Molecular light scattering and optical activity

467 Pages·2004·2.907 MB·English

by  Laurence D. Barron

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MOLECULAR LIGHT SCATTERING
AND OPTICAL ACTIVITY
Using classical and quantum methods with a strong emphasis on symmetry prin-
ciples, this book develops the theory of a variety of optical activity and related
phenomenafromtheperspectiveofmolecularscatteringofpolarizedlight.Inaddi-
tiontothetraditionaltopicofopticalrotationandcirculardichroisminthevisible
andultravioletregionassociatedwithelectronictransitions,thenewertopicofop-
tical activity associated with vibrational transitions, which may be studied using
both infrared and Raman techniques, is also treated. Ranging from the physics of
elementary particles to the structure of viruses, the subject matter of the book re-
flects the importance of optical activity and chirality in much of modern science
andwillbeofinteresttoawiderangeofphysicalandlifescientists.
Laurence Barron worked with Professor Peter Atkins for his doctorate in
theoreticalchemistryfromOxfordUniversity,followedbypostdoctoralworkwith
ProfessorDavidBuckinghamatCambridgeUniversity.Hewasappointedtoafac-
ulty position at Glasgow University in 1975, where he is currently the Gardiner
ProfessorofChemistry.Hisresearchinterestsareintheelectric,magneticandop-
ticalpropertiesofmolecules,especiallychiralphenomenaincludingRamanoptical
activitywhichhepioneeredandisdevelopingasanovelprobeofthestructureand
behaviourofproteins,nucleicacidsandviruses.

MOLECULAR LIGHT SCATTERING
AND OPTICAL ACTIVITY
Second edition, revised and enlarged
LAURENCE D. BARRON,f.r.s.e.
GardinerProfessorofChemistry,UniversityofGlasgow
  
Cambridge, New York, Melbourne, Madrid, Cape Town, Singapore, São Paulo
Cambridge University Press
The Edinburgh Building, Cambridge  , UK
Published in the United States of America by Cambridge University Press, New York
www.cambridge.org
Information on this title: www.cambridge.org/9780521813419
© L. D. Barron 2004
This publication is in copyright. Subject to statutory exception and to the provision of
relevant collective licensing agreements, no reproduction of any part may take place
without the written permission of Cambridge University Press.
First published in print format 2004
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Contents
Prefacetothefirstedition pagexi
Prefacetothesecondedition xv
Listofsymbols xviii
1 Ahistoricalreviewofopticalactivityphenomena 1
1.1 Introduction 1
1.2 Naturalopticalrotationandcirculardichroism 2
1.3 Magneticopticalrotationandcirculardichroism 10
1.4 Lightscatteringfromopticallyactivemolecules 14
1.5 Vibrationalopticalactivity 17
1.6 X-rayopticalactivity 21
1.7 Magnetochiralphenomena 22
1.8 TheKerrandCotton–Moutoneffects 23
1.9 Symmetryandopticalactivity 24
Spatialsymmetryandopticalactivity • Inversionsymmetryand
physicallaws • Inversionsymmetryandopticalrotation • Inversion
symmetryandopticalactivityinlightscattering • Motion-dependent
enantiomorphism:trueandfalsechirality • Symmetryviolation:the
fallofparityandtimereversalinvariance • Chiralityandrelativity •
Chiralityintwodimensions
2 Moleculesinelectricandmagneticfields 53
2.1 Introduction 53
2.2 Electromagneticwaves 54
Maxwell’sequations • Planemonochromaticwaves • Forceand
energy • Thescalarandvectorpotentials
2.3 Polarizedlight 61
Purepolarization • Partialpolarization
2.4 Electricandmagneticmultipolemoments 67
vii
viii Contents
Electricmultipolemoments • Magneticmultipolemoments • Static
electricmultipolefields • Staticmagneticmultipolefields •
Dynamicelectromagneticmultipolefields
2.5 Theenergyofchargesandcurrentsinelectricand
magneticfields 78
Electricandmagneticmultipolemomentsinstaticfields • Electric
andmagneticmultipolemomentsindynamicfields
2.6 Moleculesinelectricandmagneticfields 85
Amoleculeinstaticfields • Amoleculeinaradiationfield • A
moleculeinaradiationfieldatabsorbingfrequencies •
Kramers–Kronigrelations • Thedynamicmolecularpropertytensors
inastaticapproximation
2.7 Amoleculeinaradiationfieldinthepresenceof
otherperturbations 103
2.8 Moleculartransitiontensors 107
TheRamantransitionpolarizability • Theadiabaticapproximation •
ThevibrationalRamantransitiontensorsinPlaczek’sapproximation •
Vibronicinteractions:theHerzberg–Tellerapproximation
3 Molecularscatteringofpolarizedlight 123
3.1 Introduction 123
3.2 Molecularscatteringoflight 124
3.3 Radiationbyinducedoscillatingmolecularmultipolemoments 126
3.4 Polarizationphenomenaintransmittedlight 127
Refractionasaconsequenceoflightscattering • Refringent
scatteringofpolarizedlight • Simpleabsorption • Lineardichroism
andbirefringence(theKerreffect) • Electricfieldgradient-induced
birefringence:measurementofmolecularelectricquadrupole
momentsandtheproblemoforigininvariance • Naturaloptical
rotationandcirculardichroism • Magneticopticalrotationand
circulardichroism • Magnetochiralbirefringenceanddichroism •
Nonreciprocal(gyrotropic)birefringence • TheJonesbirefringence •
Electricopticalrotation(electrogyration)andcirculardichroism
3.5 PolarizationphenomenainRayleighandRaman
scatteredlight 151
Nonrefringentscatteringofpolarizedlight • Symmetricscattering •
Antisymmetricscattering • NaturalRayleighandRamanoptical
activity • MagneticRayleighandRamanopticalactivity • Electric
RayleighandRamanopticalactivity
4 Symmetryandopticalactivity 170
4.1 Introduction 170
4.2 Cartesiantensors 170