Chemically Induced Magnetic Polarization: Proceedings of the NATO Advanced Study Institute held at Sogesta, Urbino, Italy, April 17–30, 1977

411 Pages·1977·24.07 MB·English

by  R. Kaptein (auth.)

Chemically Induced Magnetic Polarization
NATO ADVANCED STUDY INSTITUTES SERIES
Proceedings oft he Advanced Study Institute Programme, which aims
at the dissemination of advanced knowledge and
theformation ofc ontacts among scientistsfrom different countries
The series is published by an international board of publishers in conjunction
with NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical and D.Reidel Publishing Company
Physical Sciences Dordrecht and Boston
D Behavioral and Sijthofflnternational Publishing Company
Social Sciences Leiden
E Applied Sciences N oordhoffInternational Publishing
Leiden
Series C - Mathematical and Physical Sciences
Volume 34 - Chemically Induced Magnetic Po/arizatioti
Chemically Induced
Magnetic Polarization
Proceedings of the NA TO Advanced Study Institute
held at Sogesta, Urbina, Italy, April 17-30, 1977
edited by
L. T. M U US, Aarhus University, Denmark
P. W. ATKINS, Oxford University, U.K.
K. A. McLAUCHLAN, OxfordUniversily, U.K.
J. B. PEDERSEN, Odense University, Denmark
D. Reidel Publishing Company
Dordrecht-Hollandf Boston-U.S.A.
Published in cooperation with NATO Scientific Affairs Division
Library of Congress Cataloging in Publication Data
Nato Advanced Study Institute, Urbino, 1977.
Chemically induced magnetic polarization.
(NA TO advanced study institutes series: Series C, Mathematical and physical
sciences; v. 34)
'Published in cooperation with NATO Scientific Affairs Division:
I. Radicals (Chemistry)-Congresses. 2. Polarization (Nuclear phy
sics)-Congresses. 3. Nuclearmagnetic resonance-Congresses. J. Muus, L. T.
II. Title. Ill. Series.
QD471.N29 1977 541'.378 77-10592
ISBN-13: 978-94-010-1267-6 e-ISBN-13: 978-94-010-1265-2
DOl: 10.1007/978-94-010-1265-2
Published by D. Reidel Publishing Company
P.O. Box 17, Dordrecht, Holland
Sold and distributed in the U.S.A., Canada, and Mexico
by D. Reidel PUblishing Company, Inc.
Lincoln Building, 160 Old Derby Street, Hingham, Mass. 02043, U.S.A.
All Rights Reserved
Copyright © 1977 by D. Reidel Publishing Company, Dordrecht, Holland
No part of the material protected by this copyright notice may be reproduced or utilized
in any form or by any means, electronic or mechanical, including photocopying,
recording or by any informational storage and retrieval system,
without written permission from the copyright owner
Softcover reprint of the hardcover 1st edition 1977
CONTENTS
PREFACE VII
LIST OF PARTICIPANTS IX
R. Kaptein:
I. INTRODUCTION TO CHEMICALLY INDUCED MAGNETIC
POLARIZATION 1
R.G. Lawler:
II. CIDNP EXHIBITED BY THERMALLY DECOMPOSING DIACYL
PEROXIDES 17
R.G. Lawler:
III. TIME-DEPENDENCE OF CIDNP INTENSITIES 29
H.D. Roth:
IV. CHEMICALLY INDUCED NUCLEAR SPIN POLARIZATION IN
PHOTO-INITIATED RADICAL ION REACTIONS 39
F.J. Adrian:
V. RADICAL PAIR MECHANISM OF CHEMICALLY INDUCED
MAGNETIC POLARIZATION 77
K.A. McLauchlan:
VI. EXPERIMENTAL OBSERVATION OF ELECTRON SPIN
POLARIZATION IN REACTIONS 107
R.W. Fessenden:
VII. CHEMICALLY INDUCED ELECTRON POLARIZATION OF
RADIOLYTICALLY PRODUCED RADICALS 119
K.A. McLauchlan:
VIII. FLASH-PHOTOLYSIS ELECTRON SPIN RESONANCE 151
J.B. Pedersen:
IX. TIME-DEPENDENCE OF ESR INTENSITIES 169
P.W. Atkins:
X. PHOTOCHEMICAL PROCESSES 181
VI TABLE OF CONTENTS
P.W. Atkins:
XI. THE TRIPLET MECHANISM 191
L.T. Muus:
XII. LIGHT MODULATED CIDEP EXPERIMENTS 205
G.L. Closs:
XIII. LOW FIELD EFFECTS AND CIDNP OF BlRADICAL
REACTIONS 225
R. Kaptein:
XIV. PAIR SUBSTITUTION EFFECTS IN CIDNP 257
R.G. Lawler:
XV. CIDNP FROM BIMOLECULAR REACTIONS OF
ORGANOMETALLIC COMPOUNDS 267
R.G. Lawler:
XVI. THE PROBLEM OF PARALLEL RADICAL AND NON
RADICAL MECHANISMS 275
J.B. Pedersen:
XVIII. EFFECTS OF DIFFUSION ON REACTION RATES 283
J.B. Pedersen:
XlIX. GENERAL RELATIONS FOR HIGH-FIELD CIDNP 297
J.H. Freed:
XIX. NUMERICAL METHODS AND MODEL DEPENDENCE IN
CHEMICALLY INDUCED DYNAMIC SPIN POLARIZATION 309
G.L. Closs:
XX. CHEMICALLY INDUCED MAGNETIC POLARIZATION IN
SYSTEMS OF BIOCHEMICAL INTEREST 357
F.J. Adrian:
XXI. TRIPLET OVERHAUSER MECHANISM OF CIDNP 369
P.W. Atkins:
XXII. THE EFFECTS OF MAGNETIC FIELDS ON CHEMICAL
REACTIONS 383
J. Bargon:
XXIII. CIDNP FROM TRIPLET PAIR RECOMBINATION 393
A.J. Hoff and H. Rademaker:
XXIV. LIGHT-INDUCED MAGNETIC POLARIZATION
IN PHOTOSYNTHESIS 399
SUBJECT INDEX 405
PREFACE
Magnetic resonance has constantly been able to surprise with
its ability to exhibit new phenomena. Just when it appears to be
entering a quiet middle age it bursts into activity with some new
manifestation of its versatility. This happened a few years ago,
when observations on anomalous intensities were looked at more
closely, and the pursuit of explanations and further evidence laid
the foundations of the subjects treated in this volume.
In organizing the NATO Advanced Study Institute we attempted
to bring together a number, but by no means all, of those who had
contributed significantly to the subject, and to obtain from them
a comprehensive and detailed exposition of the subject. We were
particularly anxious to avoid a set of lectures that dealt solely
with the theory of the subject, because much of the interest in
chemically induced magnetic polarization is due to its usefulness
in applications to chemical problems: it is a real chemical tech
nique, not just an amusing diversion for theoreticians. We set
about organizing the course with the idea of making it useful to
people who wanted to use the technique (for, after all, in the
case of nuclear polarization, CIDNP, the technique can be used in
any laboratory with minor modification of standard equipment).
In order to do that we started the course, as we start thi5 vol
ume, with a simple, straightforward introduction to the interpre
tation of CIDNP spectra, the radical pair theory, and some appli
cations to the elucidation of reaction mechanisms. Then we have
an introduction to the more involved techniques needed to look at
electron polarizations, and a similar survey of the range of its
applications.
At that point, in order to use the technique with confidence
and to obtain the maximum amount of information, it is necessary
to go more deeply into the underlying theory. At the ASI, and in
this volume, we attempted to do this ~ithout losing sight of the
reasons for doing it, and the chapters in this volume represent
the mixture of theory and experiment often encountered in labora
tories. The chapters also represent the various theories that
VIII PREFACE
are encountered:· at this level of expos~t~on, and in a subject
where the interplay of quantum mechanical, statistical, and re
active processes is so intricate, there are several ways of look
ing at the processes involved. People new to the subject initial
ly may find one way of talking about the subject more congenial
than a more sophisticated version: both approaches will be found
here.
This volume would not have appeared without the sustained
effort of a large number of people. First there are the lectur
ers: they all worked very hard to prepare an interesting and au
thoritative set of lectures well before the ASI, and gave unstint
ingly of their time and expertise during.the duration of the In
stitute. The editors of this book (who were also the organizers
of ASI) were greatly assisted by the authorities at "Sogesta",
where the Institute was held, and drew heavily on both their ex
cellent facilities and their cooperation, for both the Institute
itself and a portion of the editing of this book. We all would
like to thank Mrs. Ruth Buch, who yet again devoted so much effort
and efficiency to the organization of the ASI for several months
before it took place. Finally, but by no means least, we would
like to record our gratitude to the NATO Scientific Affairs Divi
sion for their generous financial support.
Aarhus, Odense, and Oxford. L.T. Muus
May 1977. P.W. Atkins
K.A. McLauchlan
J.B. Pedersen
LIST OF PARTICIPANTS
Professor Frank J. ADRIAN: The Johns Hopkins University, Applied
Physics Laboratory, Johns Hopkins Road, Laurel, Maryland 20810,
U.S.A.
Dr John AMMETER: Institute of Inorganic Chemistry, ETH, CH-8001
Zurich, Switzerland
Dr P. W. ATKINS: Physical Chemistry Laboratory, Oxford University,
South Parks Road, Oxford OX1 3QZ, U.K.
Mr Paul BARBARA: Department of Chemistry, Brown University,
Providence, Rhode Island 02912, U.S.A.
Dr Joachim BARGON: IBM Corporation, Research Division, Monterey
and Cottle Roads, San Jose, California 95193, U.S.A.
Dr Fuat BAYRAK~EKEN: Orta Dogu Teknik Universitesi, Teorik Kimya
Bolumu, Ankara, Turkey
Dr Hans-Dieter BECKHAUS: Chem. Laboratorium der Universitat,
Albertstr. 21, D-7800 Freiburg, B.R.D.
Dr Reinhard BENN: Max-Planck-Institut fur Kohlenforschung,
Kaiser-Wilhelm Platz I, 433-Mulheim a.d. Ruhr, B.R.D.
J.W.M. de BOER: Dept. of Physical Chemistry, Faculty of Science,
University of Nijmegen, Toernooiveld, Nijmegen, Netherlands
Dr Marie BORZO: Institut de Chimie, Universit€ de Liege, Liege,
Belgium
Dr Robert E. BOTTO: Caltech, Pasadena, California 91109, U.S.A.
Dr Roselyne BRIERE: C.E.N.G., Laboratoire COP/DRF-B.P.85-Centre
de TRI, 38041 Grenoble Cedex, France
x
LIST OF PARTICIPANTS
Dr Charles BROWN: University Chemical Laboratory, University of
Kent, Canterbury, Kent CT2-7NH, U.K.
Dr Marina BRUSTOLON: Physical Chemistry Institute, Padua, Italy
Mrs Ruth BUCH: Department of Chemistry, Aarhus University, 140
Langelandsgade, SOOO Aarhus C, Denmark
Dr Serge CAPLAIN: Univ. des Sciences et Techniques de Lille,
Lab. de Chimie Organique Physique, B.P.36, 59650 Villeneuve
d'Ascq, France
Professor G.L.CLOSS: Department of Chemistry, The University of
Chicago, Chicago, 111.60637, U.S.A.
Dr Odile CONVERT: Faculte des Sciences Paris VI, Lab. de Chimie
Organique Structurale, S Rue Cuvier, 75230 Paris Cedex 05,
France
Mr Karl-Michael DANGEL: Institut fur Organische Chemie, Universitat
Tubingen, Auf der Morgenstelle IS-74 Tubingen I, B.R.D.
Professor Nadine FEBVAY-GAROT: Facult€ de Pharmacie, Laboratoire
de Physique, Rue du Prof.Laguesse, 59045 Lille Cedex, France
Professor R.W. FESSENDEN: Radiation Laboratory, University of
Notre Dame, Notre Dame, Ind. 46556, U.S.A.
Professor H. FISCHER: Physikalisch-Chemisches Institut der
Universitat, Ramistrasse 76, CH SOOI Zurich, Switzerland
Dr J. FOSSEY: CNRS, GR.12, 2 rue H.Dunant, 94 Thiais, France
Professor Jack H. FREED: Department of Chemistry, Cornell
University, Ithaca, New York 14S53, U.S.A.
Mr S0REN FRYDKJAER: Department of Chemistry, 140 Langelandsgade,
DK-SOOO Aarhus C, Denmark
W. Carl GOTTSCHALL: Department of Chemistry, University of Denver,
University Park, Denver, Colorado S0210, U.S.A.
Dr Maurizio GUERRA: Lab. dei composti del carbonio contenenti
etero-atomie e loro applicazioni, CNR, Via Tolara di Sotto SI/A,
40064 Ozzano Emi1ia(Bologna) , Italy
Mr Richard A. HEARMON: Dpt. of Organic Chemistry, The University
of Liverpool, The Robert Robinson Lab., P.O.Box 147, Liverpool,
L69 3BX, U.K.