Spectroscopic Methods in Mineralogy and Geology

714 Pages·1988·388.085 MB·English

by  Frank C Hawthorne, Ed.

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
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REVIEWS in MINERALOGY
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ISSN 0275-0279
Volume 18: Spectroscopic Methods
in Mineralogy and Geology
ISBN 0-939950-22-7
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chemistry and structure of natural zeolites, their occurrence in ·Volume 12:Fluid InclUSions, 1984; byE.Roedder. 644pp.
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·Volume 6:Marine Minerals, 1979; R.G.Bums, Ed.380pp. ·Volume 14:Microscopic toMacroscopic: Atomic Environments
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equilibria, subsolidus phenomena and thermodynamics; compo- "Volume 15:Mathematical Crystallography, 1985;byM.B.Bois-
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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
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ontransition state theory andtheratelawsofchemical reactions; ometry and symmetry ofcrystal structures. ISBN# 0-939950-
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chemical cycles; diffusion inelectrolytes; irreversible thermody- ·Volume 16: Stable Isotopes inHigh Temperature Geological
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·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
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·Volume 17:Thermodynamic Modelling o'Geological Materials:
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[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