X-Ray Spectroscopy: An Introduction

421 Pages·1991·9.37 MB·English

by  Professor Bipin K. Agarwal Ph. D. (auth.)

Springer Series in Optical Sciences Volume 15
SpringerSeries in Optical Sciences
EditorialBoard:A.L.Schawlow K.Shimoda A.E.Siegman T.Tamir
ManagingEditor:H.K.V.Lotsch
42 PrinciplesofPhaseConjugation 55 LaserSpectroscopyVIII
ByB.Ya.Zel'dovich,N.F.Pilipetsky, Editors:W.PerssonandS.Svanberg
v.v.
and Shkunov
56 X-RayMicroscopyII
43 X-RayMicroscopy
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44 IntroductiontoLaserPhysics
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ByE.-G.Neumann
45 ScanningElectronMicroscopy
PhysicsofImageFormationandMicroanalysis
58 PhotoacousticandPhotothermalPhenomena
ByL.Reimer
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46 HolographyandDeformationAnalysis
ByW.Schumann,l-P.ZUrcher,andD.Cuche 59 PhotorefractiveCrystals
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47 TunabelSolidStateLasers
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Volumes1-41arelistedonthebackinsidecover
B.K. Agarwal
X-Ray Spectroscopy
An Introduction
Second Edition
With 239Figures
Springer-Verlag Berlin Heidelberg GmbH
Professor BIPIN K. AGARWAL, Ph. D. (deceased)
Formerly Headofthe Physics Department, Dean ofthe Faculty ofScience
University ofAllahabad, Allahabad 211001, India
Editorial Board
ARTIIUR L. SCHAWLOW, Ph. D. ProfessorANTIIONYE. SIEGMAN,Ph. D.
Department ofPhysics Electrical Engineering
Stanford University E. L. Ginzton Laboratory
Stanford, CA 94305, USA Stanford University
Stanford, CA94305, USA
Professor KOICHI SHIMODA THEODOR TAMIR, Ph. D.
Faculty ofScienceand Technology Polytechnic University
Keio University, 3-14-1 Hiyoshi, Kohoku-ku, 333 Jay Street
Yokohama223, Japan Brooklyn, NY 11201, USA
Managing Editor: Dr. HELMUT K. V.LOTSCH
ISBN978-3-540-50719-2 ISBN978-3-540-38668-1(eBook)
DOI 10.1007/978-3-540-38668-1
LibraryofCongressCataloging-in-PublicationData
Agarwal,B.K.(BipinKumar),1931-
X-rayspectroscopy:anintroduction /B.K.Agarwal.- 2nded.
p.em,- (Springerseriesinopticalsciences;v.15)
Bibliography:p.
Includesindexes.
1.X-rayspectroscopy.I.Title.II.Series.
[DNLM: 1.SpectrumAnalysis.2.X-Rays.QC482.S6A261x]
QC482.S6A341991537.5'352-dcI9DNLM/DLC
forLibraryofCongress
Thisworkissubjecttocopyright.Allrightsarereserved,whetherthewholeor part ofthematerialis
concerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broadcasting,
reproductiononmicrofilmsorinotherways,andstorageindatabanks.Duplicationofthispublicationor
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©Springer-VerlagBerlinHeidelberg1979and 1991
OriginallypublishedbySpringer-VerlagBerlinHeidelbergNewYorkin1991.
Theuseofregisterednames,trademarks,etc.inthispublicationdoesnotimply,evenintheabsenceofa
specificstatement,that suchnamesareexemptfromtherelevantprotectivelawsand regulationsand
thereforefreeforgeneraluse.
54/3020- 54310- Printedonacid-freepaper
To my Mami Ji
memory
in
Preface to the Second Edition
Anattempthas beenmade inthisedition ofthebook to retain theappeal ofthe
first edition even after the addition of new material and the deletion of other
matter which no longer appears essential.
Major revisions have been made in almost all the chapters to include new
developments.Thematerial on EXAFS has beenupdatedand putinaseparate
chapter. Thechapteronexperimental methods has beenconsiderably expanded
to includeenergydispersivetechniques. New topics likeheavy-ion bremsstrah
lung, X-ray lasers, resonant emission, appearance potential spectroscopy, and
EXAFS ofhigh-Tcsuperconductingmaterials havebeenadded. Itishoped that
readers willfind the newedition more useful and attractive.
Iam grateful to Professor R. H; Pratt, University ofPittsburgh,for reading
therevisedversionofthefirstchapter,toDr.H.Lotsch,ofSpringer-Verlag,for
encouraging metorevisethebook,and toPrashantand Seemaforhelpingmein
preparing the manuscript.
Allahabad, B.K.Agarwal
July 1989
Preface to the First Edition
Rontgen's discoveryofX-rays in1895launched asubjectwhichbecamecentral
to the development of modem physics. The verification of many of the
predictions of quantum theory by X-ray spectroscopy in the early part of the
twentieth century stimulated great interest in this area,whichhas subsequently
influencedfieldsasdiverseaschemicalphysics,nuclearphysics,and thestudyof
theelectronicpropertiesofsolids,and ledtothedevelopmentoftechniquessuch
as Auger, Raman, and X-ray photoelectron spectroscopy.
Theimprovement ofthetheoretical understandingofthe physicsunderlying
X-ray spectroscopy has beenaccompanied byadvances inexperimental techni
ques,and the subject provides an instructive example of how progress on both
these fronts can be mutually beneficial. This book strikes a balance between
historicaldescription,whichillustratesthissymbiosis,and thediscussionofnew
developments. The application of X-ray spectroscopic methods to the investi
gationofchemicalbonding receivesspecialattention,and anup-to-dateaccount
is given of the use of extended X-ray absorption fine structure (EXAFS) in
determining interatomic distances, which has attracted much attention during
the last decade.
Thismonographisintended tobeusedasabasictextforaone-yearcourseat
postgraduatelevel,and aimsto provide thegeneralbackgroundthatisessential
to enable the reader to participate fruitfully in the growing research activity in
this field.
SriArvind Agarwaland Dr. ChitraDarhavehelpedmeinmanywaysinthe
preparation of the manuscript. My whole familyjoined me in preparing and
checking the index.
Allahabad, B.K.Agarwal
April 1979
Contents
1. Continuous X-Rays . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Field ofa Point Charge Moving with Uniform Velocity . . . . 1
1.2 Radiation from an Accelerated or Decelerated Charged Particle. 3
1.3 Transverse Radiation Field due to the Acceleration ofan Electron
to Low Velocity (fJ<IA) 5
1.4 Maxwell's Equations 6
1.5 Coulomb Potential . . 7
1.6 Retarded Potentials . . 8
1.7 Lienard-Wiechert Potentials 11
1.8 Radiation from an Accelerated Charge 12
1.9 Radiation at Low Velocities . . . . . 14
1.10 Polarization of Continuous X-Rays. . 16
1.11 The Case of IiParallel to v (Relativistic) . 18
1.12 Sommerfeld's Theory for the Spatial Distribution ofContinuous
X-Rays. . . . . . . . . . . . . . . . . . 18
1.13 Frequency Spectrum ofContinuous X-Rays . . 21
1.14 Experimental Spectral and Spatial Distributions 23
1.15 Shortcomings of Classical Theory . . 25
1.16 Kramers' Semiclassical Theory . . . 27
1.17 Quantum Mechanical Considerations 38
1.17.1 Born Approximation 39
1.17.2 Sommerfeld's Result 40
1.17.3 Polarization . . . . 43
1.17.4 Screening . . . . . 46
1.18 Bremsstrahlung in Other Processes 46
2. Characteristic X-Rays 51
2.1 Line Emission . . . . . . 51
2.2 Moseley Law . . . . . . 53
2.3 Classical Oscillator Model . 54
2.4 Quantum Theory . . . 56
2.5 Ionization Function. . . 57
2.5.1 Classical Theory . 57
2.5.2 Quantum Theory . 59
2.5.3 Heavy Projectiles . 62
2.5.4 Intensity . . . . 63
2.5.5 Molecular-orbital X-Rays . 66
XII Contents
2.6 Ratio of Characteristics to Continuous Radiation. . . . . . 66
2.7 X-Ray Terms . . . . . . . . . . . . . . . . . . . . . 67
2.8 Energies of Atomic X-Ray Levelsand Energy-LevelDiagrams 70
2.9 Electric-Dipole Selection Rules. . . . . . . . . . 75
2.10 Relative Intensities of Emission Linesin a Multiplet. . . . . 77
2.11 Screeningand Spin Doublets. . . . . . . . . . . . . . . 79
2.12 Quantum Theory of Spontaneous Emission of X-Ray Lines and
Multipoles . . . . . . . . . . . . . . . . . . 89
2.12.1 Spontaneous Electric-Dipole Transition . . 90
2.12.2 Spontaneous Higher-Multipole Transitions . 91
2.13 Parity Selection Rules and Forbidden Lines 92
2.14 Absorption Discontinuities. . . . . . . . 96
2.15 Comparison of Optical and X-Ray Spectra. 101
2.16 Nomenclature of X-Ray Lines 102
3. Interaction ofX-Rays withMatter . 105
3.1 Free, Damped Oscillator. . 105
3.2 Form and Width of Lines . . 106
3.3 Forced, Damped Oscillator . 109
3.4 Complex Dielectric Constant . 110
3.5 Refractive Index . . . . . . 112
3.6 Correction of the Bragg Equation. 114
3.7 Measurement of Refractive Index. 116
3.7.1 The Method of Critical Angle of Reflection 116
3.7.2 The Method of Symmetrical Reflection . 117
3.7.3 The Method of Unsymmetrical Reflection 117
3.7.4 The Method of Refraction in a Prism. . 119
3.8 Absorption of X-Rays and Dispersion Theory . 120
3.8.1 Absorption by an Undamped Oscillator. 120
3.8.2 Absorption by a Damped Oscillator. . . 122
3.9 Kramers-Kallmann-Mark Theory of Refractive Index 126
3.10 Quantum Theory of Dispersion. 129
3.10.1 Oscillator Strength . . . . . . . . . . . . 129
3.10.2 Honl Theory. . . . . . . . . . . . . . . 134
3.10.3 Variation ofX-Ray AtomicScattering FactorintheRegion
of Anomalous Dispersion . . . . . . . . . . . . . . 137
3.11 QuantumTheory ofLineShapeand PhotoabsorptionCurveShape 140
3.12 Absorption Coefficients . . . . . . . . . 144
3.12.1 Quantum Theory of Photoabsorption 148
3.12.2 Various Attenuation Processes 149
3.13 Absorption-Jump Ratios. 150
3.14 Total Reflection . . . . . 151
3.15 X-Ray Interferometry . . . 153
4. Secondary Spectra and Satellites . 155
4.1 Photoelectric Effect. . . . 155