"/\:.5"j& LBL-140O A INORGANIC MATERIALS RESEARCH DIVISION Annual Report 1972 THIS DOCUMENT CONFIRMED'AS • UNCLASSIFIED ' ^f^' DiV*SlQN (^CLASSIFICATION ' Civ-" 1ST H r Lawrence o Berkeley Laboratory ' ,& University of California Berkeley 8 r.ffilREUT'O; 0A TH'S DCSU.ACFJT iS i mm SnSialliirgkni Enginesfin; ^w? ~fc<£t~- Cheml: Solid-Slots Chtmicol l#r«inic Physic* tso Enginoer'rna Er gTneerinjj LBL-1400 UC-2 General,Miscellaneous, and Progross Reports TID-4500 (59th Ed.) INORGANIC MATERIALS RESEARCH DIVISION ANNUAL REPORT, 1972 April 1973 -NOTICE- This report was prepared as en 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, makes any warranty, express or implied, or assumes any legal liability or responsibility for *k* acaeacy, com- pletcness 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 &l»U.ONOPTH1SDOCUMENT1SONU^ 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 Informotion Service U.S. Department of Commerce 5285 Port Royal Road Springfield, Virginia 22151 Price: Printed Copy $*8»; Microfiche $0.95 -iii- INORGANIC MATERIALS RESEARCH DIVISION ANNUAL REPORT. 1972* Contents GENERAL INTRODUCTION ix I. CHEMISTRY A. Inorganic Chemistry William h. Jolly, Principal Investigator 1. X-Ray Photoelectron Spectroscopy 1 2. Boron Hydride Chemistry 4 3. Sulfur-Nitrogen Chemistry 5 4. The Prediction of Gas-Phase lewis Acid-Base Dissociation Heats with an Empirical Four-Parameter Equation 6 5. Research Plans for Calendar Year 1973 7 6. 1972 Publications and Reports , 7 Robert E. Connick, Principal Investigator 1. Oxygen-17 NMR Study of the Rate of Water Exchange from Partially Complexed Nickel Ion 10 2. 170-NMR Studies of Water Molecules in the Second Coordination Sphere of Cr3+ 10 3. Computer Simulation of Solvent Exchange from the First Coordination Spheres of (.fetal Ions 10 4. Raman Spectrum of Triiodide Ion 10 5. Research Plans for Calendar Year 1973 10 6. 1972 Publications and Reports 11 Neil Bartlettj Principal Investigator 1. Noble-Gas and Halogen Chemistry 12 2. Fluorides, Oxyfluorides, and Oxides of the Transition Mstals 15 3. Research Plans for Calendar Year 1973 16 4. 1972 Publications and Reports 17 B. Solid State Chemistry and Physics Norman E. Phillips, Principal Investigator 1. Heat Capacity of SmS at 0 and IS kbar 19 2. Heat Capacity of PrCu? 19 3. The Heat Capacity of Dilute Cu Mi Alloys 19 4. The Low-Temperature Heat Capacity of Neodymiura 19 5. Research Plans for Calendar Year 1973 20 6. 1972 Publications and Reports 20 George Jura, Principal Investigator 1. Heat Capacities at High Pressures 21 2. Heat Capacity in Iron and Aluminum 22 3. Heat Capacity of Bismuth , 23 4. Research Plans for Calendar Year 1973 23 5. 1972 iublications and Reports 24 Gabov A. Sonbrjai, Principal Investigator 1. Low Energy Electron Diffraction Studies by Surfaces 25 2. Auger Electron Spectroscopy of Surfaces 27 3. Catalysis by Single-Crystal Surfaces 28 4. Molecular Beam Scattering by Surfaces 29 5. Research Plans for Calendar Year 1973 30 6. 1972 Publications and Reports 30 Lee F. Donaghey, Principal Investigator 1. Gas-Solid Processes 31 2. Crystallization Processes 32 3. Solid Electrolyte Studies 35 4. Research Plans for Calendar Year 1973 36 5. 1972 Publications and Reports 37 Preceding Annual Reports: UCRL-20500, LBL-425 -iv- C. Electrochemistry Charles W. Tobiac, Principal Investigator 1. Fundamental Studies of Ionic Mass Transport 38 2. Electrolysis at High Current Densities 39 3. Electrochemistry in Nonaqueous Solvents 41 4. Research Plans for Calendar Year 1973 41 5. 1972 Publications and Reports 42 Rolf H. Muller, Principal Investigator 1. Optical Studies of Interfacial Phenomena 43 2. Research Plans for Calendar Year 1973 45 3. 1972 Publications and Reports 46 John Newman, Principal Investigator 1. Analysis of Porous Electrodes with Sparingly Soluble Reactants 47 2. Potential Distribution in Axisymnetric Mercury-Pool Electrolysis Cells at Limiting Current 47 3. Mass Transfer to a Non-Newtonian Falling Film 47 4. Mass Transfer in Cylindrical Couette Flow 47 5. Corrosion of an Iron Rotating Disk 48 6. Mass Transfer Coefficient in Porous Flow Through Electrodes 48 7. The Radially Dependent Convective Warburg Problem 48 8. A Composite Expansion for the Wake Just Behind a Flat Plate 48 9. Mass Transfer to a Plane Below a Rotating Disk at High Schmidt Numbers . 49 10. The Transient Response of a Disk Electrode 49 11. Current Distribution at a Rotating Sphere Below the Limiting Current ... 49 12. Research Plans for Calendar Year 1973 50 13. 1972 Publications and Reports 50 D. Physical Chemistry Leo Brewer, Principal Investigator 1. Thermodynamic Properties of Third and Fourth Group Transition Metals with Platinum Group Metals 52 2. Application of the Regular Solution Theory co Metallic Solutions 52 3. Cptical Pumping in Rare Gas Matrices 52 4. Compilation of Ternary Phase Diagrams 52 5. Solubilities of Intermetallic Compounds in Iron 52 6. Thermodynamic Properties of Mo and its Compounds 52 7. Thermodynamic Properties and Phase Diagrams of the Alloy Systems of the Lanthanide and Actinide tetals 52 8. Research Plans for Calendar Year 1973 52 9. 1972 Publications and Reports 53 Charles B. Harris, Principal Investigator 1. Excited Triplet States in Molecules and Molecular Crystals 54 2. Coherent Energy Migration in Molecular Solids 54 3. Electron Spin Resonance Absorption in Coherent Triplet Exciton States ... 55 4. Exciton-Trap Interactions in the Coherent and Incoherent Limits 57 5. Phosphorescence Microwave Double Resonance Spectroscopy in Excited Triplet States 58 6. Breakdown of the Bom-Oppenheimer Approximation in Radiative Transitions . 59 7. Coherent Spin Phenomena in Molecular Excited States 59 8. Coherent Cptical Phenomena in Molecular Excited States 61 9. Research Plans for Calendar Year 1973 61 10. 1972 Publications and Reports 62 Alexander Pines, Principal Investigator 1. Nuclear Magnetic Double-Resonance 64 2. Nuclear Spin Thermodynanics and Multiple-Pulse Nuclear Magnetic Resonance 65 3. Research Plans for Calendar Year 1973 66 4. 1972 Publications and Reports 67 Ronald R. Eerm, Principal Investigator 1. Collision Dynamics of "Alkali-Like" Atoms 68 2. Crossed Beam Reactions of BaF2 with BCI3 68 3. Research Plans for Calendar Year 1973 69 4. 1972 Publications and Reports 69 -V- Harcld S. Johnston, Principal Investigator Introduction 71 1. Experimental Studies 71 2. Theoretical Studies 73 3. Research Plans for Calendar Year 1973 73 4. 1972 Publications and Reports 74 Bruce U. Mohan, Principal Investigator 1. Recombination of Gaseous Ions 75 2. The 02+-C2l>2 Reaction: An Endoergic Stripping Process 75 + 3. Dynamics of the 0 -H2 Reaction. I: Reactive Scattering of 0+(4s3/2) at Relative Energies below 15 eV 76 4. Dynamics of the 0+-H2 Reaction. II: Reactive and Non-Reactive Scattering at Relative Energies above 15 eV 77 5. An Apparatus for the Study of Ion-Molecule Reactions at Low Relative Collision Energies 77 6. Research Plans for Calendar Year 1973 77 7. 1972 Publications and Reports 78 William H. hiiller, Principal Investigator 1. Semiclassical Quantization of Non-Separable Systems 79 2. Penning Ionization of Hydrogen Atoms by Metastable Helium Atoms 79 3. Analytic Continuation of Classical Mechanics for Classically Forbidden Processes in Inelastic and Reactive Scattering 80 4. Semiclassical Theory of Electronic Transitions in Low Energy Atomic and hblecular Collisions Involving Several Nuclear Degrees of Freedom ... 82 5. Research Plans for Calendar Year 1973 82 6. 1972 Publications and Reports 82 Rollie J. Myers, Principal Investigator 1. Molecular Field Corrections for Electron Paramagnetic Resonance Spectroscopy + 84 2. Electron Paramagnetic Resonance Spectrum of Ti(H20)g 85 3. Proton Nuclear Magnetic Resonance on Solutions of Transition-Metal Ions . 86 4. Research Plans for Calendar Year 1973 87 5. 1972 Publications and Reports 87 Kenneth S. Pitzer, Principal Investigator 1. Solutions of Electrolytes 88 2. Other Topics 88 3. Research Plans for Calendar Year 1973 89 4. 1972 Publications and Reports 89 E. Nuclear Science Donald F. Olander, Principal Investigator 1. Laser Vaporization of Solids 90 2. A Modulated Molecular Beam Study of the Energy of Simple Gases Scattered from Pyrolytic Graphite 90 3. Molecular Beam Surface Reactions-Water Vapor on Graphite 90 4. Viscosity of Cesium up to 1600°C 91 5. Diffusion in Liquid Uranium 91 6. Oxygen Redistribution in Ceramic Nuclear Fuels 92 7. Research Plans for Calendar Year 1973 . 92 8. 1972 Publications and Reports 92 II. METALLURGY A. Crystal Imperfections Jack Washburn, Principal Investigator 1. Mechanism of Dipole Break-up 97 2. The Mechanism of Dislocation Loop Coarsening in MgO 97 3. Precipitation of Phosphorous in ion Implanted Silicon 98 4. Memory State Filaments in As-Te-I Amorphous Semiconductors 100 5. Field Ion Microscope Observations of Low Tenperature Ion Bombardment Damage in Iridium 100 6. Research Plans for Calendar Year 1973 101 7. 1972 Publications and Reports 101 -vi- B. Tlieoretical Metallurgy John W. Monn-s, Jr., Principal Investigator 1. Thermodynamics and Phase Stability 103 2. Mechanical Properties 104 3. Researdi Plans for Calendar Year 1973 106 4. 1972 Publications and Reports 106 C. Relation of Microstructure and Properties Gareth Thomas, Principal Investigator Introduction 108 1. Structure, Strength and Toughness of Fe-Cr-C Martensitic Steels 108 2. Martensitic Transformation and Strengthening of a Spinodal Fe/Ni/Cu Alloy 109 3. The Tempering of Martensite in an Iron 1.55 Nitrogen 111 4. Intergranular Fracture of Aged Cu-Ni-Fe Alloys 112 5. Short Range Order in Ni-Mo, Au-Cr, Au-V, and Au-Mn Alloys 112 K. Hign Voltage Electron Microscopy Gareth Thomas, Principal Investigator Introduction 114 1.