THE PRINCIPLES OF CHEMISTRY
CONTENTS INTRODUCTION REFERENCES BASIC PHYSICAL CONCEPTS 2 1 NUCLEAR G-RESONANCE 2 2 NATURAL LINE WIDTH AND SPECTRAL LINE SHAPE 2 3 RECOIL ENERGY LOSS IN FREE ATOMS AND THERMAL BROADENING OF TRANSITION LINES 2 4 RECOIL-FREE EMISSION AND ABSORPTION 2 5 THE M€OSSBAUER EXPERIMENT 2 6 THE M€OSSBAUER TRANSMISSION SPECTRUM 2 6 1 THE LINE SHAPE FOR THIN ABSORBERS 2 6 2 SATURATION FOR THICK ABSORBERS EXPERIMENTAL 3 1 THE M€OSSBAUER SPECTROMETER 3 1 1 THE M€OSSBAUER DRIVE SYSTEM 3 1 2 RECORDING THE M€OSSBAUER SPECTRUM 3 1 3 VELOCITY CALIBRATION 3 1 4 THE M€OSSBAUER LIGHT SOURCE 3 1 5 PULSE HEIGHT ANALYSIS: DISCRIMINATION OF PHOTONS 3 1 6 M€OSSBAUER DETECTORS 3 1 7 ACCESSORY CRYOSTATS AND MAGNETS 3 1 8 GEOMETRY EFFECTS AND SOURCE–ABSORBER DISTANCE 3 2 PREPARATION OF M€OSSBAUER SOURCES AND ABSORBERS 3 2 1 SAMPLE PREPARATION 3 2 2 ABSORBER OPTIMIZATION: MASS ABSORPTION AND THICKNESS 3 2 3 ABSORBER TEMPERATURE 3 3 THE MINIATURIZED SPECTROMETER MIMOS II 3 3 1 INTRODUCTION 3 3 2 DESIGN OVERVIEW 3 3 3 BACKSCATTER MEASUREMENT GEOMETRY 3 3 4 TEMPERATURE DEPENDENCE AND SAMPLING DEPTH 3 3 5 DATA STRUCTURE, TEMPERATURE LOG, AND BACKUP STRATEGY 3 3 6 VELOCITY AND ENERGY CALIBRATION 3 3 7 THE ADVANCED INSTRUMENT MIMOS IIA HYPER?NE INTERACTIONS 4 1 INTRODUCTION TO ELECTRIC HYPER?NE INTERACTIONS 4 1 1 NUCLEAR MOMENTS 4 1 2 ELECTRIC MONOPOLE INTERACTION 4 1 3 ELECTRIC QUADRUPOLE INTERACTION 4 1 4 QUANTUM MECHANICAL FORMALISM FOR THE QUADRUPOLE INTERACTION 4 2 M€OSSBAUER ISOMER SHIFT 4 2 1 RELATIVISTIC EFFECTS 4 2 2 ISOMER SHIFT REFERENCE SCALE 4 2 3 SECOND-ORDER DOPPLER SHIFT 4 2 4 CHEMICAL INFORMATION FROM ISOMER SHIFTS 4 3 ELECTRIC QUADRUPOLE INTERACTION 4 3 1 NUCLEAR QUADRUPOLE MOMENT 4 3 2 ELECTRIC FIELD GRADIENT 4 3 3 QUADRUPOLE SPLITTING 4 3 4 INTERPRETATION AND COMPUTATION OF ELECTRIC FIELD GRADIENTS 4 4 MAGNETIC DIPOLE INTERACTION AND MAGNETIC SPLITTING 4 5 COMBINED ELECTRIC AND MAGNETIC HYPER?NE INTERACTIONS 4 5 1 PERTURBATION TREATMENT 4 5 2 HIGH-FIELD CONDITION: GNMNB EQVZZ/2 4 5 3 LOW-FIELD CONDITION: EQVZZ/2 GNMNB 4 5 4 EFFECTIVE NUCLEAR G-FACTORS FOR EQVZZ/2 GNMNB 4 5 5 REMARKS ON LOW-FIELD AND HIGH-FIELD M€OSSBAUER SPECTRA 4 6 RELATIVE INTENSITIES OF RESONANCE LINES 4 6 1 TRANSITION PROBABILITIES 4 6 2 EFFECT OF CRYSTAL ANISOTROPY ON THE RELATIVE INTENSITIES OF HYPER?NE SPLITTING COMPONENTS 4 7 57FE-M€OSSBAUER SPECTROSCOPY OF PARAMAGNETIC SYSTEMS 4 7 1 THE SPIN-HAMILTONIAN CONCEPT 4 7 2 THE FORMALISM FOR ELECTRONIC SPINS 4 7 3 NUCLEAR HAMILTONIAN AND HYPER?NE COUPLING 4 7 4 COMPUTATION OF M€OSSBAUER SPECTRA IN SLOW AND FAST RELAXATION LIMIT 4 7 5 SPIN COUPLING 4 7 6 INTERPRETATION, REMARKS AND RELATION WITH OTHER TECHNIQUES QUANTUM CHEMISTRY AND M€OSSBAUER SPECTROSCOPY 5 1 INTRODUCTION 5 2 ELECTRONIC STRUCTURE THEORY 5 2 1 THE MOLECULAR SCHR€ODINGER EQUATION 5 2 2 HARTREE–FOCK THEORY 5 2 3 SPIN-POLARIZATION AND TOTAL SPIN 5 2 4 ELECTRON DENSITY AND SPIN-DENSITY 5 2 5 POST-HARTREE–FOCK THEORY 5 2 6 DENSITY FUNCTIONAL THEORY 5 2 7 RELATIVISTIC EFFECTS 5 2 8 LINEAR RESPONSE AND MOLECULAR PROPERTIES 5 3 M€OSSBAUER PROPERTIES FROM DENSITY FUNCTIONAL THEORY 5 3 1 ISOMER SHIFTS 5 3 2 QUADRUPOLE SPLITTINGS 5 3 3 MAGNETIC HYPER?NE INTERACTION 5 3 4 ZERO-FIELD SPLITTING AND G-TENSORS 5 4 NUCLEAR INELASTIC SCATTERING 5 4 1 THE NIS INTENSITY 5 4 2 EXAMPLE 1: NIS STUDIES OF AN FE(III)–AZIDE (CYCLAM-ACETATO) COMPLEX 5 4 3 EXAMPLE 2: QUANTITATIVE VIBRATIONAL DYNAMICS OF IRON FERROUS NITROSYL TETRAPHENYLPORPHYRIN MAGNETIC RELAXATION PHENOMENA 6 1 INTRODUCTION 6 2 M€OSSBAUER SPECTRA OF SAMPLES WITH SLOW PARAMAGNETIC RELAXATION 6 3 M€OSSBAUER RELAXATION SPECTRA 6 4 PARAMAGNETIC RELAXATION PROCESSES 6 4 1 SPIN–LATTICE RELAXATION 6 4 2 SPIN–SPIN RELAXATION 6 5 RELAXATION IN MAGNETIC NANOPARTICLES 6 5 1 SUPERPARAMAGNETIC RELAXATION 6 5 2 COLLECTIVE MAGNETIC EXCITATIONS 6 5 3 INTERPARTICLE INTERACTIONS 6 6 TRANSVERSE RELAXATION IN CANTED SPIN STRUCTURES M€OSSBAUER-ACTIVE TRANSITION METALS OTHER THAN IRON 7 1 NICKEL (61NI) 7 1 1 SOME PRACTICAL ASPECTS 7 1 2 HYPER?NE INTERACTIONS IN 61NI 7 1 3 SELECTED 61NI M€OSSBAUER EFFECT STUDIES 7 2 ZINC (67ZN) 7 2 1 EXPERIMENTAL ASPECTS 7 2 2 SELECTED 67ZN M€OSSBAUER EFFECT STUDIES 7 3 RUTHENIUM (99RU, 101RU) 7 3 1 EXPERIMENTAL ASPECTS 7 3 2 CHEMICAL INFORMATION FROM 99RU M€OSSBAUER PARAMETERS 7 3 3 FURTHER 99RU STUDIES 7 4 HAFNIUM (176,177,178,180HF) 7 4 1 PRACTICAL ASPECTS OF HAFNIUM M€OSSBAUER SPECTROSCOPY 7 4 2 MAGNETIC DIPOLE AND ELECTRIC QUADRUPOLE INTERACTION 7 5 TANTALUM (181TA) 7 5 1 EXPERIMENTAL ASPECTS 7 5 2 ISOMER SHIFT STUDIES 7 5 3 HYPER?NE SPLITTING IN 181TA (6 2 KEV) SPECTRA 7 5 4 METHODOLOGICAL ADVANCES AND SELECTED APPLICATIONS 7 6 TUNGSTEN (180,182,183,184,186W) 7 6 1 PRACTICAL ASPECTS OF M€OSSBAUER SPECTROSCOPY WITH TUNGSTEN 7 6 2 CHEMICAL INFORMATION FROM DEBYE–WALLER FACTOR MEASUREMENTS 7 6 3 CHEMICAL INFORMATION FROM HYPER?NE INTERACTION 7 6 4 FURTHER 183W STUDIES 7 7 OSMIUM (186,188,189,190OS) 7 7 1 PRACTICAL ASPECTS OF M€OSSBAUER SPECTROSCOPY WITH OSMIUM 7 7 2 DETERMINATION OF NUCLEAR PARAMETERS OF OSMIUM M€OSSBAUER ISOTOPES 7 7 3 INORGANIC OSMIUM COMPOUNDS 7 8 IRIDIUM (191,193IR) 7 8 1 PRACTICAL ASPECTS OF 193IR M€OSSBAUER SPECTROSCOPY 7 8 2 COORDINATION COMPOUNDS OF IRIDIUM 7 8 3 INTERMETALLIC COMPOUNDS AND ALLOYS OF IRIDIUM 7 8 4 RECENT 193IR M€OSSBAUER STUDIES 7 9 PLATINUM (195PT) 7 9 1 EXPERIMENTAL ASPECTS 7 9 2 PLATINUM COMPOUNDS 7 9 3 METALLIC SYSTEMS 7 10 GOLD (197AU) 7 10 1 PRACTICAL ASPECTS 7 10 2 INORGANIC AND METAL-ORGANIC COMPOUNDS OF GOLD 7 10 3 SPECI?C APPLICATIONS 7 11 MERCURY (199,201HG) SOME SPECIAL APPLICATIONS 8 1 SPIN CROSSOVER PHENOMENA IN FE(II) COMPLEXES 8 1 1 INTRODUCTION 8 1 2 SPIN CROSSOVER IN [FE(2-PIC)3]CL2SOL 8 1 3 EFFECT OF LIGHT IRRADIATION (LIESST EFFECT) 8 1 4 SPIN CROSSOVER IN DINUCLEAR IRON(II) COMPLEXES 8 1 5 SPIN CROSSOVER IN A TRINUCLEAR IRON(II) COMPLEX 8 1 6 SPIN CROSSOVER IN METALLOMESOGENS 8 1 7 EFFECT OF NUCLEAR DECAY: M€OSSBAUER EMISSION SPECTROSCOPY 8 2 57FE M€OSSBAUER SPECTROSCOPY: UNUSUAL SPIN AND VALENCE STATES 8 2 2 IRON(II) WITH INTERMEDIATE SPIN, S ¼ 8 2 3 IRON IN THE HIGH OXIDATION STATES IV–VI 8 2 4 IRON IN LOW OXIDATION STATES 8 3 MOBILE M€OSSBAUER SPECTROSCOPY WITH MIMOS IN SPACE AND ON EARTH 8 3 1 INTRODUCTION 8 3 2 THE INSTRUMENT MIMOS II 8 3 3 EXAMPLES 8 3 4 CONCLUSIONS AND OUTLOOK NUCLEAR RESONANCE SCATTERING USING SYNCHROTRON RADIATION (M€OSSBAUER SPECTROSCOPY IN THE TIME DOMAIN) 9 1 INTRODUCTION 9 2 INSTRUMENTATION 9 3 NUCLEAR FORWARD SCATTERING (NFS) 9 3 1 QUADRUPOLE SPLITTING: THEORETICAL BACKGROUND 9 3 2 EFFECTIVE THICKNESS, LAMB–M€OSSBAUER FACTOR 9 4 NFS APPLICATIONS 9 4 1 POLYCRYSTALLINE MATERIAL VERSUS FROZEN SOLUTION (EXAMPLE: “PICKET-FENCE” PORPHYRIN AND DEOXYMYOGLOBIN) 9 4 2 TEMPERATURE-DEPENDENT QUADRUPOLE SPLITTING IN PARAMAGNETIC (S ¼ 2) IRON COMPOUNDS (EXAMPLE: DEOXYMYOGLOBIN) 9 4 3 DYNAMICALLY INDUCED TEMPERATURE-DEPENDENCE OF QUADRUPOLE SPLITTING (EXAMPLE: OXYMYOGLOBIN) 9 4 4 MOLECULAR DYNAMICS OF A SENSOR MOLECULE IN VARIOUS HOSTS (EXAMPLE: FERROCENE (FC)) 9 4 5 TEMPERATURE-DEPENDENT QUADRUPOLE SPLITTING AND LAMB–M€OSSBAUER FACTOR IN SPIN–CROSSOVER COMPOUNDS (EXAMPLE: [FEII(TPA)(NCS)2]) 9 4 6 COHERENT VERSUS INCOHERENT SUPERPOSITION OF FORWARD SCATTERED RADIATION OF HIGH-SPIN AND LOW-SPIN DOMAINS (EXAMPLE: [FEII(TPA)(NCS)2]) 9 4 7 ORIENTATION-DEPENDENT LINE-INTENSITY RATIO AND LAMB–M€OSSBAUER FACTOR IN SINGLE CRYSTALS (EXAMPLE: (CN3H6)2[FE(CN)5NO]) 9 5 ISOMER SHIFT DERIVED FROM NFS (INCLUDING A REFERENCE SCATTERER) 9 6 MAGNETIC INTERACTION VISUALIZED BY NFS 9 6 1 MAGNETIC INTERACTION IN A DIAMAGNETIC IRON COMPLEX (EXAMPLE: [FEO2(SC6HF4)(TPPIVP)]) 9 6 2 MAGNETIC HYPER?NE INTERACTION IN PARAMAGNETIC IRON COMPLEXES (EXAMPLES: [FE(CH3COO)(TPPIVP)] WITH S ¼ 2 AND [TPPFE(NH2PZH)2]CL WITH S ¼ 1/2) 9 6 3 MAGNETIC HYPER?NE INTERACTION AND SPIN–LATTICE RELAXATION IN PARAMAGNETIC IRON COMPLEXES (EXAMPLES: FERRIC LOW-SPIN (FEIII, S ¼ 1/2) AND FERROUS HIGH-SPIN (FEII, S ¼ 2)) 9 6 4 SUPERPARAMAGNETIC RELAXATION (EXAMPLE: FERRITIN) 9 6 5 HIGH-PRESSURE INVESTIGATIONS OF MAGNETIC PROPERTIES (EXAMPLES: LAVES PHASES AND IRON OXIDES) 9 7 NFS VISUALIZED BY THE NUCLEAR LIGHTHOUSE EFFECT (NLE) (EXAMPLE: IRON FOIL) 9 8 SYNCHROTRON RADIATION BASED PERTURBED ANGULAR CORRELATION, SRPAC (EXAMPLE: WHOLE-MOLECULE ROTATION OF FC) 9 9 NUCLEAR INELASTIC SCATTERING 9 9 1 PHONON CREATION AND ANNIHILATION 9 9 2 DATA ANALYSIS AND DOS (EXAMPLE: HEXACYANOFERRATE) 9 9 3 DATA ANALYSIS USING ABSORPTION PROBABILITY DENSITY (EXAMPLE: GUANIDINIUM NITROPRUSSIDE) 9 9 4 IRON–LIGAND VIBRATIONS IN SPIN-CROSSOVER COMPLEXES 9 9 5 BOSON PEAK, A SIGNATURE OF DELOCALIZED COLLECTIVE MOTIONS IN GLASSES (EXAMPLE: FC AS SENSOR MOLECULE) 9 9 6 PROTEIN DYNAMICS VISUALIZED BY NIS 9 10 NUCLEAR RESONANCE SCATTERING WITH ISOTOPES OTHER THAN 57FE