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Inorganic Materials Research Division Annual Report 1971

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LBL-425 UC-2 Genera!,Miscellaneous, and Progress Reports TID-4500 (59th Ed.) d INORGANIC MATERIALS RESEARCH DIVISION ANNUAL REPORT 1971 April 1972 -NOTICE- This report was prepared as an account of work sponsored by the United States Government. Neither the United States nor the United States Atomic Energy Commission, nor any of their employees, nor any of their contractors, subcontractors, or their employees, mBkes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, com­ pleteness or usefulness of any information, apparatus, product or process disclosed, or represents that its use would not infringe privately owned rights. Lawrence Berkeley Laboratory University of California Berkeley, California MOTflWJTW* Of THIS BOCUWtMT IS OtH-WTM Work done under U.S. Atomic Energy Commission Contract No. W-7405-eng-48 Printed in the United States of America Available from National Technical Information Service U.S. Department of Commerce 5285 Port Royal Road Springfield, Virginia 22151 Price: Printed Copy $3.00; Microfiche $0.95 -iii- INORGANIC MATERIALS RESEARCH DIVISION ANNUAL REPORT. 1971* Contents GENERAL INTRODUCTION xi I. CHEMISTRY A. Inorganic Chemistry William L. Jolly, Principal Investigator 1. X-Ray Photoelectron Spectroscopy 1 2. Studies of the Hydrides of Groups TV and V 2 3. Studies in Liquid Ammonia 5 4. Boron Hydride Chemistry 6 5. Sulfur-Nitrogen Chemistry 7 f. Research Plans for Calendar Year 1972 7 7. 1971 Publications and Reports 8 Robert E. Conniak, Prinoipal Investigator 1. Water Exchange from the First Coordination Sphere of Some Diamagnetic Ions 10 2. Oxygen-17 NMR Studies of Waters in the Second Coordination Sphere of Cr3+ ..... 10 3. Oxygen-17 NMR Study of the Rate of Water Exchange from Partially Complexed Nickel Ion 11 4. Research Plans for Calendar Year 1972 11 5. 1971 Publications and Reports 11 Neil Bartlett, Prinoipal Investigator 1. Noble Gas and Halogen Chemistry 12 2. Structural Investigations of High Valence Cations . 13 3. Research Plans for Calendar Year 1972 14 4. 1971 Publications and Reports 15 B. Solid State Chemistry and Physics Norman E. Phillips, Principal Investigator 1. Calorimetric Evidence for a Singlet Ground State in CuFe 16 2. Low Temperature Heat Capacity of Cerium 17 3. Heat Capacity of AuGd Alloys 17 4. Pressure Dependence of the Low Temperature Heat Capacity of V2O3 ...... 18 5. Temperature Measurements 18 6. Dilution Refrigerator 18 7. Low Temperature, High Pressure Calorimetry 18 8. New Adiabatic Demagnetization Cryostat and Calorimeter 19 9. Research Plans for Calendar Year 1972 19 10. 1971 Publications and Reports 19 George Jura, Prinoipal Investigator 1. Pressure (Up to 40 Kbar) as a Parameter in the Study of Vibrational Excition Levels and Crystalline Potentials of Molecular Crystals: Naphthalene and N-Paraffins ..... 23 2. Heat Capacity of Iron as a Function of Pressure and Temperature 21 3. Specific Heats and Heats of Transition of Bismuth as a Function of . Temperature and Pressure 21 4. Research Plans for Calendar Year 1972 22 5. 1971 Publications and Reports 22 Gabor A. Somorjai, Prinoipal Investigatcr 1. Low Energy Electron Diffraction Studies of Surfaces . , 24 2. Auger Electron Spectroscopy of Surfaces 26 3. Molecular Beam Scattering From Surfaces 27 4. Studies of the Vaporization Kinetics of Hydrogen Bonded Liquids 27 5. Research Plans for Calendar Year 1972 -• 28 6. 1971 Publications and Reports 28 Lee F. Donaghey, Principal Investigator 1. Czochralski Crystal Growth 30 2. Chemical Vapor Deposition 31 3. Chalcogenide Spinel 31 "JU' "Preceding Annual Reports: UCRL-19155, UCRL-20500 -iv- 4. Transport in Solids 31 5. Magnetic Susceptibility Measurements 31 6. Computer Simulation 32 7. Research Plans for Calendar Year 1972 32 8. 1971 Publications and Reports 32 C. Electrochemistry Charles W. Tobias, Principal Investigator 1. Fundamental Studies of Ionic Mass Transport 34 2. Electrolysis at High Current Densities 35 3. Electrochemistry in Nonaqueous Solvents 37 4. Research Plans for Calendar Year 1972 37 5. 1971 Publications and Reports 38 Rolf H. Muller, Principal Investigator 1. Optical Studies of Interfacial Phenomena 39 2. Research Plans for Calendar Year 1972 41 3. 1971 Publications and Reports 42 John Newman, Principal Investigator 1. Diffusion in Aqueous KOH Solutions 43 2. Heat Transfer to Turbulent Gas-Solids Suspension Flow In Pipes 43 3. Mass Transfer to a Plane Below a Rotating Disk 43 4. Diffusion of a Binary Fluid Across sin Initially Sharp Boundary; Bouyancy-Driven Hydrodynamic Instability Due to Heat of Mixing 44 5. Empirical Correlation for Turbulent Couette Flow 44 6. Corrosion of Rotating Disks 44 7. Mass Transfer Coefficient in Porous Flow-Through Electrodes 45 8. Warburg Impedance of a Rotating Jisk Electrode 45 9. Fluid Flow in a Propagating Crack 45 10. Mass Transfer to a Rotating Sphere at High Schmidt Numbers 45 11. Mass Transfer in Electrochemical Systems 45 12. Research Plans foT Calendar Year 1972 46 13. 1971 Publications and Reports 46 D. Physical Chemistry Leo Brewer, Principal Investigator 1. Energies of the Electronic Configurations of the Singly, Doubly, and Triply Ionized Lanthanides and Actinides 48 2. Radiative Lifetimes of TiO and VO 48 3. Thermodynamic Properties of Solutions of Third and Fourth Group Transition Metals with Platinum Group Metals 48 4. Photochemistry of Iodine and Ultraviolet Spectrum of I2 ... 48 5. Research Plans for Calendar Year 1972 48 6. 1971 Publications and Reports 49 Charles B. Harris, Principal Investigator 1. Introduction 50 2. The Dynamics of Coherent Exciton Migration 50 3. The Dynamics of Coherent Triplet Exciton Trapping .... 51 4. Optica.'ly Detected Magnetic Resonance and the Measurement of Intramolecular Energy Transfer Processes in Triplets 51 5. Properties of Molecules in Excited Triplet States 52 6. Research Plans for Calendar Year 1972 53 7. 1971 Publications and Reports 53 Ronald R. Herm, Principal Investigator 1. Photodissociation of Nal Vapor and the Energy Dependence of the Quenching of Na*(^p 2p) by Foreign Gases 55 2. Molecular Beam Kinetics: Reactions of Mg, Ca, and Ba with CI2, Brj, and IC1 55 3. Molecular Beam Kinetics: Reactions of Ca and Ba with HI, NO2, SOj, PCI3, SnCl4, CCI4, CH3I, CH2I2, and 2-Nitropropane ,56 4. Molecular Beam Kinetics: Magnetic Deflection and Product Velocity , Analysis of the Li + Br2 Reaction : 57 5. Research Plans for Calendar Year 1972 1 58 6. 1971 Publications and Reports '59 -v- Harold S. Johnston, Principal Investigator 1. Introduction 60 2. Catalytic Reduction of Stratospheric Ozone 60 3. Dissociation of Homonuclear Diatomic Molecules at High Temperatures .... 61 4. Molecular Modulation Spectrometry 61 5. Fluorescence of Sulfur Dioxide . 62 6. Research Plans for Calendar Year 1972 62 7. 1971 Publications and Reports 63 Bruce ,'!. Mohan, Principal Investigator 1. Molecular Orbital Correlation Diagrams and Ion-Molecule Reaction Dynamics 64 2. Determination of Intermolecular Potentials from Large Angle Elastic Scattering 64 3. Deconvolution of Molecular Beam Inelastic Scattering Data 65 4. Nonreactive Scattering in the Ne* - H2 and Ne+ - He Systems 65 5. Dynamics of the Reactions of O2 with H2, D2, and Iffl 66 6. Thermal Ion-Molecule Reactions in Gaseous Methane-Oxygen Mixtures 67 7. Research Plans for Calendar Year 1972 67 8. 1971 Publications and Reports 67 William H. Miller, Prinaival Investigator 1. The Classical S-Matrix for Rotational Excitation; Quenching of Quantum Effects in Molecular Collisions . 68 2. Collisional Quenching of Metastable Hydrogen Atoms 68 3. Molecular Ramsauer-Townsend Effect in Very Low Energy He^-He'1 Scattering 69 4. Classical Path Approximation for the Boltzmann Density Matrix 69 5. The Classical S-Matrix for Linear Reactive Collisions of H + CI2 70 6. Predissociation in the Schumann-Runge Bands of O2 71 7. Research Plans for Calendar Year 1972 71 8. 1971 Publications and Reports 73 Rollie J. Myers, Principal Investigator 1. Spin Relaxation in a-NiS04-6H2C' 74 2. Electron-Electron Double Resonance in Solutions 74 3. Measurement of Transition Metal Ion Relaxation in Solution 75 4. Research Plans for Calendar Year 1972 76 5. 1971 Publications and Reports 76 Kenneth S. Pitser, Principal Investigator 1. Research Plans for Calendar Year 1972 78 2. 1971 Publication 78 E. Nuclear Science Donald R. O'Umder, Principal Investigator 1. An Apparatus for Investigation of Gas-Solid Reactions by Modulated Molecular Beam Mass Spectronetiy 79 2. Reactions of Modulated Molecular Beams with Pyrolytic Graphite 79 3. The Rate of Oxidation of the Basal and Prismatic Surfaces of Pyrolytic Graphite in the Transition Regime Between Chemical and Diffusional Control 80 4. Theory of lie Gas Centrifuge 80 5. Laser Vaporization of Solids 81 6. The Viscosity of Molten Uranium Dioxide 81 1. Ressarch Plans for Calendar Year 1972 82 8. 1971 Publications and Reports 82 METALLURGY A. Crystal Imperfections Jack Washburn, Principal Investigator 1. Field Ion Electron Microscope Observations on Peritectoid Growth of Ni4W 83 2. Transmission Electron Microscopic Studies on Magnesium Oxide 84 3. Atom Probe Field Ion Microscope 86 4. Research Plans for Calendar Year 1972 86 5. 1971 Publications and Reports 87 -vi- B. Mechanisms of Plastic Deformation John E. Dorn (deceased Sept. 24, 1971) and John W. Morris, Jr., Principal Investigators 1. Research on Mechanisms of Dislocation Glide 88 2. Research on Plastic Deformation 88 3. Research Plans for Calendar Year 1972 90 1. 1971 Publications and Reports 90 C. Thermodynamics of Inhomogeneous Materials John W. Morris, Jr., Principal Investigator 1. Research Plans for Calendar Year 1972 92 2. 1971 Publications and Reports 92 D. Relation of Structure to Properties Gareth Thomte, Principal Investigator Steels 93 1. The Enhancement of Strengthening Dislocated Martensite 94 2. Structure and Mechanical Properties of Fe-Cr-C-Co Steels 95 3. Orientation Dependence on Deformation Induced z and a Martensite in Fe-Ni-Cr Single Crystals 95 Phase Transformations 96 4. Early Stages of Ordering in NijMo 96 5. Field Ion Microscopic Study of Antiparallel Twins in Ni,)Mo 97 6.
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