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Dynamic Light Scattering: Applications of Photon Correlation Spectroscopy PDF

429 Pages·1985·8.506 MB·English
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Dynamic Light Scattering Applications of Photon Correlation Spectroscopy Dynamic Light Scattering Applications of Photon Correlation Spectroscopy Edited by Robert Pecora Stanford University Stanford, Cafijornia Plenum Press • New Yo rk and London Library of Congress Cataloging in Publication Data Main entry under tide: Dynamic light scattering. Includes bibliographies and index. 1. Light beating spectroscopy. 2. Light-Scattering. I. Pecora, Robert, 1938- QC454.L63D96 1985 535.8'4 84-24831 ISBN-13: 978-1-4612-9459-7 e-ISBN-13: 978-1-4613-2389-1 DO!: 10.1007/978-1-4613-2389-1 © 1985 Plenum Press, New York A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 Softcover reprint of the hardcover 1s t edition 1985 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher Contributors Victor A. Bloomfield Department of Biochemistry, University of Minnesota, St. Paul, Minnesota B.Chu Department of Chemistry, State Un iversity of N ew York, Stony Brook, N ew Y ork N. C. Ford, Jr. Langley-Ford Instruments, Amherst, Massachusetts c. C. Han National Bureau ofStandards, Washington D.C. Norman A. Mazer Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts; and Department of Medicine, Brigham and Women's Hospital, Boston, Massachusetts G. D. Patterson Department oJ Chemistry, Carnegie-M eI/on University, Pittsburgh, Pennsylvania R. Pecora Department oJChemistry, StanJord University, StanJord, California P. N. Pusey Royal Signals and Radar Establishment, Malvern, Worcestershire, England D. W. Schaefer Sandia National Laboratories, Albuquerque, New Mexico Toyoichi Tanaka Department oJ Physics and Center Jor Materials Science and Engineering, Massachusetts Institute ofTechnology, Cambridge, Massachusetts R. J. A. Tough Royal Signals and Radar Establishment, Malvern, Worcestershire, England Kar! Zero Department oJ Chemistry, Stariford Un iversity, Stariford, California v Preface In the twenty years since their inception, modern dynamic light-scattering techniques have become increasingly sophisticated, and their applications have grown exceedingly diverse. Applications of the techniques to problems in physics, chemistry, biology, medicine, and fluid mechanics have prolifer ated. It is probably no longer possible for one or two authors to write a monograph to cover in depth the advances in scattering techniques and the main areas in which they have made a major impact. This volume, which we expect to be the first of aseries, presents reviews of selected specialized areas by renowned experts. It makes no attempt to be comprehensive; it emphasizes a body of related applications to polymeric, biological, and colloidal systems, and to critical phenomena. The well-known monographs on dynamic light scattering by Berne and Pecora and by Chu were published almost ten years ago. They provided comprehensive treatments of the general principles of dynamic light scat tering and gave introductions to a wide variety of applications, but natu rally they could not treat the new applications and advances in older ones that have arisen in the last decade. The new applications include studies of interacting particles in solution (Chapter 4); scaling approaches to the dynamics of polymers, including polymers in semidilute solution (Chapter 5); the use of both Fabry-Perot interferometry and photon correlation spectroscopy to study bulk polymers (Chapter 6); studies of micelIes and microemulsions (Chapter 8); studies of polymer gels (Chapter 9). In addi tion, the considerable advances made in the study of critical phenomena are reviewed (Chapter 7), as weil as progress in the application of the depolar ized dynamic scattering technique to a wide variety of systems. A survey of the uses of the light-scattering and laser Doppler veiocimetry to study systems of biological interest is given in the final chapter (Chapter 10). The current volume contains much introductory material for the begin ner in light scattering. Chapter 2, for instance, should be especially useful for such readers and should be of aid to anyone contemplating setting up a dynamic light-scattering laboratory. The serious novice is, however, urged vii viii Preface to consult the two monographs mentioned above for background informa tion about time correlation functions, the electromagnetic theory of scat tering, the elementary theory of Brownian motion, hydrodynamics, generalized hydrodynamics, molecular reorientation in liquids, dynamics of a single polymer chain, and nonequilibrium thermodynamics, as weB as other topics in their relation to dynamic light scattering. It is a pleasure to express my thanks to the authors, who have taken so much time from their busy schedules to contribute to this volume. Stanford, California Robert Pe co ra Contents Chapter I Introduction .......................................................................... . R. Pecora References ............................................................... 6 Chapter 2 Light Scattering Apparatus .......... ... ........ ................................... 7 N. C. Ford, Jr. 2.1. Introduction ...... ........... ........ ..... .............................. 7 2.2. Electromagnetic W a ves . . . . . . . . . . . . . .. . . .. . . . . . . .. . .. . . . . .. . . . .. . . . . . . 8 2.3. Light Scattering ........................................................ 11 2.3.1. Background................................................... 11 2.3.2. Fluctuations................................................... 12 2.3.3. The Coherence Area ......................................... 15 2.3.4. Time Dependence ............................................ 16 2.3.5. Local Oscillator...... ................. ........................ 19 2.4. The Light Scattering Experiment................................... 19 2.4.1. Introduction .................................................. 19 2.4.2. The Light Source............................................. 20 2.4.3. The Spectrometer........... .. ..................... ........... 26 2.4.4. The Detector. . . . . . .. . . . .. . . . . . . .. .. . . . . . . . . . . . . . . . . . . . . .. . . .. . . 29 2.4.5. Signal Analyzers .............................................. 35 2.5. Signal-to-Noise Ratio................................................. 40 2.5.1. Introduction .................................................. 40 2.5.2. Effects due to Finite Intensity ............................. 40 2.5.3. Effects due to Finite Experiment Duration............. 42 2.5.4. Effects due to Unwanted Scattered Light............... 43 2.6. Data Analysis.. ....... ......... ... .... .. ..... .. .......... .. ..... ...... .. 46 2.6.1. Introduction ........................ .................. ........ 46 2.6.2. Selecting the Theoretical Form............................ 46 2.6.3. U se of the X2 Test.... ............ ............................. 48 ix x Contents 2.6.4. Summary of Possible Forms............................... 49 2.6.5. Polydispersity................................................. 50 2.7. SpeciaIApparatus...................................................... 51 2.7.1. Electrophoretic Light Scattering.. ..... .......... ......... 51 2.7.2. Fabry-Perot Interferometers .. ....... ............. ........ 53 2.7.3. SoftwareCorrelators......................................... 56 2.7.4 Cross-Correlation Experiment ........ ..... ...... ..... ..... 56 2.8. Conc1usions............................................................. 57 References and Notes................................................. 57 Chapter 3 Dynamic Depolarized Ligbt Scattering ................. . . . . . . . . . . . . . . . . . . . . . . . . 59 Karl Zero and R. Pecora 3.1. Introduction ....... ....... ....... ..... .... ... ...... ..... .... ...... ...... 59 3.2. Principles of Depolarized Scattering. ... ... .. ........... . ..... ... .. 60 3.2.1. Scattering Configurations .................................. 60 3.2.2. Physical Principles ........................................... 61 3.3. Rigid Macromolecules in Dilute Solution........ ........ ... ..... 65 3.3.1. Hydrodynamics of Rigid Macromolecules.............. 65 3.3.2. Interferometric Studies ...................................... 68 3.3.3. Photon Correlation Studies .. ...... ... .. ...... ........... .. 69 3.4. Rod-Shaped Macromolecules in Semidilute Solutions ........ 72 3.5. Flexible Macromolecules............. .... ....... ......... ...... ...... 75 3.6. Rotation of Small Moleeules in Viscous Media................. 79 3.7. Resonance-Enhanced Depolarized Dynamic Light Scattering .................. ..... ... .... .. ......... .. ..... ...... ..... ..... 80 References and Notes.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 Chapter 4 Particle Interactions ........ ....... ..... ....... ...... ..... . ... .. ..... . .......... .. ... 85 P. N. Pusey and R. J. A. Tough 4.1. Introduction ........... ............ ........................ ..... ........ 85 4.2. Quantities Measured by Light Scattering ..... ....... .. ..... .. ... 90 4.2.1. Introduction ....... ...... ... ........ ...... ....... ............. 90 4.2.2. Monodisperse Systems ........ ... ........ ........... ... ..... 91 4.2.3. Polydisperse Systems.......................... .......... .... 92 4.2.4. Discussion..................................................... 94 4.3. Theory ................................................................... 96 4.3.1. Introduction .................................................. 96 4.3.2. Stokes-Einstein Relations.................................. 97 4.3.3. The Generalized Smoluchowski Equation.............. 101 Contents xi 4.3.4. Hydrodynamic Interactions ................................ 103 4.3.5. Short-Time Motions..... .... ..... ...... ....... ......... ..... 108 4.3.6. Projection Operator Analysis.............................. 114 4.3.7. Dynamics in the Small-q Limit-Cooperative and Self-Diffusion ................................................ 120 4.4. Charged Particles in Dilute Suspension (Negligible Hydrodynamic Interactions) ...................................... 126 4.4.1. Introduction .................................................. 126 4.4.2. Single-Particle Motions (q > qm' all r) .................. 130 4.4.3. The First Cumulant (rB ~ r ~ ru all q) .............. ... 136 4.4.4. Low-q Limit and the Effect of Polydispersity.......... 137 4.4.5. Memory Effects ...... ......... .... ............... .......... ... 142 4.5. Effects ofHydrodynamic Interactions............................. 144 4.5.1. Introduction .................................................. 144 4.5.2. Theory of the Collective Diffusion Coefficient in the Hydrodynamic Regime ............ ..... .................... 145 4.5.3. Experimental Results ........................................ 149 4.5.4. Microemulsions .............................................. 154 4.5.5. Hydrodynamic Effects at Finite q......................... 158 4.6. Small-Ion Effects ...................................................... 159 4.7. Conclusions ..................... ........................................ 162 4.8. Addendum .......... ............ .... .................... ....... ......... 164 References and Notes. ................................................. 171 Chapter 5 Quasielastic Light Scattering from Dilute and Semidilute Polymer Solution. . . .. . . . . . .. . . .. . . . . . . . . . . . .. . . . .. . . . . . . . . . . . . . . . .. . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . 181 D. W. Schaefer and C. C. Han 5.1. In trod uction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . . . . . .. . . .. . . . . . . . . . . . . . . . . . 181 5.2. The Single Chain....................................................... 182 5.2.1. Basic Polymer Statistics..................................... 182 5.2.2. Dynamical Regimes.......................................... 186 5.2.3. Center-of-Mass Diffusion (qR ~ 1)....................... 193 5.2.4. Internal Dynamics and the Dynamic Structure Factor .......................................................... 200 5.3. Vi rial Regime............................................................ 214 5.4. Semidilute Solutions................................................... 217 5.4.1. Introduction .................................................. 217 5.4.2. Dynamical Regimes. ........ ...... ....... ............... ..... 221 5.4.3. Conclusions ................................................... 240 References ............................................................... 241

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