]

Freie Universitat Berlin ¨

Institut für Experimentalphysik

Arnimallee 14

D-14195 Berlin, Germany

E-Mail: [email protected]

Series Editors:

Professor A. W. Castleman, Jr.

152 Davey Laboratory, University Park, PA 16802, USA

Professor J.P. Toennies

Max-Planck-Institut für Stromungsforschung, Bunsenstrasse 10 ¨

37073 Gottingen, Germany ¨

Professor K. Yamanouchi

University of Tokyo, Department of Chemistry

Hongo 7-3-1, 113-0033 Tokyo, Japan

Professor W. Zinth

Universitat M¨ unchen, Institut f ¨ ur Medizinische Optik ¨

Ottingerstr. 67, 80538 M ¨ unchen, Germany ¨

ISSN 0172-6218

ISBN-10 3-540-68037-3 Springer Berlin Heidelberg New York

ISBN-13 978-3-540-68037-6 Springer Berlin Heidelberg New York

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The cover picture showswave packet interferencesin excited Bromine dimers

Preface

Dynamical processes in molecules like bond shaking, breaking or making commonly take place on a time scale from the pico- down to the femtosecond range.

The advent of equally fast laser sources and real-time observation schemes like

pump-probe spectroscopy has facilitated the direct insight into such processes

when initiated by light. In parallel the development of advanced computational

methods treating the dynamics of photoexcited molecular systems allowed a

convergence between theoretical description and experimental observation of

such ultrafast dynamical processes. Consequently, the idea emerged, not only

to analyze, but also to control molecular dynamics in real time by adequately

designed light fields. Stimulated by theoretical concepts for influencing the

motion of molecular wave packets by means of simple few-parameter electromagnetic field sequences, experiments were driven toward a practical realization of arbitrarily shaped laser pulses. This development culminated in the

active feedback control of even complex systems. In addition this offers the

unique possibility not only to determine the outcome of chemical reactions,

but also to retrieve specific information about the chosen dynamical pathways,

that is, to perform analysis by control.

This book illustrates a vital research field by covering a broad spectrum of

molecular systems with growing complexity while demonstrating at the same

time the convergence of experimental and theoretical approaches. After a general introduction in Chapter 1, Chapter 2 starts with small isolated molecules

in the unperturbed environment of the gas phase and Chapter 3 proceeds

to more complex systems, but still in vacuum. A higher level of complexity

is then reached in Chapter 4 where small molecules in a rare gas matrices

are discussed serving as prototype examples for condensed phase dynamics.

This establishes the links toward applications which first focus in Chapter 5

on ultrafast dynamics at surfaces and interfaces. Then larger molecules and

clusters in intense laser fields are treated in Chapter 6. Chapter 7 interrogates

the vibrational, Chapter 8 the electronic spectroscopy of solvated systems. Finally, in Chapter 9 the ladder of complexity reaches out to real-time analysis

of photoinduced processes in biological systems. The structure of this outline

VI Preface

reflects the coordinated activities of the Collaborative Research Center Sfb450

named - like this book - “Analysis and Control of Ultrafast Photoinduced

Processes”. This Sfb comprises currently seventeen experimental and theoretical research groups in the larger Berlin area.

On a Sfb workshop, held here in Spring 2006 together with internationally

renowned researchers, the idea emerged, to write a book which should achieve

two goals: The first one is to provide a systematic and didactic introduction

into the field suitable for graduate students from Physics, Chemistry, and

Biology. The second one, is to present the state-of-affairs of the field such that

it may serve as a useful reference for the experts. The complexity-oriented

treatment of the theme was an essential element for realizing this concept.

This was assured by the assignment of coordinators to the chapters, who

harmonized the individual contributions.

Most of the results documented in the following would not have been possible without the generous financial support from the Deutsche Forschungsgemeinschaft through the Collaborative Research Center Sfb450 “Analysis and

Control of Ultrafast Photoinduced Processes” during the last eight years. We

are also most grateful to the participating institutions, in particular, the Freie

Universit¨at Berlin, which hosts our administration. In this regard we are indebted to the professional and enthusiastic support of Peter Abt and Sigrid

Apelt.

Berlin, Oliver K¨uhn

October 2006 Ludger W¨oste

Contents

1 Introduction ................................................ 1

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2 Analysis and control of small isolated molecular systems . . . . 25

2.1 Motivation and outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

2.2 Probing the dynamics of electronically excited states . . . . . . . . . . 27

2.3 Probing the dynamics of the transition state . . . . . . . . . . . . . . . . . 47

2.4 Optimal control of dynamical processes . . . . . . . . . . . . . . . . . . . . . 68

2.5 Optimal control on ultracold molecules . . . . . . . . . . . . . . . . . . . . . . 122

2.6 Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

3 Complex systems in the gas phase . . . . . . . . . . . . . . . . . . . . . . . . . . 153

3.1 Motivation and outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

3.2 Theoretical basis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160

3.3 Experimental approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166

3.4 Exemplary results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

3.5 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

4 Coherence and control of molecular dynamics in rare gas

matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257

4.2 Chromophore-matrix interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . 263

4.3 Extraction and application of intramolecular coherences . . . . . . . 287

4.4 Coherent matrix response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

4.5 IR-driven photochemistry in rare gas matrices:

The cis-trans isomerization of nitrous acid (HONO). . . . . . . . . . . 312

4.6 Interaction potentials: The diatomics-in-molecules approach. . . . 318

4.7 Classical simulations of adiabatic molecular dynamics . . . . . . . . . 324

4.8 Semiclassical simulations of nonadiabatic dynamics . . . . . . . . . . . 330

VIII Contents

4.9 Alignment and orientation of molecules in matrices . . . . . . . . . . . 337

4.10 Quantum simulations of wave packet dynamics in

reduced dimensionality: From analysis to coherent spin control . 352

4.11 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377

5 Ultrafast dynamics of photoinduced processes at surfaces

and interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387

5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387

5.2 Surface femtochemistry: Basic concepts . . . . . . . . . . . . . . . . . . . . . 389

5.3 Ultrafast dynamics of associative H2 desorption

from Ru(001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393

5.4 Diffusion of O on Pt(111) induced by femtosecond laser pulses . 405

5.5 Theory of ultrafast nonadiabatic processes at surfaces and

their control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418

5.6 Ultrafast photoinduced heterogeneous electron transfer:

Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432

5.7 Ultrafast photoinduced electron transfer

from anchored molecules into semiconductors . . . . . . . . . . . . . . . . 437

5.8 Ab initio time-domain simulations of photoinduced electron

transfer in dye-sensitized TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464

5.9 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478

6 Molecules and clusters in strong laser fields . . . . . . . . . . . . . . . . . 485

6.1 Light matter interaction in the high field regime . . . . . . . . . . . . . . 485

6.2 Strong-field control in small molecules. . . . . . . . . . . . . . . . . . . . . . . 491

6.3 Strong field chemistry and control . . . . . . . . . . . . . . . . . . . . . . . . . . 510

6.4 Ionization and fragmentation dynamics in fullerenes . . . . . . . . . . 538

6.5 Time-dependent electron localization function:

A tool to visualize and analyze ultrafast processes . . . . . . . . . . . . 553

6.6 Cluster dynamics in ultraintense laser fields . . . . . . . . . . . . . . . . . . 575

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607

7 Vibrational dynamics of hydrogen bonds . . . . . . . . . . . . . . . . . . . . 619

7.1 Significance of hydrogen bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . 619

7.2 Molecular vibrations as probe of structure

and dynamics of hydrogen bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . 620

7.3 Ultrafast nonlinear infrared spectroscopy . . . . . . . . . . . . . . . . . . . . 630

7.4 Disordered hydrogen-bonded liquids . . . . . . . . . . . . . . . . . . . . . . . . 640

7.5 Hydrogen bonds with ordered molecular topologies . . . . . . . . . . . 652

7.6 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679

Contents IX

8 Observing molecular structure changes and dynamics in

polar solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689

8.1 Analysis of electronic and vibrational coherence... . . . . . . . . . . . . 690

8.2 A novel experimental approach: Ultrafast X-ray absorption

spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729

9 Biological systems: Applications and perspectives . . . . . . . . . . . 733

9.1 Investigation of diverse biological systems . . . . . . . . . . . . . . . . . . . 733

9.2 Measuring transient electric fields within proteins. . . . . . . . . . . . . 739

9.3 Multipulse transient absorption spectroscopy:

A tool to explore biological systems . . . . . . . . . . . . . . . . . . . . . . . . . 750

9.4 Laser pulse control of excitation energy dynamics

in biological chromophore complexes . . . . . . . . . . . . . . . . . . . . . . . . 774

9.5 Light induced singlet oxygen generation . . . . . . . . . . . . . . . . . . . . . 783

9.6 Metastable conformational structure and dynamics: Peptide

between gas phase via clusters and aqueous solution . . . . . . . . . . 796

9.7 Detection and identification of bacteria in air using

femtosecond spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807

9.8 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 818

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 820

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831

List of Contributors

M. Bargheer

Max-Born-Institut f¨ur Nichtlineare

Optik und Kurzzeitspektroskopie

Max-Born-Str. 2a

D-12489 Berlin, Germany

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Analysis and Control of Ultrafast Photoinduced Reactions

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