Atomic and Molecular Photoabsorption: Absolute Partial Cross Sections

533 Pages·2015·9.09 MB·English

by  Joseph Berkowitz

Atomic and Molecular Photoabsorption
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Atomic and Molecular
Photoabsorption
Absolute Partial Cross Sections
Joseph Berkowitz
Argonne National Laboratory, Argonne, IL, USA
AMSTERDAM lBOSTON lHEIDELBERGl LONDON
NEWYORK lOXFORDlPARIS lSANDIEGO
SANFRANCISCOl SINGAPORElSYDNEYlTOKYO
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Contents
Preface xi
Acknowledgment xiii
1. Alternative Designations of Absolute Partial Cross
Sections
1
1.1 TheSo-CalledComplete, orPerfect,Experiment 1
1.2 Multichannel QuantumDefectTheory(MQDT) 3
1.3 TheMolecularOrbitalPicture; One-Hole IonizedStates
from EachOrbital 6
1.4 IonizationCross-Sections CanAlsoBePartitioned
AccordingtoTheirFinal IonicState 6
References 7
2. Atoms
9
2.1 Absolute Partial Cross-Sections of Helium
9
2.1.1 Introduction 9
2.1.2 TotalPhotoabsorption 13
2.1.3 PartialCross-Sections 15
2.1.4 AbovetheHe2þ Threshold 15
References 20
2.2 AbsolutePartialCross-Sectionsof AtomicLithium
23
2.2.1 Introduction 23
2.2.2 PartialCross-Sectionsbelow64.41eV 24
2.2.3 Photoelectron Spectroscopy 26
2.2.4 PhotoionizationMassSpectroscopy 34
References 37
2.3 Absolute Partial Cross-Sections of Atomic
Nitrogen
40
2.3.1 Introduction 40
2.3.2 Photoelectron Spectroscopy 40
2.3.3 PhotoionizationMassSpectrometry 42
References 47
2.4 AbsolutePartialCross-SectionsofAtomicOxygen
48
2.4.1 Introduction 48
2.4.2 Photoelectron Spectroscopy 48
2.4.3 PhotoionizationMassSpectrometry 55
References 57
v
vi Contents
2.5 Absolute Partial Cross-Sections of Neon
59
2.5.1 ValenceShell Photoionization 59
2.5.2 Photoionization intheVicinityoftheK-Shell 65
References 68
2.6 Absolute Partial Cross-Sections of Sodium
70
2.6.1 Introduction 70
2.6.2 PhotoelectronSpectroscopy 70
2.6.3 Photoionization MassSpectrometry 72
2.6.4 K-ShellIonization 74
References 75
2.7 Absolute Partial Cross-Sections of Atomic
Chlorine
77
2.7.1 PhotoelectronSpectroscopy 77
2.7.2 Photoionization MassSpectrometry 80
References 81
2.8 Absolute Partial Cross-Sections of Argon
83
2.8.1 OuterValenceRegion(15.76e29.24eV) 83
2.8.2 InnerValenceRegiontoL-EdgeApproach
(29.24e235eV) 85
2.8.3 PassingthroughtheL-Edge(w240e1300 eV) 88
2.8.4 TheK-Edge Region(w3190e3500eV) 95
2.8.5 MechanismsofFormationofArnþ 97
References 102
3. Diatomic Molecules
107
3.1 Absolute Partial Cross-Sections of H
2 107
3.1.1 Ion-PairFormation 107
3.1.2 VibrationalIntensities 107
3.1.3 VibrationalAutoionization 111
3.1.4 DissociativeIonization,ElectronicallyExcited
States 111
3.1.5 DoublePhotoionization 117
References 118
3.2 Absolute Partial Cross-Sections of N
2 120
3.2.1 OuterValenceRegion 120
3.2.2 InnerValenceRegion 124
3.2.3 PartialCross-SectionsNear theK-Edge 131
References 141
3.3 Absolute Partial Cross-Sections of Molecular
Oxygen
144
3.3.1 OuterValenceRegion 144
3.3.2 InnerValenceRegion 151
3.3.3 PartialCross-SectionsNear theK-Edge 160
References 166
Contents vii
3.4 Absolute Partial Cross-Sections of Carbon
Monoxide
169
3.4.1 Outer Valence Region 169
3.4.2 InnerValenceRegion 174
3.4.3 PartialCross-SectionsNear theCarbonK-Edge 181
3.4.4 PartialCross-SectionsNear theOxygenK-Edge 190
References 195
3.5 Absolute Partial Cross-Sections of NO
198
3.5.1 Introduction 198
3.5.2 ValenceShell AbsolutePartialCross-Sections 198
3.5.3 ValenceShell 204
3.5.4 Approaching theNK-EdgeofNO 209
3.5.5 Approaching theO K-Edge ofNO 213
References 215
3.6 Absolute Partial Cross-Sections of HCl
218
3.6.1 Introduction 218
3.6.2 PartialCross-Sectionsfor theOuter-and
Inner-ValenceOrbitals 219
3.6.3 PhotoionizationMassSpectrometry:Absolute
PartialCross-SectionsofIons,Outer-and
Inner-ValenceRegion 222
3.6.4 PartialCross-SectionsforCoreExcitations
andDecay 225
3.6.5 PhotoionizationMassSpectrometry:Absolute
PartialCross-SectionsofIons,CoreRegion 230
References 236
4. Triatomic Molecules
239
4.1 Absolute Partial Cross-Sections of H O
2 239
4.1.1 Introduction 239
4.1.2 Absolute PartialCross-Sections,Outer andInner
ValenceOrbitals 239
4.1.3 PhotoionizationMassSpectrometry:Absolute
PartialCross-SectionsofIons,Outer andInner
ValenceRegion 242
4.1.4 Absolute PartialCross-SectionsNear the
O K-EdgeofH2O 247
References 254
4.2 Absolute Partial Cross-Sections of CO
2 257
4.2.1 Introduction 257
4.2.2 Absolute PartialCross-Sections,Valence
Shells 258
4.2.3 PhotoionizationMassSpectrometry:Absolute
PartialCross-SectionsofIons,Outer
andInnerValence Regions 261
viii Contents
4.2.4 TheCoreExcitationandIonization 266
References 276
4.3 Absolute Partial Cross-Sections of N O
2 278
4.3.1 Introduction 278
4.3.2 AbsolutePartialCross-Sections, Valence
Shells 279
4.3.3 Photoionization MassSpectrometry:Absolute
PartialCross-SectionsofIons, Outer
andInnerValenceRegions 284
4.3.4 TheCoreExcitationandIonization 291
References 300
4.4 Absolute Partial Cross-Sections of NO
2 302
4.4.1 Introduction 302
4.4.2 AbsolutePartialCross-Sections 303
4.4.3 Photoionization MassSpectrometry:Absolute
PartialCross-SectionsofIons, Outer
andInnerValenceRegions 307
4.4.4 CoreExcitationandIonization 318
References 321
4.5 Absolute Partial Cross-Sections of H S
2 323
4.5.1 Introduction 323
4.5.2 AbsoluteCross-Sections,OuterandInner
ValenceOrbitals 323
4.5.3 Photoionization MassSpectrometry:Absolute
PartialCross-SectionsofIons, ValenceRegion 327
4.5.4 AbsolutePartialCross-Sections forCore
ExcitationandDecay 333
References 343
4.6 Absolute Partial Photoionization Cross-Sections
of SO
2 346
4.6.1 Introduction 346
4.6.2 AbsolutePartialCross-Sections ofValence
IonizationBands 349
4.6.3 Photoionization MassSpectrometry:Absolute
PartialCross-SectionsofIons, ValenceRegion 350
4.6.4 AbsolutePartialCross-Sections forCore
ExcitationandDecay 356
References 369
4.7 Absolute Partial Photoionization Cross-Sections
of Ozone
372
4.7.1 Introduction 372
4.7.2 AbsoluteCross-Sections,OuterandInner
ValenceOrbitals 373
4.7.3 Photoionization MassSpectrometry:Absolute
PartialCross-SectionsofIons, ValenceRegion 379
4.7.4 Conclusions(ValenceShellIonization) 383
Contents ix
4.7.5 TheK-EdgeRegion 383
References 388
5. Polyatomic Molecules
391
5.1 Absolute Partial Cross-Sections of NH
3 391
5.1.1 Introduction 391
5.1.2 Absolute PartialCross-Sectionsofthe Outer
andInnerValence Shells 392
5.1.3 PhotoionizationMassSpectrometry:Absolute
PartialCross-SectionsofIons,ValenceRegion 395
5.1.4 PartialCross-SectionsforCoreExcitation
andDecay 400
References 406
5.2 Absolute Partial Cross-Sections of CH
4 408
5.2.1 Introduction 408
5.2.2 Absolute Cross-Sections,OuterandInner
ValenceShells 410
5.2.3 Absolute IonCross-Sections,OuterandInner
ValenceShells 412
5.2.4 PartialCross-SectionsforCoreExcitation
andDecay 414
References 420
5.3 Absolute Partial Cross-Sections of Acetylene
(C H )
2 2 423
5.3.1 Introduction 423
5.3.2 Absolute Cross-Sections,OuterandInner
ValenceShells 424
5.3.3 Absolute IonCross-Sections,OuterandInner
ValenceShells 426
5.3.4 PartialCross-SectionsforCoreExcitation
andDecay 435
References 439
5.4 Absolute Partial Cross-Sections of Ethylene
(C H )
2 4 442
5.4.1 Introduction 442
5.4.2 Absolute Cross-Sections,OuterandInner
ValenceShells 443
5.4.3 Absolute IonCross-Sections,OuterandInner
ValenceShells 445
5.4.4 PartialCross-SectionsforCoreExcitation
andDecay 452
References 456
5.5 Absolute Partial Cross-Sections of Ethane
(C H )
2 6 459
5.5.1 Introduction 459