Spectroscopic Methods in Mineralogy and Geology PDF
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REVIEWS IN MINERALOGY VOLUME 18 SPECTROSCOPIC METHODS IN MINERALOGY ANDGEOLOGY Frank C. Hawthorne EDITOR: AUTHORS: GORDON E. BROWN, Jr.t,2 FRANK C. HAWTHORNE Department ofEarthSciences MICHAEL F. HOCHELLA, Jr.1,2 University of Manitoba JONATHAN F. STEBBINS 1 Winnepeg, Manitoba R3T 2N2 Canada GLENN A. WAYCHUNAS 2 ANTHONY C. HESS 1. Department of Geology PAUL F. McMILLAN 2. Center for Materials Research Department ofChemistry Stanford University Arizona State University Stanford, California 94305 Tempe, Arizona 85287 GEORGES CALAS ANNE M. HOFMEISTER JACQUELINE PETIAU Geophysical Laboratory Laboratoire de Mineralogic- Cristal- 2801 Upton StreetN.W. lographie, C.N.R.S. A.U. 09 Washington, D.C. 20009 Universites Paris 6et 7 R.JAMES KIRKPATRICK Tour 16, 4, place Jussieu Department of Geology 75252 Paris Cedex 05, France Inversity of Illinois SUBRATA GHOSE Urbana, lllinois 61801 Mineral Physics Group GEORGE R. ROSSMAN Department ofGeological Sciences Division of Geological &Planetary Sci. University of Washington California Institute ofTechnology Seattle, Washington 98195 Pasadena, California 91125 SERIES EDITOR: Paul H. Ribbe Department of Geological Sciences Virginia Polytechnic Institute &State University Blacksburg, Virginia 24061 ii COPYRIGHT 1988 MINERALOGICAL SOCIETY of AMERICA Printed byBookCrafters, Inc., Chelsea, Michigan REVIEWS in MINERALOGY (Formerly: SHORT COURSE NOTES) ISSN 0275-0279 Volume 18: Spectroscopic Methods in Mineralogy and Geology ISBN 0-939950-22-7 ADDITIONAL COPIES ofthisvolume aswellasthose listed below may beobtained from theMINERALOGICAL SOCIETY ofAMERICA, 1625 IStreet, N.W., Suite 414, Washington, D.C. 20006 U.S.A. Reviews inMineralogy ·Volume 9B: Amphiboles: Petrology and Experimental Phase ·VolumeSixc1h:aSputelfrisdeonMtihneerasltorugcyt.ures197o4f;suPlf.idHes.Raibnbde,sulEfods.al2ts8;4pthpe. RboelleastioT(nohscr,ecuerre1cn9hc8ae2ps;terDsa.ndRon.thVepeohbrayles);neigrenalenaodtiuosnPs.amHo.pfhRimbiboeblteaesm,;orEpedhxsipc.eri3m9ae0mnptaphlpi-. crystal chemistry andchemical bonding ofsulfides, synthesis, phase studies. ISBN# 0-939950-11~1. equilibria, andpetrology. I$BN# 0-939950-01-4. ·Volume 2:Feldspar Mineralogy. 2ndEdition, 1983; P.H.Ribbe, ·Volume 10:Characterization ofMetamorphism through Mineral Ed.362pp. Thirteen chapters onfeldspar chemistry, struc- Equilibria, 1982; J.M.Ferry, Ed.397pp. Ninechapters on ture andnomenclature; AI,Si order/disorder inrelation todomain analgebraic approach toCOmposition and reaction spaces and textures, diffraction patterns, lattice parameters andoptical prop. theirmanipulation; theGibbs' formulation ofphaseequilibria; geo- erties; determinative methods; scbsondus phase relations, micro- logicthermobarometry; buffering, infiltration, isotope fractionation, structures, kinetics andmechanisms ofexsolution, anddiffusion; compositional zoning and inclusions; characterization of meta- color and interference colors; chemical properties; deformation. morphic fluids. ISBN# 0-939950-12~X. ISBN# O~939950~14~6. ·Volume 11: Carbonates: Mineralogy and Chemistry, 1983; t:l. 'volume 3:Oxide Minerals, 1976;D.Rumble III,Ed.502pp. J.Reeder, Ed.394pp. Ninechapters oncrystal chemistry, Eight chapters on experimental studies. crystal chemistry, and polymorphism, microstructures andphase relations oftherhom- structures ofoxide minerals; oxide minerals inmetamorphic and bohedral and orthorhombic carbonates; the kinetics of CaC03 igneous terrestrial rocks, lunar rocks, andmeteorites. ISBN# 0- dissolution andprecipitation; trace elements andisotopes insec- 939950-03-0. imentary carbonates; theoccurrence. sol,ubllity andsolid solution 'Volume 4:Mineralogy and Geology o' Natural Zeolites, 1977; behavior ofMg-calcites; geologic thermobarometry using meta- F. A. Mumplon, Ed. 232 pp. Ten chapters onthe crystal morphlc carbonates. ISBN# 0~939950-15-4. chemistry and structure of natural zeolites, their occurrence in ·Volume 12:Fluid InclUSions, 1984; byE.Roedder. 644pp. sedimentary andlow-grade metamorphic rocks andclosed hydro- Nineteen chapters providing anintroduction tostudies ofalltypes logic systems, their commercial properties andutilization. ISBN# offluid inclusions, gas, liquid ormelt, trapped inmaterials from O~939950~04~9. theearth andspace, andtheir application totheunderstanding of "Volume 5:Orthosilicates, 2nd Edition, 1982; P.H.Rlbbe, Ed. geological processes. ISBN# 0-939950~16-2, 4te5r0s popn.silicateliegbaarun'ests,"Collaivsinsiefisc,atiosnpinelsofaSnidlicahteusm"itesp;luszir1c2onchaanpd- ·Volume 13:Micas, 1984; S.W.Bailey, Ed.584pp. Thirteen ttthhhoeesilaiacclautitmneisdin.eumoInrtdhseoilxisceialdict.easte,IsS;BtoNp#atizta,nOit~ea9n3d9(s9ps5hc0eo~nre1es3),-8.ocfhlomriitsocide,llanestoauusroliteo.r- cttirhcoaalolpgteyprrsopoefortmnieiscs,atrsu.cotcuIcSreuBsrNr,e#nccer0sy,-s9t3a9lp9a5cr0ah-ge1em7n-ise0ts.riys,, sgpeeocctrhoesmcoisptircy aannddoppe-- ·Volume 6:Marine Minerals, 1979; R.G.Bums, Ed.380pp. ·Volume 14:Microscopic toMacroscopic: Atomic Environments Ten chapters on manganese and iron oxides, the silica poIy~ to Mineral Thermodynamics, 1985; S.W. Kieffer and A.Na- morphs, zeolites, clayminerals, marine phosphorites, barites and vrotsky, Eds. 428 pp. Eleven chapters attempt toanswer placer minerals; evaporite mineralogy and chemistry. ISBN# the question, "What minerals exist under given constraints of 0-939950-06-5. pressure, temperature, and composition, and why?" Includes ·Vchoalupmteers7:oPnyrpoyxreonxeesn,e 1c9r8y0s;talC.cTh.ePmrieswtriytt., Esdp.ec5tr2o5scpopp.y, phNaisnee w18o~rk9e.d examples attheendofsomechapters. ISBN# 0-939950- equilibria, subsolidus phenomena and thermodynamics; compo- "Volume 15:Mathematical Crystallography, 1985;byM.B.Bois- sition and mineralogy ofterrestrial, lunar. and meteoritic pyrex- en,Jr.andG.V.Gibbs. 406pp. Amatrix andgrouptheoretic enes. ISBN# O~939950~07-3. treatment ofthepoint groups, Bravais lattices, andspace groups 'volume 8:Kinetics of Geochemical Processes, 1981; A. C. presented with numerous examples andproblem sets, including Lassga and R.J.Kirkpatrick, Eds. 398pp. Eight chapters solutions tocommon crystallographic problems involving thege- ontransition state theory andtheratelawsofchemical reactions; ometry and symmetry ofcrystal structures. ISBN# 0-939950- kinetics ofweathering, diagenesis, igneous crystallization andge0- 19-7. chemical cycles; diffusion inelectrolytes; irreversible thermody- ·Volume 16: Stable Isotopes inHigh Temperature Geological namics. ISBN# 0~939950~08-1. Processes, 1986;J.W.Valley, H.P.Taylor, Jr.,andJ.R.O'Neil, ·Volume 9A: Amphiboles and Other Hydrous Pyriboles-Min- Eds. 570 pp. Starting with thetheoretical, kinetic andex- eralogy, 1981; O.R.Veblen, Ed.372pp. Seven chapters perimental aspects ofisotopic fractionation, 14chapters dealwith onbiopyribole mineralogy and polysomatism; thecrystal chem- stable isotopes intheearly solarsystem, inthemantle, andinthe istry, structures andspectroscopy ofamphiboles; subsolidus re- igneous and metamorphic rocks andore deposits, aswell asin lations; amphibole andserpentine asbestos-mineralogy, occur- magmatic volatiles, natural water, seawater, andinmeteoric-hy- rences, andhealth hazards. ISBN# 0-939950-10-3. drothermal systems. ISBN #0-939950-20-0. ·Volume 17:Thermodynamic Modelling o'Geological Materials: Minerals, Fluids, Mett., 1987; H.P.Eugster and I.S.E_Car- michael, Ed•. 500 pp. Thermodynamic analysis ofphase equilibria insimple and multi-component mineral systems, and thermodynamic models ofcrystalline solutions, igneous gases and fluid,orefluid, metamorphic fluids, andsilicate melts, arethesub- [ects ofthis 14-chapter volume. ISBN # 0-939950-21~9. iii SPECTROSCOPIC METHODS in Mineralogy and Geology PREFACE and ACKNOWLEDGMENTS Both mineralogy and geology began asmacroscopic observational sciences. Toward the end of the 19th century, theoretical crystallography began to examine the microscopic consequences oftranslational symmetry, and with the advent of crystal structure analysis at the beginning ofthis century, the atomic (crystal) structure ofminerals became accessible to us. Almost immediately, the results were used toexplain atthe qualitative level many ofthe macroscopic physical properties ofminerals. However, itwas soon realized that the (static) arrangement of atoms in a mineral is only one aspect of its constitution. Also of significance are itsvibrational characteristics, electronic structure and magnetic properties, factors that play an even more important role when we come toconsider the behavior ofthe minerals in dynamic processes. It was as probes of these types of properties that spectroscopy began to playa significant role inmineralogy. During the 1960's, a major effort in mineralogy involved the characterization of cation ordering in minerals, and this work began to have an impact in petrology via the thermodynamic modeling of inter- and intra-crystalline exchange. This period saw great expansion in the use of vibrational, optical and Mossbauer spectroscopies for such work. This trend continued into the 1970s, with increasing realization that adequate characterization of the structural chemistry of a mineral often requires several complementary spectroscopic and diffraction techniques. The last decade has seen the greatest expansion intheuse ofspectroscopy inthe Earth Sciences. There has been a spate of new techniques (Magic Angle Spinning Nuclear Magnetic Resonance, Extended X-ray Absorption Fine-Structure and other synchrotron- related techniques) and application of other more established methods (inelastic neutron scattering, Auger spectroscopy, photoelectron spectroscopy). Furthermore, scientific attention has been focused more onprocesses than oncrystalline minerals, and the materials of interest have expanded to include glasses, silicate melts, gels, poorly-crystalline and amorphous phases, hydrothermal solutions and aqueous fluids. In addition, many of the important intereactions occur atsurfaces ornear surfaces, and consequently itisnotjust the properties and behavior ofthe bulk materials that arerelevant. This is an exciting time to be doing Earth Sciences, particularly as the expansion in spectroscopic techniques and applications is enabling us to look at geochemical and geophysical processes in a much more fundamental way than was previously possible. However, the plethora oftechniques isvery forbidding tothe neophyte, whether agraduate student or an experienced scientist from another field. There are an enormous number of texts in the field of spectroscopy. However, very few have a slant towards geological materials, and virtually none stress the integrated multi-technique approach that isnecessary for use in geochemical and geophysical problems. Ihope that this volume will fill this gap and provide ageneral introduction tothe use ofspectroscopic techniques in Earth Sciences. Ithank all of the authors for trying tomeet most ofthe deadlines associated with the production ofthis volume. It ismy opinion that the primary function ofthis volume (and its associated Short Course) is instructive. With this in mind, Ialso thank each ofthe authors for the additional effort necessary to write a(relatively) brief but clear introduction to avery complex subject, and for good-humoredly accepting my requests to include more explanation and shorten their manuscripts. We are all indebted to Paul Ribbe, series editor of Reviews in Mineralogy, and his assistants Marianne Stem and Margie Sentelle, for putting together this volume, despite our tardiness in supplying them with the necessary copy. Iwould like tothank Barbara Minich, without whom we would have had avolume but no Short Course. Lastly, I would like to thank the CNR Centro di Studio per la Cristallografia Strutturale and the Istituto di Mineralogia, both at the Universita di Pavia. Italy, for help and support during the preparation ofthis volume. Frank C. Hawthome Pavia, Italy February 29,1988 iv REVIEWS in MINERALOGY, Volume 18 FOREWORD The authors of this volume presented a short course, entitled "Spectroscopic Methods in Mineralogy and Geology", May 13-15, 1988, in Hunt Valley, Maryland. The course was sandwiched between thefirst V.M. Goldschmidt Conference, organized bythe Geochemical Society and held at Hunt Valley, and the spring meeting of the American Geophysical Union, held in Baltimore. This was the sixteenth short course organized by theMineralogical Society ofAmerica, and thisvolume isthenineteenth book published in theReviews ofMineralogy series [see list of available titles onthe opposite page -- all are currently available atmoderate costfrom MSA]. The fourteen chapters of this volume were assembled from author-prepared copy. Mrs. Marianne Stern was responsible for most of the paste-up, and Mrs. Margie Sentelle assisted with typing andformatting. Paul H. Ribbe Series Editor Blacksburg, VA TABLE OF CONTENTS Page 11 COPYRIGHT; ADDITIONAL COPIES iii PREFACE AND ACKNOWLEDGMENTS iv FOREWORD Chapter 1 G. Calas and F. C. Hawthorne INTRODUCTION TO SPECTROSCOPIC METHODS 1 RADIATION 1 Electromagnetic radiation 2 Particle beams 2 UNITS 4 INTERACTION OF RADIATION AND MATTER 4 A BRIEF SURVEY OF SPECTROSCOPIC METHODS 5 Atomic resonance spectroscopy 5 Vibrational spectroscopy 5 Energy loss spectroscopy 5 Electronic resonances followed byrelaxation processes 8 Magnetic resonance 8 TIMES CALES 9 REFERENCES Chapter 2 P. F. McMillan and A. C. Hess SYMMETRY, GROUP THEORY AND QUANTUM MECHANICS 11 QUANTUM MECHANICS v 11 Introduction 15 The particle inabox 17 The hydrogen atom 22 The simple harmonic oscillator 24 Spectroscopic transitions 25 Infrared absorption 26 Absorption duetoelectronic transitions: UV/visible spectroscopy 28 Magnetic resonance 29 Raman scattering 31 Summary 31 SYMMETRY ANDGROUP THEORY 31 Introduction 32 Symmetry elements andoperations 32 Identity element Properrotationaxis 34 Mirrorplane Improper rotationaxis Inversion center 34 Sets of symmetry operations 34 Groups 37 Combination of symmetry operations: multiplication tables 38 Matrix representations ofsymmetry operations en 38 Proper rotations 40 Improper rotation axisSn Reflection inamirrorplane (J 40 Identity operation Inversion centeri 40 Matrix representation of symmetry point groups 41 Irreducible representations 42 Reduction ofmatrix representations 45 Similarity transformations 46 Doubly- andtriply-degenerate representations 47 Point group character tables 49 Reduction of agroup representation 50 Example: thevibrational modesofwater 52 Orthogonality 53 Orthogonality properties ofmatrixcharacters 54 An alternative method forreduction ofgrouprepresentations 55 Example: thevibrational modes ofmethane 56 Infrared and Raman activevibrations ofcrystals 59 Selection rules ofelectronic transitions 60 REFERENCES Chapter 3 F. C. Hawthorne and G. A. Waychunas SPECTRUM-FITTING METHODS 63 INTRODUCTION 63 GENERAL PHILOSOPHY 64 SETTING UPTHEMODEL 64 Datareduction 64 Background modeling 64 Linear interpolation Non-linear interpolation 65 Modeling theband shape 67 CRITERION OF"BEST FIT" 67 Least-squares method 70 MINIMIZATION METHODS 70 Pattern search 72 Simplex method 72 Gradient method vi 73 Analytical solution methods 73 Linearfunctions 75 Linearization ofnon-linearfunctions 76 SOME ASPECTS OF SPECTRUM REFINEMENT 76 Tactics 77 Correlation and constraints 78 False minima andmodel testing inleast-squares fitting 79 Signal-to-noise effects infitting 79 Variations onX?goodness-of-fit parameter 81 Variations in spectral lineshape 81 Excited-state lifetime Doppler andcollisioneffects 81 Saturation effects Relaxation effects 86 Distribution ofphysical states 86 Spectrometer resolution Spectrometeraberrations 86 Fourier processing ofspectral data 87 Fourier transforms andintegrals 87 Properties of Fourier transforms 87 Similarity theorem 90 Addition theorem Shifttheorem 90 Convolution theorem Autocorrelation theorem 90 Rayleigh's theorem Convolution-deconvolution 91 Fourier filtering 91 Correlation functions 94 Fourier "ripples" --limitations offinite data sets 94 Maximum entropy methods 95 REFERENCES 96 ApPENDIX A: SOME STATISTICAL DEFINITIONS Chapter 4 P. F. McMillan and A. M. Hofmeister INFRARED AND RAMAN SPECTROSCOPY 99 INTRODUCTION 100 VIBRATIONAL THEORY OF MOLECULES AND CRYSTALS 100 Classical models 100 Quantum mechanical models 101 Interaction with light: infrared andRaman spectroscopy 103 Crystal latticevibrations 105 INSTRUMENTATION FOR INFRARED AND RAMAN EXPERIMENTS 106 Infrared sources 106 Raman sources --lasers 107 Spectrometers andinterferometers 110 Infrared detectors 112 Raman detectors 113 Infrared windows, cellmaterial anddispersing media 113 Infrared beam splitters andpolarizers 114 Instrument calibration 115 EXPERIMENTAL INFRARED AND RAMAN SPECTROSCOPY 115 Samplepreparation andmeasurement techniques 116 Infrared absorption spectroscopy of minerals 116 Infrared reflection spectroscopy 120 Infrared powder transmission spectra 121 Far-infrared spectroscopy 122 Polarized infrared andRaman spectroscopy 123 Micro-Raman spectroscopy vii 124 Micro-infrared techniques 124 Fourier transform Raman spectroscopy 125 Resonance Raman spectroscopy 125 Hyper-Raman scattering 126 Stimulated Raman, inverse Raman and CARS 127 Spectroscopy athigh pressures andtemperatures 127 VIBRATIONALSPECTRAOFMINERALS 127 Simple structures: diamond, graphite androck salt 129 Fluorite andrutile structures 132 Corundum andilmenite 134 Perovskites 136 Spinel 139 Olivines, garnets andA12SiOSpolymorphs 140 Chain andring silicates 143 Amphiboles andmicas 144 Silica polymorphs 145 Feldspars, cordierite and other framework aluminosilicates 146 Carbonate minerals 148 SUMMARY 148 BIBLIOGRAPHY 148 General introduction tovibrational theory and spectroscopy 149 Vibrations ofmolecules and crystals 149 Symmetry andgroup theory useful forvibrational spectroscopy 149 Infrared and Raman spectroscopy 149 Compilations and series 150 REFERENCES Chapter 5 Subrata Ghose INELASTIC NEUTRON SCATTERING 161 INTRODUCTION 161 Basic properties oftheneutron 162 Neutron scattering cross-section 162 Neutron sources 163 Applications ofinelastic neutron scattering 165 LATTICEDYNAMICSANDNEUTRONSCATTERING 165 Basic concepts oflattice dynamics 167 Analysis forthephonon dispersion curves: Phenomenological models 169 Phonon dispersion relations: Theory ofinelastic neutron scattering 169 Coherentonephonon inelasticscattering 169 Anharmonic effects 171 Coherent inelastic neutron spectroscopy 171 Triple-axisspectrometer 173 Experimental results: Phonon dispersion relations inforsterite, Mg2Si04 178 Phonon density of states 178 Neutron intensity distributionfrom apowder sample: Coherent scattering-incoherent approximation 178 Inelastic neutronscattering spectrometer withapulsed sourcefor the measurement ofthephonon density ofstates 180 Phonon density ofstates of'forsterite 180 Incoherent inelastic neutron scattering 180 Incoherent inelastic neutronscatteringspectrafrom zeolites containingorganicradicalsandwatermolecules 183 INELASTICMAGNETICSCATTERING 183 Magnetically dilute (uncoupled) systems viii 183 Magnetically coupled systems 185 Ferromagnets Antiferromagnets andferrimagnets 187 QUASI-ELASTIC NEUTRON SCATTERING 187 Diffusive motion of water molecules inclay minerals and zeolites 188 CONCLUSIONS 190 ACKNOWLEDGMENTS 190 SUGGESTEDREADING 191 REFERENCES Chapter 6 George R. Rossman VIBRATIONAL SPECTROSCOPY OF HYDROUS COMPONENTS 193 INTRODUCTION 193 GENERAL CONCEPTS 193 THE EXPERIMENT 195 INTENSITIES 195 SPECIFICApPLICATIONS 196 Amphiboles 196 Micas 198 HYDROUS SPECIESINNOMINALLY ANHYDROUS MINERALS 198 Beryl Cordierite 200 Feldspar Garnet 201 Natural glasses 201 Olivine Silica 203 Other minerals 204 SUMMARY 204 REFERENCES Chapter 7 George R. Rossman OPTICAL SPECTROSCOPY 207 INTRODUCTION 207 RESOURCES 207 GENERAL CONCEPTS 209 UNITS 212 THE EXPERIMENT 213 INTENSITIESANDSELECTION RULES 214 Laporte selection rule 214 Spin-forbidden transitions 214 The rules can be bent when ions get together 217 Beer's Law plots 217 IDENTIFICATIONOFTHEOXIDATION STATES OFCATIONS 217 Titanium 218 Vanadium Chromium Manganese Iron 223 Cobalt Nickel Copper 223 GUIDE TOMINERAL OPTICAL SPECTRALDATA 233 REFERENCES 244 ApPENDIX: DETAILED EXAMPLE, Fe2+ at the M(2) SITE in ORTHOPYROXENE 244 The symmetry of the cation polyhedra in orthopyroxenes 253 A final comment 254 References -Appendix ix Chapter 8 Frank C. Hawthorne MbsSBAUER SPECTROSCOPY 255 INTRODUCTION 255 RADIOACTIVEDECAY 256 Nuclear spin 256 EMISSION, ABSORPTION ANDMOMENTUM TRANSFER 259 Second-order Doppler shift 260 Resonant Mossbauer absorption 262 Which isotopes areuseful? 262 Selection rules 263 Line shape 264 Line width 265 MbsSBAUER PARAMETERS 265 Chemical (isomer) shift 267 Quadrupole splitting 270 Magnetic splitting 273 Goldanskii-Karyagin effect 275 Combined hyperfine interactions 275 Electricmonopole andquadrupoleinteractions 276 Electricmonopole andmagneticdipoleinteractions 276 Electricquadrupoleandmagneticdipoleinteractions 276 INSTRUMENTATION 276 Drive mechanism 278 eosine smearing 278 Detectors 280 Heaters and Cryostats 280 Absorber preparation 281 Calibration 281 Spectrum quality 283 SPECTRUM REFINEMENT 283 Mathematical description ofthespectrum 284 Least-squares refinement 285 Use ofconstraints 286 Goodness-of-fit criteria 288 Standard deviations and error-of-propagation analysis 289 The correct answer 290 INTERPRETATION OFISOMERSHIFT 290 Oxidation state 291 Ligancy 291 Coordination number 291 Partial isomer shifts 295 INTERPRETATIONOFQUADRUPOLE SPLITTING 296 Oxidation state 298 Lone pair electrons 298 Coordination andpartial quadrupole splittings 300 DETERMINATION OFOXIDATION STATES 300 119Sn 121Sb 57Fe 301 151Eu 301 DETERMINATION OFSITE-OCCUPANCIES 303 SITE-OCCUPANCIES INMINERALS 303 Garnets 306 Olivines x 306 Pyroxenes 307 Orthopyroxenes 309 Clinopyroxenes 309 Generalconsiderations 309 Applications 310 Amphiboles 310 Fe-Mg-Mn amphiboles Calcicamphiboles 311 Alkaliamphiboles Generalconsiderations 311 Applications 312 Micas 312 Dioctahedralmicas Trioctahedralmicas 314 Applications 314 NEXT-NEAREST-NEIGHBOR EFFECTS 314 Wi.istite 316 Spinels and thiospinels 316 Pyroxenes 317 Other minerals 317 INTERV ALENCE CHARGE-TRANSFER IN MINERALS 320 EU3S4 320 Minerals withfiniteFe-containing octahedral clusters 320 Minerals withchains ofFeoctahedra 320 Deerite 321 Ilvaite 321 Summary 321 Some general considerations 321 'MAGNETIC PROPERTIES OF MINERALS 323 Origin ofmagnetism 323 Magnetic properties ofsolids 323 Diamagnetism Paramagnetism 324 Ferromagnetism Antiferromagnetism 324 Ferrimagnetism 325 Mossbauer spectroscopy andmagnetic structure 326 Applications tominerals 326 Garnets Fayalite Chainsilicates 327 Summary 327 OXIDATION STUDIES 327 Trioctahedral micas 329 197Au MbsSBAUER SPECTROSCOPY 329 CONVERSION ELECTRON MbsSBAUER SPECTROSCOPY 329 Basic principles 331 Instrumentation 331 Application tominerals 332 SUMMARY 333 ACKNOWLEDGMENTS 333 REFERENCES Chapter 9 R. James Kirkpatrick MAS NMR SPECTROSCOPY OF MINERALS AND GLASSES 341 INTRODUCTION 341 THEORY 342 Quantum mechanical description 344 Classical description
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