EPR of Free Radicals in Solids: Trends in Methods and Applications

649 Pages·2003·15.436 MB·English

by  Anders Lund, Wei Liu (auth.), Anders Lund, Masaru Shiotani (eds.)

EPR OF FREE RADICALS IN SOLIDS
Progress in Theoretical Chemistry and Physics
VOLUME 10
Honorary Editors:
W.N. Lipscomb (Harvard University, Cambridge, MA, U.S.A.)
I. Prigogine (Université Libre de Bruxelles, Belgium)
Editors-in-Chief:
J. Maruani (Laboratoire de Chimie Physique, Paris, France)
S. Wilson (Rutherford Appleton Laboratory, Oxfordshire, United Kingdom)
Editorial Board:
H. Ågren (Royal Institute of Technology, Stockholm, Sweden)
D. Avnir (Hebrew University of Jerusalem, Israel)
J. Cioslowski (Florida State University, Tallahassee, FL, U.S.A.)
R. Daudel (European Academy of Sciences, Paris, France)
E.K.U. Gross (Universität Würzburg Am Hubland, Germany)
W.F. van Gunsteren (ETH-Zentrum, Zürich, Switzerland)
K. Hirao (University of Tokyo, Japan)
I. Hubac˘(Komensky University, Bratislava, Slovakia)
M.P. Levy (Tulane University, New Orleans, LA, U.S.A.)
G.L. Malli (Simon Fraser University, Burnaby, BC, Canada)
R. McWeeny (Università di Pisa, Italy)
P.G. Mezey (University of Saskatchewan, Saskatoon, SK, Canada)
M.A.C. Nascimento (Instituto de Quimica, Rio de Janeiro, Brazil)
J. Rychlewski (Polish Academy of Sciences, Poznan, Poland)
S.D. Schwartz (Yeshiva University, Bronx, NY, U.S.A.)
Y.G. Smeyers (Instituto de Estructura de la Materia, Madrid, Spain)
S. Suhai (Cancer Research Center, Heidelberg, Germany)
O. Tapia (Uppsala University, Sweden)
P.R. Taylor (University of California, La Jolla, CA, U.S.A.)
R.G. Woolley (Nottingham Trent University, United Kingdom)
The titles published in this series are listed at the end of this volume.
EPR of Free Radicals
in Solids
Trends in Methods and Applications
Edited by
Anders Lund
Department of Physics and Measurement Technology,
Linköping University, Sweden
and
Masaru Shiotani
Department of Applied Chemistry,
Graduate School of Engineering, Hiroshima University, Japan
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
Library of Congress Cataloging-in-Publication Data
ISBN 978-1-4419-5246-2 ISBN 978-1-4757-5166-6 (eBook)
DOI 10.1007/978-1-4757-5166-6
Printed on acid-free paper
All Rights Reserved
©2003Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 2003
No part of this work 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, with the exception
of any material supplied specifically for the purpose of being entered
and executed on a computer system, for exclusive use by the purchaser of the work.
Contents
Preface xi
Acknowledgments xiii
Contributing Authors XV
Part 1: Trends in Methods
Chapter 1.
Continuous wave EPR of radicals in solids 3
Anders Lund and Wei Liu
1. INTRODUCTION
2. RADICAL STRUCTURE
3. SATURATION PROPERTIES OF RADICALS
4. INTERNAL MOTION OF RADICALS
5. DIFFUSION OF RADICALS
6. REFERENCES
Chapter 2.
Pulsed EPR of paramagnectic centers in solid phases 39
Marina Brustolon and Antonio Barbon
1. INTRODUCTION
2. THEORY
VI EPR offree radicals in solids
3. THE DETERMiNATiON OF ELECTRON SPiN LONGiTUDINAL
RELAXATION
4. THE DETEKMINATION OF ELECTKON SPIN TKANSVEKSE
RELAXATION
5. THE DETERMINATION OF HYPERFINE INTERACTIONS
6. REFERENCES
Chapter 3.
Dynamical effects in CW and pulsed EPR 95
Nikol~s P. Benetis
1. INTRODUCTION
2. TYPES OF DYNAMICAL PROCESSES ACCESSIBLE BY EPR
3. SELECTED EXM1PLES OF CONFORMATIONAL REORGANIZATION
AND LIBRATION
4. FUNDAMENTAL DYNAMICAL PARAMETERS
5. MAGNETIC RELAXATION
6. CHEMICAL EXCHANGE
7. iNERTIAL EFFECTS OF ROTATION
8. DYNM1ICS BY CW-ENDOR SPECTROSCOPY
9. PULSED-EPR TECHNiQUES
10. LIBRATIONAL MOTION STUDIED BY ED-EPR
11. REFERENCES
Chapter 4.
Quantum effects in deuterium labelled radicals at low temperature 153
Masaru Shiotani and Kenji Komaguchi
1. INTRODUCTION
2. HIGH KESOLUTION ESR AND NUCLEAR SPIN-KOTATION COUPLING
OF METHYL RADICALS
3. HYDROGEN ATOM - HYDROGEN MOLECULE PAIR FORMATION IN
ARGON
4. PARA-HYDROGEN ~OLECULE AND HIGH RESOLUTION ESR SPECTRA
5. JAHN-TELLER DISTORTION OF Tct AND D3h MOLECULES AND HID
ISOTOPE EFFECTS
6. DEUTERIUM ISOTOPE EFFECTS ON METHYL HYDROGEN
CONFORMATION
7. STATIC AND DY'IAMTC STRUCTURES OF CYCLOHEXANE AND
RELATED RADICAL CATIONS
8. HYDROGEN ATOM ABSTRACTION VIA TU'JNELLING
EPR offree radicals in solids vii
9. REFERENCES
Chapter 5.
XSophe- Sophe-XeprView: A computer simulation software suite for
the analysis of continuous wave EPR spectra 197
Graeme R. Hanson, Kevin E. Gates, Christopher.!. Noble,
Anthony Mitchell, Simon Benson, Mark Gr(ffin, Kevin Burrage
1. INTRODUCTION
2. THk XSOPHk X-WINDOW (iRAPHICAL lJSkR INTERFACE
3. SOPHE
4. ROLE OF FREQUENCY (AND TEMPERATURE) IN EXTRACTING SPIN
HAMILTONIAN PARAMETERS
5. FUTURE DIRECTIONS FOR XSOPHE
6. CONCLUSIONS
7. REFERENCES
Chapter 6.
The calculation of the hyperfine coupling tensors of biological radicals
239
Fuqiang Ban, James W. Gauld, Stacey D. Wetmore and Russell J. Boyd
I. INTRODUCTION
2. THEORETICAL BACKGROUND
3. THEORETICAL STUDIES OF AMINO ACID RADICALS
4. CONCLUDING REMARKS
5. REFERENCES
Chapter 7.
Ab initio and density functional calculations of electronic g-tensors for
organic radicals 267
Martin Kaupp
1. INTRODUCTION
2. THEHAMILTONIAN
3. QUANTUM CHEMICAL APPROACHES
4. PERFORMANCE OF AR INITIO AND DFf MF.THODS, VALIDATION
STUDIES
5. APPLICATIONS TO BIOLOGICALLY RELEVANT RADICALS
6. CONCLUSIONS AND OUTLOOK
viii EPR offree radicals in solids
7. REFERENCES
Chapter 8.
Radiolabelled radicals derived from volatile organic compounds (VOCs)
sorbed on reactive surfaces: implications for atmospheric chemistry and
pollution control 303
Christopher J. Rhodes
1. INTRODUCTION
2. METHODS
3. ZEOLITES AI\D CLAY SURFACES
4. CARBON PARTICLES
5. ONGOING FURTHER STUDIES
6. CONCLUSIONS
7. REFERENCES
Part II: Trends in Applications 335
Chapler9.
EPR studies of atomic impurities in rare gas matrices 337
Henrik Kunttu and .Tussi Eloranta
1 . INTRODUCTION
2. EXPERD\1ENTAL TECHNIQUES
3. ATOMIC IMPURITIES IN RARE GAS MATRICES
4. THEORETICAL TREATMENTS FOR ATOMIC IMPURITIES
5. REFERENCES
Chapter 10.
Organic radical cations and neutral radicals produced by radiation in
low-temperature matrices 363
Vladimir Feldman
1. INTRODUCTION
2. EXPERIMENTAL APPROACHES AND OVERVIEW OF RESULTS
3. POSITIVE HOLE MIGRATION AND TRAPPIN(;
4. MATRIX EFFECTS ON TRAPPING AND REACTIONS OF RADICAL
CATIONS
EPR offree radicals in solids ix
5. SELECTIVITY OF THE PRIMARY RADIATION-INDUCED CHEMICAL
EVENTS
6. CONCLUSIONS AND OUTLOOK
7. REFERENCES
Chapter 11.
Molecule-based exchange-coupled high-spin clusters 407
Takeji Takui, Hideto Matsuoka, Kou Furukawa,
Shigeaki Nakazawa, Kazunolm Sato, Daisuke Shiomi
1. INTRODUCTION
2. THEORETICAL BACKGROUND
3. SPECTRAL SIMULATION BASED ON A HYBRID EIGENFIELD METHOD
AND PERTURBATION TREATMENTS
4. SOLUTION ESR SPECTROSCOPY FOR MOLECULAR HIGH-SPIN
SYSTEMS WITH EXCHANGE INTERACTION COMPARABLE TO
HYPERFINE [\/TERACTIONS
5. HIGH SPIN CHEMISTRY OF VARIOUS MOLECULAR CLUSTERS;
UTILIZATION OF HIGH-FIELD/HIGH-FREQUENCY ESR AND PULSED
ESR SPECTROSCOPY
6. METAL HIGH-SPIN CLUSTERS OF BIOLOGICAL IMPORTANCE;
MANGANESE CLUSTERS IN PHOTOSYSTEM 11
7. CONCLUSIONS
8. REFERENCES
Chapter 12.
High spin molecules directed towards molecular magnets 491
Martin Baumgarten
1. INTRODUCTION
2. BIRADICALS- THETRIPLETSTATE
3. TRIRADICALS-THE QUARTET STATE
4. TETRARADICALS-THE QUINTET STATE
5. HIGHER SPIN STATES, S ~ 5/2
6. CONCLUSION AND OUTLOOK
7. REFERENCES