Ultrafast IR and raman spectroscopy 2001 fayer

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Ultrafast Infrared and Raman Spectroscopy edited by M D Fayer Stanford University Stanford, California Marcel Dekker, Inc TM Copyright © 2001 by Taylor & Francis Group, LLC New York • Basel ISBN: 0-8247-0451-7 This book is printed on acid-free paper Headquarters Marcel Dekker, Inc 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities For more information, write to Special Sales/Professional Marketing at the headquarters address above Copyright  2001 by Marcel Dekker, Inc All Rights Reserved Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher Current printing (last digit): 10 PRINTED IN THE UNITED STATES OF AMERICA Copyright © 2001 by Taylor & Francis Group, LLC PRACTICAL SPECTROSCOPY A SERIES Infrared and Raman Spectroscopy (in three parts), edited by Edward G Brame, Jr., and Jeanette G Grasselli X-Ray Spectrometry, edited by H K Herglotz and L S Birks Mass Spectrometry (in two parts), edited by Charles Merritt, Jr., and Charles N McEwen Infrared and Raman Spectroscopy of Polymers, H W Siesler and K Holland-Moritz NMR Spectroscopy Techniques, edited by Cecil Dybowski and Robert L Lichter Infrared Microspectroscopy: Theory and Applications, edited by Robert G Messerschmidt and Matthew A Harthcock Flow Injection Atomic Spectroscopy, edited by Jose Luis Burguera Mass Spectrometry of Biological Materials, edited by Charles N McEwen and Barbara S Larsen Field Desorption Mass Spectrometry, László Prókai 10 Chromatography/Fourier Transform Infrared Spectroscopy and Its Applications, Robert White 11 Modern NMR Techniques and Their Application in Chemistry, edited by Alexander I Popov and Klaas Hallenga 12 Luminescence Techniques in Chemical and Biochemical Analysis, edited by Willy R G Baeyens, Denis De Keukeleire, and Katherine Korkidis 13 Handbook of Near-Infrared Analysis, edited by Donald A Burns and Emil W Ciurczak 14 Handbook of X-Ray Spectrometry: Methods and Techniques, edited by René E Van Grieken and Andrzej A Markowicz 15 Internal Reflection Spectroscopy: Theory and Applications, edited by Francis M Mirabella, Jr 16 Microscopic and Spectroscopic Imaging of the Chemical State, edited by Michael D Morris 17 Mathematical Analysis of Spectral Orthogonality, John H Kalivas and Patrick M Lang 18 Laser Spectroscopy: Techniques and Applications, E Roland Menzel 19 Practical Guide to Infrared Microspectroscopy, edited by Howard J Humecki 20 Quantitative X-ray Spectrometry: Second Edition, Ron Jenkins, R W Gould, and Dale Gedcke 21 NMR Spectroscopy Techniques: Second Edition, Revised and Expanded, edited by Martha D Bruch 22 Spectrophotometric Reactions, Irena Nemcova, Ludmila Cermakova, and Jiri Gasparic 23 Inorganic Mass Spectrometry: Fundamentals and Applications, edited by Christopher M Barshick, Douglas C Duckworth, and David H Smith 24 Infrared and Raman Spectroscopy of Biological Materials, edited by HansUlrich Gremlich and Bing Yan 25 Near-Infrared Applications in Biotechnology, edited by Ramesh Raghavachari 26 Ultrafast Infrared and Raman Spectroscopy, edited by M D Fayer 27 Handbook of Near-Infrared Analysis: Second Edition, Revised and Expanded, edited by Donald A Burns and Emil W Ciurczak 28 Handbook of Raman Spectroscopy: From the Research Laboratory to the Process Line, edited by Ian R Lewis and Howell G M Edwards 29 Handbook of X-Ray Spectrometry: Second Edition, Revised and Expanded, edited by René E Van Grieken and Andrzej A Markowicz 30 Ultraviolet Spectroscopy and UV Lasers, edited by Prabhakar Misra and Mark A Dubinskii 31 Pharmaceutical and Medical Applications of Near-Infrared Spectroscopy, Emil W Ciurczak and James K Drennen III 32 Applied Electrospray Mass Spectrometry, edited by Birendra N Pramanik, A K Ganguly, and Michael L Gross ADDITIONAL VOLUMES IN PREPARATION Preface The field of ultrafast infrared and Raman spectroscopy is advancing at a remarkable rate New techniques and laser sources are making it possible to investigate a wide range of problems in chemistry, physics, and biology, using ultrafast time domain vibrational spectroscopy Although the first infrared measurements were made by Isaac Newton in the early 1700s, it is only recently that an explosion of activity using ultrafast pulsed techniques has moved vibrational spectroscopy along the path that magnetic resonance spectroscopy followed almost from its inception Vibrational spectroscopy examines the internal mechanical degrees of freedom of molecules and the external mechanical degrees of freedom of condensed matter systems It is the direct connection among vibrational spectra, molecular structure, and intermolecular interactions that has made vibrational spectroscopy an indispensable tool in the study of molecular matter In addition, most chemical, physical, and biological processes are thermal Such processes involve the time evolution of the mechanical degrees of freedom of molecules on their ground electronic state potential surfaces This is the purview of vibrational spectroscopy The advent of ultrafast pulsed vibrational spectroscopy, using both resonant infrared and Raman methods, is fundamentally changing the nature of the information that can be obtained about condensed matter molecular materials It is now possible to examine the structural evolution of systems on the time scales on which the important events are occurring All the powerful methods of magnetic resonance, from solid-state nuclear magnetic resonance (NMR) to medical magnetic resonance imaging, depend on measuring the time evolution of a spin system following the application of one or more radio frequency pulses In the visible and ultraviolet, ultrafast optical pulse sequences have been used for many years to measure both population dynamics and coherence phenomena At low Copyright © 2001 by Taylor & Francis Group, LLC temperatures, electronic transitions of complex molecules can have narrow, homogeneous line widths even if the absorption spectra display broad, inhomogeneous lines In low-temperature crystals and glasses, optical coherence methods, such as photon echoes and stimulated photon echoes, have been highly successful at extracting a great deal of information about dynamics and intermolecular interactions As visible pulse durations became increasingly short, photon echoes and related sequences have been applied to molecules in room-temperature liquids Many elegant experiments have begun to extract some information from such systems However, there is an intrinsic problem: Because of the exceedingly short electronic dephasing times of complex molecules at high temperatures, ultrashort pulses (tens of femtoseconds or less) are required to perform the experiments Ultrashort pulses have very large bandwidths, resulting in the excitation of a vast number of vibronic transitions in complex molecules Experiments of this type cannot be described properly in terms of two states coupled to a medium The complex multistate superposition that is initially prepared by the broad bandwidth radiation field has a time evolution that depends on the nature and magnitude of the many states that comprise the superposition as well as the system’s interactions with the medium It is difficult to develop a detailed understanding of such experiments except when they are performed on simple molecules (e.g., diatomics) The electronic absorption spectra of complex molecules at elevated temperatures in condensed matter are generally very broad and virtually featureless In contrast, vibrational spectra of complex molecules, even in room-temperature liquids, can display sharp, well-defined peaks, many of which can be assigned to specific vibrational modes The inverse of the line width sets a time scale for the dynamics associated with a transition The relatively narrow line widths associated with many vibrational transitions make it possible to use pulse durations with correspondingly narrow bandwidths to extract information For a vibration with sufficiently large anharmonicity or a sufficiently narrow absorption line, the system behaves as a two-level transition coupled to its environment In this respect, time domain vibrational spectroscopy of internal molecular modes is more akin to NMR than to electronic spectroscopy The potential has already been demonstrated, as described in some of the chapters in this book, to perform pulse sequences that are, in many respects, analogous to those used in NMR Commercial equipment is available that can produce the necessary infrared (IR) pulses for such experiments, and the equipment is rapidly becoming less expensive, more compact, and more reliable It is possible, even likely, that coherent IR pulse-sequence vibrational spectrometers will Copyright © 2001 by Taylor & Francis Group, LLC become available for general use, much as NMR spectrometers have gone from home-built, specialized machines to instruments widely used in many areas of science While the internal vibrational modes of molecules can display sharp spectral features, the vibrational spectra of modes of bulk matter are broad and relatively featureless Nonetheless, Raman and infrared methods can be used to study the bulk, the intermolecular degrees of freedom of condensed matter systems A great deal of information on bulk degrees of freedom has been extracted from electronic spectroscopy, particularly at low temperatures Such experiments, however, rely on the influence of the medium on an electronic transition Using ultrafast Raman techniques, including multidimensional methods, and emerging far-IR methods, it is possible to examine the bulk properties of matter directly A remarkable collection of individuals has been assembled to contribute to the book — experimentalists and theorists who are at the forefront of the advances in ultrafast infrared and Raman spectroscopy They discuss a diverse set of important chemical, physical, and biological problems and a broad range of experimental and theoretical methods While the experimentalists all use theory to understand their results, the inclusion of top theorists adds to the comprehensive nature of the book The theorists are developing descriptions of the new techniques and methods for interpreting the results The wealth of data that has emerged from the application of new methods has spawned a great deal of theoretical effort In turn, new theoretical methods drive the experiments by placing them in proper context and indicating lines for new experimental endeavors The experiments discussed in this book are diverse, but they break down into two broad categories: (1) resonant infrared methods in which ultrafast IR pulses are tuned to the wavelength of the vibrational transition and (2) Raman methods (in some instances referred to as impulsive stimulated scattering), in which two visible wavelengths have a difference in frequency equal to the vibrational frequency In some experiments, infrared and Raman techniques are combined in a single measurement There is another manner in which the experiments can be separated into two broad categories In some of the experiments, the time evolution of vibrational populations are studied For example, a particular vibration may be excited with an infrared pulse of light, and then the time evolution of the population is followed with either infrared or Raman probe techniques In other experiments, a chemical reaction is begun with an ultrafast visible pulse, and the time evolution of the chemical reaction is followed with ultrafast infrared pulses that monitor the time dependence Copyright © 2001 by Taylor & Francis Group, LLC of the vibrational spectrum In another class of experiments, vibrational coherence experiments are performed Experiments such as the infrared vibrational echo or Raman vibrational echo are closely analogous to NMR spin echo Such experiments, in one- and two-dimensional incarnations, examine the time evolution of the phase relationship among vibrations Both population and coherence experiments provide information on the dynamics and interactions of condensed matter systems In addition, time domain vibrational experiments can extract spectroscopic information that is hidden in a conventional measurement of the infrared or Raman spectra This book will provide the reader with a picture of the state of the art and a perspective on future developments in the field of ultrafast infrared and Raman spectroscopy M D Fayer Copyright © 2001 by Taylor & Francis Group, LLC Contents Preface Contributor Ultrafast Coherent Raman and Infrared Spectroscopy of Liquid Systems Alfred Laubereau and Robert Laenen Probing Bond Activation Reactions with Femtosecond Infrared Haw Yang and Charles Bonner Harris Applications of Broadband Transient Infrared Spectroscopy Edwin J Heilweil The Molecular Mechanisms Behind the Vibrational Population Relaxation of Small Molecules in Liquids Richard M Stratt Time-Resolved Infrared Studies of Ligand Dynamics in Heme Proteins Manho Lim, Timothy A Jackson, and Philip A Anfinrud Infrared Vibrational Echo Experiments Kirk D Rector and M D Fayer Structure and Dynamics of Proteins and Peptides: Femtosecond Two-Dimensional Infrared Spectroscopy Peter Hamm and Robin M Hochstrasser Copyright © 2001 by Taylor & Francis Group, LLC Two-Dimensional Coherent Infrared Spectroscopy of Vibrational Excitons in Peptides Andrei Piryatinski, Vladimir Chernyak, and Shaul Mukamel Vibrational Dephasing in Liquids: Raman Echo and Raman Free-Induction Decay Studies Mark A Berg 10 Fifth-Order Two-Dimensional Raman Spectroscopy of the Intermolecular and Vibrational Dynamics in Liquids David A Blank, Graham R Fleming, Minhaeng Cho, and Andrei Tokmakoff 11 Nonresonant Intermolecular Spectroscopy of Liquids John T Fourkas 12 Lattice Vibrations that Move at the Speed of Light: How to Excite Them, How to Monitor Them, and How to Image Them Before They Get Away Richard M Koehl, Timothy F Crimmins, and Keith A Nelson 13 Vibrational Energy Redistribution in Polyatomic Liquids: Ultrafast IR-Raman Spectroscopy Lawrence K Iwaki, John C De`ak, Stuart T Rhea, and Dana D Dlott 14 Coulomb Force and Intramolecular Energy Flow Effects for Vibrational Energy Transfer for Small Molecules in Polar Solvents James T Hynes and Rossend Rey 15 Vibrational Relaxation of Polyatomic Molecules in Supercritical Fluids and the Gas Phase D J Myers, Motoyuki Shigeiwa, M D Fayer, and Binny J Cherayil 16 Vibrational Energy Relaxation in Liquids and Supercritical Fluids James L Skinner, Sergei A Egorov, and Karl F Everitt Copyright © 2001 by Taylor & Francis Group, LLC 680 Skinner et al It is now interesting to consider the classical h¯ ! limits of these two expressions Actually, in the first instance it is inappropriate to take this limit, since just the opposite limit ˇ¯hω10 × is invoked in truncating the state space to two levels However, in the second instance, one can smoothly take the classical limit, and one finds that in this case T1 is given by the usual classical Landau-Teller result: 1 D T1 kT dt cos ω0 t hF t F icl 13 where the subscript cl on the angular brackets indicates that this is now a classical time correlation function We have used the fact that in the classical limit any time autocorrelation function is real and even There are also situations when one is not in the classical limit, and so Equation (13) would not seem applicable, and instead one would like to approximate one of the quantum mechanical expressions for T1 by relating the relevant quantum time-correlation function to its classical analog For the sake of definiteness, let us consider the case where the oscillator is harmonic and the oscillator-bath coupling is linear in q, as discussed above In this case k1!0 can be written as ˆ ω0 G h¯ ω0 14 dt eiωt G t 15 k1!0 D k0 D where ˆ ω D G 1 ˆ ω is the Fourier transform of the with G(t) D hF(t)F i That is, G quantum force-force time-correlation function We (5,6) and others (7,14,16–18) have discussed at some length various approximate schemes ˆ ω to its classical analog for relating G ˆ cl ω D G 1 dt eiωt Gcl t 16 with Gcl t D hF(t)F icl Here we list three such schemes: The “standard” scheme, where ˆ ω D G 1Ce ˇ¯hω ˆ cl ω G Copyright © 2001 by Taylor & Francis Group, LLC 17 VER in Liquids and Supercritical Fluids The “harmonic” scheme, where ˆ ω D G 681 ˇ¯hω ˆ Gcl ω e ˇ¯hω 18 The Egelstaff scheme (7), where ˆ ω D eˇ¯hω/2 G 1 dt eiωt Gcl t2 C ˇ¯h/2 19 Each of these schemes satisfies the important property of detailed balance: ˆ G ω De ˇ¯hω ˆ ω G 20 The standard scheme has been the most popular one for the last 20 years or so The harmonic scheme gets its name because if the bath is harmonic (more precisely, if F can be represented as a linear combination of harmonic coordinates), then this scheme is exact (16,19) By comparing these schemes to results from exactly solvable models we have concluded that the standard scheme is really not very accurate at high frequencies and that the harmonic and Egelstaff schemes are more promising (5,6) A fourth scheme satisfying detailed balance, ˆ ω D eˇ¯hω/4 G ˇ¯hω e ˇ¯hω 1/2 ˆ cl ω G 21 may also have some merit (6) Here is a fascinating result: if the harmonic scheme of Equation (18) is applied to Equation (14), using Equation (12) for T1 recovers exactly the classical Landau-Teller result, as recently shown by Bader and Berne (16) Thus, if the oscillator and bath are both harmonic and are bilinearly coupled, the exact quantum result and the exact classical result are identical! This provides some justification for using the purely classical result of Equation (13) even in situations where one clearly is not in the classical limit III I2 IN LIQUID AND SUPERCRITICAL XENON With the goal of describing some VER experiments on the solute iodine in Xe solvent (1), in this section we specialize to the case of a diatomic solute in an atomic solvent In fact, we consider a simplified model where the diatomic solute is replaced with a “breathing” sphere (2) We take the Copyright © 2001 by Taylor & Francis Group, LLC 682 Skinner et al oscillator Hamiltonian for the one-dimensional breathing coordinate to be harmonic: Hq D ω02 q2 p2 C 22 The bath consists of the translational motions of the solute and all the solvent atoms Since all potentials are spherically symmetrical, we write Hb D T C ri C i s rij 23 i
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Xem thêm: Ultrafast IR and raman spectroscopy 2001 fayer , Ultrafast IR and raman spectroscopy 2001 fayer , I. COHERENT ANTI-STOKES RAMAN SPECTROSCOPY OF SIMPLE LIQUIDS, II. TIME-RESOLVED IR SPECTROSCOPY OF STRONGLY ASSOCIATED LIQUIDS, Ethanol Oligomers in Solution: Spectral Holes and Vibrational Lifetime Shortening, H-Bonded Dimers: Librational Substructure of the OH Band of Proton Donors, E. Investigations of Isotopic Water Mixtures, A. The Dynamics of Reaction Intermediates — Vibrational Relaxation and Molecular Morphology Change, B. The Activation Barrier — The Bond-Breaking Step, A. The Reaction Intermediates — Solvation-Partitioned Pathways and Intersystem Crossing, B. The Reaction Barrier — Solvent Molecule Rearrangement, C. The Reaction Mechanism — Resolving a Convolved Chemical Reaction, A. Clarification of the Reaction Pathway, B. The Nature of the Reaction Barrier — Atom Transfer, E. Vibrational Coherent Control with Chirped Picosecond Infrared Excitation, F. Ultraviolet Photochemistry: Self-Association Reactions of Mn(CO)3CpR Species and [CpFe(CO)2]2 in Solution, G. Primary Electron Transfer Dynamics of Dye-Sensitized Semiconductor Solar Cell Devices, IV. CONCLUSIONS AND FUTURE DIRECTIONS, A. Vibrational Energy Relaxation and Vibrational Friction, B. The Instantaneous Vibrational Friction and the Instantaneous Normal Modes of the Solvent, III. HOW COLLECTIVE IS VIBRATIONAL ENERGY RELAXATION?, IV. HOW DOES DIELECTRIC FRICTION EFFECT VIBRATIONAL ENERGY RELAXATION?, V. VIBRATIONAL ENERGY RELAXATION AT HIGH FREQUENCIES, A. Vibrational Spectrum of Orientationally Constrained CO, A. Laser Photolysis: A Sledgehammer or a Scalpel?, B. Evidence for a Ligand Docking Site in the Heme Pockets of Mb and Hb, C. Orientation of Bound and ‘‘Docked’’ CO, E. Origin of the Barrier to CO Rebinding, A. The Vibrational Echo Method, III. VIBRATIONAL ECHO STUDIES OF DYNAMICS IN LIQUIDS AND CLASSES, A. Vibrational Echo Spectroscopy Theory, C. Experimental Demonstrations of VES, A. Vibrational Echo Results and Dephasing Mechanisms, B. Coupling of Protein Fluctuations to the CO Ligand at the Active Site, III. SPECTRAL DIFFUSION OF VIBRATIONAL TRANSITIONS, A. Theory of Vibrational Third-Order Nonlinear Spectroscopy, D. The Three-Pulse Photon Echo Experiment, E. Spectral Diffusion of Small Molecules in Water, F. Spectral Diffusion of Vibrational Probes in Enzyme-Binding Pockets, A. An Excitonic Model for the Amide I Band, C. Two-Dimensional IR Spectroscopy on the Amide I Band, D. Spectral Diffusion of the Amide I Band, E. 2D-IR Spectroscopy Using Semi-Impulsive Methods, II. THREE-PULSE MULTIDIMENSIONAL FEMTOSECOND OPTICAL SPECTROSCOPIES, IV. VIBRATIONAL EXCITONS IN CYCLIC PENTAPEPTIDE, A. Absolute Value of the 2D Signal, B. Real and Imaginary Parts of the 2D Signal, A. One-Dimensional Measurements: Raman Line Shape and Free Induction Decays, B. A Two-Dimensional Measurement: The Raman Echo, III. IMPLEMENTING COHERENT RAMAN EXPERIMENTS, C. Special Problems of Seventh-Order Spectroscopy, A. Concentration Fluctuations in CH3I:CDCl3, B. Density Fluctuations in Acetonitrile, D. A Viscoelastic Theory of Vibrational Dephasing, E. Solvent-Assisted IVR in Ethanol, A. General: Nonresonant Nonlinear Optical Response, C. Cascaded Fifth-Order Electronically Nonresonant Scattering, B. Intramolecular Vibrations in Carbon Tetrachloride, B. Intermolecular Motions in CS2, C. Intramolecular Vibrations in Carbon Tetrachloride and Chloroform, V. SYMMETRIC-TOP LIQUIDS: ORIENTATIONAL DIFFUSION, VI. SYMMETRIC-TOP LIQUIDS: INTERMOLECULAR SPECTRA, IV. SUMMARY AND FUTURE PROSPECTS, B. Force Correlation Function Approach, B. Pseudo-vibrational Cascade in Nitromethane, C. Dynamics of Doorway Vibrations, E. Fermi Resonance and Overtones, G. Spectral Evolution in Associated Liquids, II. COULOMBIC FORCE EFFECTS ON VET, III. SOLUTE INTRAMOLECULAR EFFECTS ON VET, B. Gas Phase Vibrational Dynamics, IV. THEORY OF T1 IN SUPERCRITICAL FLUIDS, V. COMPARISON OF THEORY AND EXPERIMENT, II. GENERAL THEORY OF VIBRATIONAL ENERGY RELAXATION, III. I2 IN LIQUID AND SUPERCRITICAL XENON, V. W(CO)6 IN SUPERCRITICAL ETHANE

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