Table Of ContentEPR of Free Radicals in Solids I
Progress in Theoretical Chemistry and Physics
VOLUME24
HonoraryEditors:
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PrYvesChauvin(InstitutFranc¸aisduPe´trole,Tours,France)
Editors-in-Chief:
J.Maruani(formerlyLaboratoiredeChimiePhysique,Paris,France)
S.Wilson(formerlyRutherfordAppletonLaboratory,Oxfordshire,U.K.)
EditorialBoard:
V.Aquilanti(Universita´ diPerugia,Italy)
E.Bra¨ndas(UniversityofUppsala,Sweden)
L.Cederbaum(Physikalisch-ChemischesInstitut,Heidelberg,Germany)
G.Delgado-Barrio(InstitutodeMatema´ticasyF´ısicaFundamental,Madrid,Spain)
E.K.U.Gross(FreieUniversita¨t,Berlin,Germany)
K.Hirao(UniversityofTokyo,Japan)
E.Kryachko(BogolyubovInstituteforTheoreticalPhysics,Kiev,Ukraine)
R.Lefebvre(Universite´Pierre-et-Marie-Curie,Paris,France)
R.Levine(HebrewUniversityofJerusalem,Israel)
K.Lindenberg(UniversityofCaliforniaatSanDiego,CA,U.S.A.)
R.McWeeny(Universita` diPisa,Italy)
M.A.C.Nascimento(InstitutodeQu´ımica,RiodeJaneiro,Brazil)
P.Piecuch(MichiganStateUniversity,EastLansing,MI,U.S.A.)
M.Quack(ETHZu¨rich,Switzerland)
S.D.Schwartz(YeshivaUniversity,Bronx,NY,U.S.A.)
A.Wang(UniversityofBritishColumbia,Vancouver,BC,Canada)
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EPR of Free Radicals
in Solids I
Trends in Methods and Applications
Second Edition
Editedby
ANDERSLUND
UniversityofLinko¨ping,Sweden
MASARU SHIOTANI
UniversityofHiroshima,Japan
123
Editors
AndersLund MasaruShiotani
DepartmentofPhysics,Chemistry GraduateSchoolofEngineering
andBiology HiroshimaUniversity
Linko¨pingUniversity Higashi-Hiroshima
Linko¨ping Japan
Sweden
ISSN1567-7354
ISBN978-94-007-4892-7 ISBN978-94-007-4893-4(eBook)
DOI10.1007/978-94-007-4893-4
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Preface
During the last 10 years, significant progress has been made in the study of free
radicalprocessesinsolidsbyapplyingmodernEPR(ESR)methods.Theprogress
has been possible by instrumental advancements in continuous wave (CW) and
pulse EPR, by development of sensitive detection methods, by the application of
sophisticated matrix isolation techniques and by the advancement in quantitative
EPR,tomentionafewrecentexperimentaltrends.Onthetheoreticalside,methods
based on first principles have been developed and applied for the calculation
of hyperfine couplings, zero-field splittings and g-factors as well as in spectral
simulations.Softwareforthesepurposes,developedduringthelastdecade,isalso
available.Notallofthosedevelopmentscanbetreatedindetailinasinglevolume.
We havethereforeasked severalmain contributorsto the developmentof the field
to presentchaptersin selected areas, where recentreviewsseem to be missing. In
thisrespect,thebookisanupdateofapreviouseditionofthiswork,withasimilar
organizationofthecontent.
The first volume is concerned with trends in experimental and theoretical
methods.Inthefirstchapter,CWEPRandENDORmethodsforstudiesofradical
structureinsinglecrystalsandpowdersarereviewed.Mostofthefollowingseven
chaptersgive accountsof noveldevelopmentsthat so far are only available in the
journal literature. The chapter by Brustolon and Barbon describes the different
pulsedtechniquesasappliedtoradicalsandspinprobesinsolidmatrices.Methods
to extractdynamicalparametersfromCW and pulsed EPR are summarised in the
chapter by Benetis and Dmitriev, which also contains an account of relaxation
phenomena.Newsimulationschemes,includingtheinfluenceofdynamics,arealso
presented. Single crystal measurement is the most straightforward but not always
applicable method for complex systems, where often only powder spectra can be
obtained. For these systems, analyses by simulation techniques based on exact
diagonalisationarebeginningtoreplacethepreviouslyusedperturbationmethods,
as describedin the chapterbyHansonand coworkers.An extendedversionof the
softwarepresentedinthepreviouseditionisoutlined,includingnowalsoprocedures
for the analysis of pulse EPR and several other new features. The software is
availablecommercially.Studiesofquantumeffectsin isotopicallylabelledmethyl
vii
viii Preface
radicalstrappedininertmatricesatlowtemperatureareamajorpartofthechapter
by Shiotani and Komaguchi. A detailed theoretical analysis was possible due to
the extremelyhigh resolution of the EPR spectra at low temperature.The chapter
by Boyd and coworkersillustrates the usefulness of advancedquantum chemistry
methods for the theoretical interpretation of hyperfine coupling tensors. Ab initio
and density functional methods are applicable even for the biological systems.
The calculated parameters have been frequently employed for the assignment of
experimentalspectra in recent work. The methodsfor the calculation ofg-tensors
havebeendevelopedevenmoreduringthelast10yearsasdescribedinthechapter
by Kaupp. The accurate g-tensor data obtained by high-field EPR measurements
can for instance now be analyzed taking into account environmental interactions
withtheradical.Anewchapteronthecalculationofthezero-fieldsplittingtensors
was introduced in this edition. The subject is of relevance for high-spin clusters
and molecules treated in two chapters in the second volume. The theory is also
applicableinEPRstudiesofsystemscontainingpairsofradicals.
The second volume presents applications involving studies of radiation and
photo-inducedinorganicandorganicradicalsininertmatrices.High-spinmolecules
and complexesare also consideredas well as radicalprocesses in photosynthesis.
Recent advancementsin environmentalapplications including EPR dosimetry are
summarised.Therearetrendsbothtowardssimplificationbyusingmatrixisolation
infrozennoblegasmatriceswithaccompanyingincreaseofresolutionasillustrated
inthechapterbyKunttuandElorantaandintheworkbyShiotaniandKomaguchi
inthefirstvolume,andtowardsstudiesofcomplexsystemstreatedinthechapters
by Takui et al., by Baumgarten, Kawamori and by Feldman. In the former case
an overview of the matrix isolation technique for the studies of atoms and small
radicalsembeddedin solid rare gases is presented,while Feldman presentsrecent
development in the EPR studies of reactive intermediates from irradiation of
moderately large organic molecules using matrix isolation. Two chapters address
theissueofhigh-spinsystems,theonebyBaumgarteninorganicsystems,theother
byTakuietal.alsoinmetal-basedmolecularclusters.Bothsubjectshaverelevance
for the development of molecular magnets. The potential application of EPR for
quantum computing is also considered in a newly written chapter, with emphasis
on pulse ENDOR methods. The chapter by Kawamori describes studies of plant
photosystemII by pulsed EPR, dual modeCW EPR and pulsed electron–electron
doubleresonance,thelatterto obtaindistancesbetweenradicalpairstrappedafter
illumination.Accuratemeasurementoftheconcentrationofradicalsisanimportant
issueinEPRdosimetryandotherkindsofquantitativeEPR,whichisaddressedin
thechapterbyYordanovetal. Thissubjectrelatesto otherapplicationsof EPRin
theenvironmentalsciences,discussedinachapterbyRhodes.Inthiscontext,myon
spin resonance provides new means to considerably lower the detection limit in
heterogeneoussystems.Inthefinalchapter,recentdevelopmentsofopticaldetection
tolowerthedetectionlimitandtoobtaintime-resolutioninthecharacterisationof
defectcentresinsemiconductormaterialsarepresentedbyChen.
The titles of the chapters have been retained from the old edition, with one
exception.Thecontentofeachchapterintheneweditiondiffersingeneralfromthat
Preface ix
intheoldbytheadditionofnewresultsanddeletionofoldermaterial,however.The
sizehasneverthelessincreased,inpartalsoduetotheinclusionoftwonewchapters.
Sometechnicalproblemswiththeprintingoffigures,figurelegendsandtheindex
of the previous work have been corrected. The chapters of the first edition were
frequently referred to as additional reading in a work we recently prepared for a
broaderaudience[AndersLund,Masaru Shiotani,ShigetakaShimada:‘Principles
and Applications of ESR Spectroscopy’, Springer (2011)]. We hope that the new
editionwillbeofvalueforthispurposeaswellasforfutureresearchinvolvingfree
radicals.
AndersLund
MasaruShiotani
