Molecular light scattering and optical activity PDF
Preview Molecular light scattering and optical activity
This page intentionally left blank 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 - ---- eBook (NetLibrary) - --- eBook (NetLibrary) - ---- hardback - --- hardback Cambridge University Press has no responsibility for the persistence or accuracy of s for external or third-party internet websites referred to in this publication, and does not guarantee that any content on such websites is, or will remain, accurate or appropriate. 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HermanMelville,MobyDick 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
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