Structural Glasses and Supercooled Liquids E-Book

Peter G. Wolynes

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 829

Veröffentlichungsjahr: 2012

Beschreibung

With contributions from 24 global experts in diverse fields, and edited by world-recognized leaders in physical chemistry, chemical physics and biophysics, Structural Glasses and Supercooled Liquids: Theory, Experiment, and Applications presents a modern, complete survey of glassy phenomena in many systems based on firmly established characteristics of the underlying molecular motions as deduced by first principle theoretical calculations, or with direct/single-molecule experimental techniques. A well-rounded view of a variety of disordered systems where cooperative phenomena, which are epitomized by supercooled liquids, take place is provided. These systems include structural glasses and supercooled liquids, polymers, complex liquids, protein conformational dynamics, and strongly interacting electron systems with quenched/self-generated disorder. Detailed calculations and reasoned arguments closely corresponding with experimental data are included, making the book accessible to an educated non-expert reader.

Leseprobe

Contents

Cover

Title Page

Copyright

Preface

Contributors

Chapter 1: Supercooled Liquid Dynamics: Advances and Challenges

1.1 Introduction

1.2 Primary Relaxations

1.3 Secondary Relaxations

1.4 Fragility

1.5 Heterogeneity

1.6 Physical Aging

1.7 Alcohols

1.8 Concluding Remarks

References

Chapter 2: The Random First-Order Transition Theory of Glasses: A Critical Assessment

2.1 Introduction

2.2 Glass Theory: Where Should One Start?

2.3 Finite dimensions: droplets, cavities, and RFOT

2.4 Dynamics in the Mosaic State

2.5 The Elusive MCT/RFOT Crossover

2.6 Comparison with Other Theoretical Approaches

2.7 Discussion and conclusions

Acknowledgements

Appendix 2.A: Analytical Approaches to Metastable States and Configurational Entropies

Appendix 2.B: A Toy Model of Entropy Driven Cavity Melting

List of Acronyms

List of relevant temperatures (in decreasing order)

List of relevant length scales

List of symbols with different meanings

References

Chapter 3: Dielectric Spectroscopy of Glassy Dynamics

3.1 Introduction

3.2 Dielectric Spectroscopy

3.3 The Phenomenology of Glassy Dynamics as Revealed by Dielectric Spectroscopy

3.4 Broadband Dielectric Spectra of Glass-Forming Liquids

3.5 Summary

References

Chapter 4: Glasses and Replicas

4.1 Introduction

4.2 Complexity

4.3 The Replica Approach to Structural Glasses: General Formalism

4.4 The Replica Approach to Structural Glasses: Some Results

4.5 Conclusion

Acknowledgments

References

Chapter 5: Glassiness in Uniformly Frustrated Systems

5.1 Introduction

5.2 Uniformly Frustrated Systems: A Model Hamiltonian Approach to Glass Formation

5.3 Entropy Crisis and Mean-Field Formalism

5.4 Glass Formation in Uniformly Frustrated Systems

5.5 Replica Landau Theory

5.6 Replica Instantons and Entropic Droplets

5.7 Summary

Acknowledgments

References

Chapter 6: Random First-Order Phase Transition Theory of the Structural Glass Transition

6.1 Introduction

6.2 Density-Functional Models for the Glass Transition

6.3 Static Theory of the Glass Transition

6.4 Dynamical Theory of the Glass Transition

6.5 Scaling and Droplet Considerations

6.6 Discussion

Acknowledgments

References

Chapter 7: Fragile Glass Formers: Evidence for a New Paradigm, and a New Relation to Strong Liquids

7.1 Introduction

7.2 Normal and Ideal Glass Formers

7.3 Strong and Fragile Liquids, Thermodynamic Fragility, and The Heat-Capacity Challenge

7.4 Meeting the Heat-Capacity Challenge with Cooperative Models, and Sub-TG Phase Changes

7.5 Liquid–Liquid Transitions, Heterogeneities, and Viscosity–Diffusivity Decoupling

7.6 Ultrastable Glasses by Vapor-Deposition Routes

7.7 The Bigger Picture: Water as a Rosetta Stone for the Glass Problem

7.8 Support for the General Picture from Correlation Length, and Correlation Time Considerations

7.9 What Factors Promote the High Fragility Needed to Produce the First-Order Phase Transition?

7.10 The Boson Peak and Debye–Waller Factor in Relation to the Glass Transition and Liquid Fragility

7.11 Anharmonicity and the Glass Transition

7.12 Relation of Boson Peaks to Floppy Modes of Underconstrained Covalent Glasses, and Their Connection to Relaxation

7.13 Concluding Remarks

References

Chapter 8: Dynamics in the Crossover Region of Supercooled Liquids

8.1 Introduction

8.2 Dynamic Crossover in Orientational Degree of Freedom

8.3 Signatures of Dynamical Crossover in Energy Landscape

8.4 Dynamics of A Supercooled Polydisperse Liquid

8.5 Intriguing Glassy Relaxation Across the Isotropic Nematic Transition in Thermotropic Liquid Crystals

8.6 Nonmonotonic Temperature Dependency of Specific Heat: A Kinetic Model of Nonequilibrium Relaxation

8.7 Towards A Unified Theory of Relaxation in Supercooled Liquid

8.8 Concluding Remarks

Acknowledgements

References

Chapter 9: Glassy Dynamics of Proteins

9.1 Introduction

9.2 Myoglobin, the Hydrogen Atom of Biology

9.3 Barrier Control, CS, and the EL

9.4 Relaxation Processes in Supercooled Liquids and Glasses

9.5 Gating and α-Slaving

9.6 Internal CO Transit and βh Slaving

9.7 The Hierarchical EL

9.8 Low-Temperature Motions

References

Chapter 10: Theories of Structural Glass Dynamics: Mosaics, Jamming, and All That

10.1 Motivation

10.2 Thermodynamics

10.3 Kinetic Consequences of the Dynamical Mosaic in the Liquid State

10.4 Activated Transport and its Observable Consequences

10.5 Concluding Remarks

Acknowledgments

Appendix 10.A: Localization length in a stable solid

References

Index

Color Plates

Copyright © 2012 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Structural glasses and supercooled liquids: theory, experiment, and applications / Edited By Peter G. Wolynes, Vassiliy Lubchenko.

p. cm.

Includes index.

ISBN 978-0-470-45223-3 (hardback)

1. Glass–Analysis. I. Wolynes, P. G. (Peter G.) II. Lubchenko, Vassiliy.

TA450.S886 2012

620.1′44–dc23

2011045245

ISBN: 9780470452233

Preface

However, during the reign of Tiberius Caesar, a certain artisan invented how to temper glass to make it flexible and ductile. When received by the Caesar, the artisan handed a vase to the Caesar who, in indignant disbelief, threw the vase on the floor. The artisan however picked up the vase, which had deformed as though made of bronze, and then straightened it using a small hammer. Upon this, the Caesar asked the artisan: “Does anyone else know how this property of glass is achieved?” After a negative answer, the Caesar ordered the artisan beheaded, lest this property became known, gold was treated as dirt, and all metals were devalued. Conversely, if glass vases did not break, they would be better than gold and silver.1

From St. Isidore of Seville (c. 560 -636) Etymologies, Book XVI, “Stones and Metals.”

Glasses are fascinating because they defy our intuitive association between stability and uniqueness. While crystals, which possess no structurally distinct low-energy configurations, are eternally stable, a given structure that appears stable against perturbation neither needs to be periodic nor unique. Often very stable mechanically, glasses are actually highly degenerate solids whose fluidity is a continuous function of temperature, in contrast with periodic crystals which melt discontinuously.

The answer to this seeming contradiction is simple: Since stability is usually required not on infinite, but only on finite timescales, sufficiently stable states need not strictly be unique, but only sufficiently rare. This inherent, direct connection between kinetics and thermodynamics of the glass transition was advocated already in the 1950s, preceded by the insightful work of Simon, Kauzmann, and Bernal, among others. Fleshing out these ideas quantitatively has, however, proved to be difficult. One problem is that standard thermodynamics at the macroscopic scale becomes strictly valid only at infinite time, and is thus not rigorously applicable to glasses, which are only metastable. Ergodicity breaking, which haunted the very father of statistical mechanics Ludwig Boltzmann, is realized with vengeance in glasses. On the other hand, kinetic treatments at the molecular scale that work well in conventional fluids become quickly bogged down by cooperative effects arising at high liquid densities.

A tremendous amount of progress in meeting these challenges has been made over the past decades. Experimental tools to characterize quantitatively both the kinetic and thermodynamic peculiarities in glass formers are widespread. Microscopic imaging and single-molecule techniques to directly determine the spatial extent of cooperativity preceding the glass transition have recently been developed, thus providing strict tests for theoretical descriptions. Many novel vitreous compounds with unique properties have been manufactured. We have learned that glasses are indeed different from their periodic counterparts both with regard to their bulk properties and local motions, both nuclear and electronic. For instance, it is a safe bet that the reader of this volume presently uses optical drives that exploit the unique optoelectronic anomalies of chalcogenide glasses. On the other hand, many seemingly disparate physical systems, such as proteins and their assemblies in protoplasm, show signatures of the glass transition.

Paralleling experimental developments, much progress has been achieved in theoretical understanding of both the thermodynamics and the kinetics of the glass transition. The mathematics behind the mechanism connecting the decrease in the density of states and the viscous slowdown, which precede the glass transition, has been well-developed. Many beautiful connections have been uncovered between the physics of supercooled liquids and optimization problems in computer science, social science, and economics. Theoretical tools to describe ergodicity breaking in glassformers have been developed. The arsenal from liquid-state theory is continuously growing, suggesting the ability to predict the structure and glassforming ability of specific substances is in near sight.

The aim of the present volume is to bring the reader several modern views of the glass transition and relaxations in glassy systems, from leading practitioners in the field, both from a theoretical and experimental perspective. Both ancient and recent attempts to categorize the structural glass transition or create new glassy materials seem to have involved some risk. Nor have these attempts been without irony: Reaching an agreement on what would really constitute a microscopic theory of the glass transition appears to be subject to a viscous drag not unlike that preceding the physical glass transition itself. We hope the present volume will help ease this perception of there being an intellectual logjam and allow more scientists to see through glass clearly.

Peter G. Wolynes

Vassiliy Lubchenko

Note

1. The Latin original (as can be found at http://www.thelatinlibrary.com/isidore/16.shtml) reads: Ferunt autem sub Tiberio Caesare quendam artificem excogitasse vitri temperamentum, ut flexibile esset et ductile. Qui dum admissus fuisset ad Caesarem, porrexit phialam Caesari, quam ille indignatus in pavimentum proiecit. Artifex autem sustulit phialam de pavimento, quae conplicaverat se tamquam vas aeneum; deinde marculum de sinu protulit et phialam correxit. Hoc facto Caesar dixit artifici: ‘Numquid alius scit hanc condituram vitrorum?’ Postquam ille iurans negavit alterum hoc scire, iussit illum Caesar decollari, ne dum hoc cognitum fieret, aurum pro luto haberetur et omnium metallorum pretia abstraherentur; et revera, quia si vasa vitrea non frangerentur, melius essent quam aurum et argentum.

Contributors

C. Austen Angell, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA

Biman Bagchi, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, India

Giulio Biroli, Institut de Physique Théorique (IPhT), CEA, and CNRS URA 2306, Gif-sur-Yvette, France

Jean-Philippe Bouchaud, (1) Science and Finance, Capital Fund Management, Paris, France and (2) École Polytechnique, Palaiseau, France

Guo Chen, (1) Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM, USA and (2) Department of Applied Physics, Chalmers University of Technology, Göteborg, Sweden

Maxim Dzero, Department of Physics, Kent State University, Kent, OH, USA

Paul W. Fenimore, Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM, USA

Hans Frauenfelder, Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM, USA

Stefan Kastner, Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Augsburg, Germany

Theodore R. Kirkpatrick, Institute for Physical Sciences and Technology and Department of Physics, University of Maryland, College Park, MD, USA

Melanie Köhler, Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Augsburg, Germany

Alois Loidl, Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Augsburg, Germany

Vassiliy Lubchenko, Departments of Chemistry and Physics, University of Houston, Houston, TX, USA

Peter Lunkenheimer, Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Augsburg, Germany

Marc Mézard, Laboratoire de Physique Théorique et Modeles Statistiques, Université de Paris SudCNRS, Orsay, France

Giorgio Parisi, Dipartimento di Fisica, Università di Roma La Sapienza Rome, Italy

Ranko Richert, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA

Jörg Schmalian, Institute for Theory of Condensed Matter, Karlsruhe Institute of Technology, Karlsruhe, Germany

Devarajan Thirumalai, Institute for Physical Sciences and Technology and Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, USA

Peter G. Wolynes, Department of Chemistry and Center for Theoretical Biological Physics, Rice University, Houston, TX, USA