Ultrafast hydrogen bonding dynamics and proton transfer processes in the condensed phase / edited by Thomas Elsaesser and Huib J. Bakker.

Format:

Book

Contributor:

Elsässer, T. (Thomas)

Bakker, Huib J.

Series:

Understanding chemical reactivity ; v. 23.

Understanding chemical reactivity ; v. 23

Language:

English

Subjects (All):

Hydrogen bonding.

Proton transfer reactions.

Condensed matter.

Physical Description:

vii, 186 pages : illustrations ; 25 cm.

Place of Publication:

Dordrecht ; Boston : Kluwer Academic Publishers, [2002]

Summary:

Hydrogen bonds represent type of molecular interaction that determines the structure and function of a large variety of molecular systems. The elementary dynamics of hydrogen bonds and related proton transfer reactions, both occurring in the ultra fast time domain between 10-14 and 10-11s, form a research topic of high current interest. In this book addressing scientists and graduate students in physics, chemistry and biology, the ultra fast dynamics of hydrogen bonds and proton transfer in the condensed phase are reviewed by leading scientists, documenting the state of the art in this exciting field from the viewpoint of theory and experiment. The nonequilibrium behavior of hydrogen-bonded liquids and intramolecular hydrogen bonds as well as photo induced hydrogen and proton transfer are covered in 7 chapters, making reference to the most recent literature.

Contents:

1 Ultrafast Dynamics of Hydrogen Bonding and Proton Transfer in the Condensed Phase / T. Elsaesser, H.J. Bakker 1

2 Infra-Red Spectra of Hydrogen Bonded Systems: Theory and Experiment / S. Bratos, J-Cl. Leicknam, G. Gallot, H. Ratajczak 5

2 Classical Infra-Red Spectroscopy 7

2.1 Phenomenological Description 7

2.2 Statistical Theory of Band Shapes. Semi-Emipiral Theories 10

2.3 Statistical Theory of Band Shapes. Molecular Dynamics Simulations 16

2.4 Power and Limits of Classical Infra-red Spectroscopy 18

3 Time-Resolved Infra-red Spectroscopy 19

3.1 Basic Information 19

3.2 Femtochemistry of Water 19

3.3 Phenomenological Description 21

3.4 Statistical Theory of Band Shapes 24

3 Femtosecond Mid-Infrared Spectroscopy of Water / H.J. Bakker 31

2 Femtosecond Mid-Infrared Spectroscopy 32

2.1 Generation of Femtosecond Mid-Infrared Pulses 32

2.2 Nonlinear Vibrational Spectroscopy of Water 33

2.3 Aqueous Samples 36

3 Energy Transfer in Liquid Water 38

3.1 Vibrational Relaxation of HDO:D[subscript 2]O 38

3.2 Vibrational Relaxation of Liquid H[subscript 2]O 41

3.3 Vibrational Relaxation of the O-D Stretch Vibration of Liquid Water 44

3.4 Vibrational Relaxation of Water in Aqueous Solvent Shells 44

3.5 Resonant Intermolecular Energy Transfer in Liquid H[subscript 2]O 48

4 Hydrogen-Bond Dynamics of Liquid Water 51

4.1 Experimental Results 52

4.2 Brownian Oscillator Model 55

4.3 Hydrogen-Bond versus Deuterium-Bond Dynamics 58

4.4 Hydrogen-Bond Dynamics of Water in Aqueous Solvent Shells 60

4.5 Relation between Hydrogen-Bond Length and Local Liquid Structure 64

5 Refined Quantum-Mechanical Modeling of the Spectral Response of Liquid Water 65

4 Proton Transfer Reactions and Hydrogen Bonding in Solution / P.M. Kiefer, J.T. Hynes 73

2 Adiabatic Proton Transfer 75

3 Nonadiabatic Tunneling Proton Transfer 84

5 Ab-Initio Reaction Paths and Potential-Energy Functions for Excited-State Intra- and Intermolecular Hydrogen-Transfer Processes / A.L. Sobolewski, W. Domcke 93

2 Theoretical Methodology 96

2.1 Reaction Path Concept 96

2.2 Electronic-Structure Methods 96

3 Theoretical Results 98

3.1 An ESIHT Model System: Malonaldehyde 98

3.1.1 Hydrogen Transfer 100

3.1.2 Hydrogen Detachment 102

3.2 'Real' ESIHT Systems 104

3.3 ESIHT in H-Bonded Molecular Complexes 106

3.4 A Generic Mechanistic Model of the ESIHT Reaction and Photostability 108

3.5 Photoinduced Hydrogen Transfer to the Solvent 109

6 Ultrafast Excited State Hydrogen Transfer in the Condensed Phase / T. Elsaesser 119

2 Experimental Techniques 123

3 Vibrational Spectroscopy of Ultrafast Hydrogen Transfer 128

3.1 Resonance Raman Spectroscopy 128

3.2 Femtosecond Infrared Spectroscopy 132

4 Excited State Hydrogen Transfer: Transient Electronic Spectra 136

5 Vibrational Relaxation and Redistribution Induced by Hydrogen Transfer 143

7 Proton Dissociation and Solute-Solvent Interactions Following Electronic Excitation of Photoacids / E. Pines, D. Pines 155

1.1 Neutral and Cationic Photoacids 157

1.2 A General Description of Photoacidity 160

1.2.1 Neutral Photoacids 160

1.2.2 Cationic Photoacids 162

2 Kinetic Processes Initiated by Photoacid Proton Dissociation 163

2.1 Diffusion-Controlled Proton Transfer Reactions 163

2.2 Proton Transfer to Solvent (PTTS) from Photoacids 166

2.3 Proton Transfer in Bulk Water (The Grotthus Mechanism) 171

3 Hydrogen Bonding Interaction of Photoacids 174

4 Solvation Dynamics and Hydrogen Bonding Interactions of Photoacids 177.

Notes:

Includes bibliographical references and index.

ISBN:

1402010931

OCLC:

51172432