T H E
J O U R N A L
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PHYSICAL CHEMISTRY Registered in U. S. Patent Office 0 Copyright, 1975, by the American Chemical Society
VOLUME 79, N U M B E R 26
DECEMBER 18, 1975
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Electrons in FluidsThe Nature of Metal-Ammonia Solutions MICHIGANSTATEUNIVERSITY,EAST LANSING,MICHIGAN MONDAYJUNE 30-THURSDAY JULY 3,1975
Introductory Remarks James L. Dye Department of Chemistry, Michigan State University, East Lansing, Michigan 48824 Publication costs assisted by Colloque Weyl lV
The fourth international conference on metal-ammonia solutions was held June 29-July 3, 1975 at Michigan State University, East Lansing, Michigan. The original Colloque Weyl was held on the occasion of the 100th anniversary of Weyl’s discovery of metal-ammonia solutions. I t convened in June 1963 a t the Catholic University of Lille, France under the direction of Professor Gerard Lepoutre and marked the first time that chemists and physicists with a common interest in the solvated electron met to exchange ideas about this interesting species in metal-ammonia solutions. Through the years, as the importance of electrons in fluids, not only in ammonia, but also in other polar and nonpolar solvents became apparent to workers in a variety of fields ranging from radiation chemistry to the physics of liquid metals, the scope of the conference expanded to include more than just metal solutions in ammonia. However, the major goal of the Weyl colloquium is to contribute to the understanding of metal--ammonia solutions. After a lapse of 6 years, Colloque Weyl I1 was held a t Cornel1 University, Ithaca, New York in June 1969, with Professor M. J. Sienko directing the arrangements. At that time an informal agreement was reached to hold such a conference every 3 years and to meet in the United States for alternate meetings. Colloque Weyl I11 was convened by Professor J. Jortner of Tel Aviv University, Israel, a t Kib-
butz Hanita in June 1972. At that time, tentative plans were made to hold the fourth conference a t Michigan State University in 1975. In view of the interdisciplinary nature of this field, the scope of the meeting included related work on electrons in polar and nonpolar fluids, the problem of electronic states in disordered systems, and the metal-insulator transition. The organizers of Colloque Weyl IV are grateful to the National Science Foundation, the donors of the Petroleum Research Fund (administered by the American Chemical Society) and the Dow Chemical Company for partial support of the conference. We also acknowledge the cooperation of the Department of Chemistry and the Continuing Education Service of Michigan State University. We are grateful t o the Session Chairmen for their help with the program. Special thanks are due Ann Tsiminakis of the Continuing Education Service for her skillful handling of arrangements for the conference and to Naomi Hack, who worked very effectively with the Chairman of the Organizing Committee from the inception of the conference to the publication of the manuscripts and discussion. Organizing Committee: R. Dewald (Tufts), J. Jortner (Tel Aviv), G. Lepoutre (Lille), U. Schindewolf (Karlsruhe), M. Sienko (Cornell), J. Thompson (Texas). 2789
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List of Participants and Affiliation J. Acrivos - San Jose State University C. Andrews - Michigan State University S. Arai - Wako-Shi, Japan D. A. Armstrong - University of Calgary, Canada J. K. Baird - Oak Ridge National Laboratory G. Bakale - Case-Western Reserve University H. Bale - University of North Dakota J. Belloni .- University of Paris, Orsay, France A. Bernas - University of Paris, Orsay, France B. Bockrath - Energy Research and Development Administration, Pittsburgh, Pa. D. Bowen - University of Texas-El Paso G. Caflisch - University of Wisconsin-Madison R. Catterall - University of Salford, England J. Ceraso - Michigan State University J. Chase - University of Toronto, Canada L. Chia - New York University P. Chieux - Institut Laue-Langevin, Grenoble, France M. Cohen - University of Chicago L. V. Coulter - Boston University M. DaGue - Michigan State University P. Damay - Lille, France M. DeBacker - Lille, France B. J. DeBettignies, Villeneuve, France P. Delahay - New York University R. Dewald - Tufts University L. Dorfman - Ohio State University R. Firestone - Ohio State University J. W. Fletcher - AEC, Chalk River, Ontario, Canada G. Freeman - University of Alberta, Canada K. Fueki - Nagoya University, Japan W. S. Glaunsinger - Arizona State University S. Golden - Brandeis University G. Hall - University of Toronto, Canada T. Higashimura - Kyoto University, Japan R. Holroyd - Brookhaven National Laboratory J. W. Hunt - University of Toronto, Canada D. Huppert - Bell Laboratories, Murray Hill, N.J. C. Subhash Jain - University of Chicago
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J. Jortner - University of Tel-Aviv, Israel M. Katsumoto - Lille, France N. Kestner - Louisiana State University L. Kevan - Wayne State University N. Klassen - National Research Council of Canada W. Koehler - Texas Christian University A. M. Koulkes-Pujo - C.E.N. Saclay, France P. Krebs - University of Karlsruhe, Germany J. J. Lagowski - University of Texas-Austin N. Lau - Tufts University J. P. Lelieur - Lille, France G. Lepoutre - Lille, France W. Love - Arizona State University R. F. Marzke - Arizona State University E. Mei - Michigan State University E. Minnich - Elmira College, New York S. Nehari - Brandeis University and Tel-Aviv University L. Nemec - New York University M. Newton - Brookhaven National Laboratory S. 0. Nielsen - AECRE, Denmark A. Patterson, Jr. - Yale University W. Peer - University of Texas-Austin A. K. Pikaev, Academy of Sciences, Moscow, USSR K. Plowman - McGill University, Montreal, Canada S. Rice - Oxford University, England P. Rusch - Chemical Abstracts Service, Columbus, Ohio P. Schettler - Juniata College, Pennsylvania U. Schindewolf - University of Karlsruhe, Germany W. A. Seddon - AEC, Chalk River, Ontario, Canada M. Sienko - Cornel1 University M. Silver - University of North Carolina W. S. Struve - Iowa State University J. Thompson - University of Texas-Austin T. Tuttle - Bandeis University R. VonDreele - Arizona State University B. Webster - University of Glasgow, Scotland T. White - Arizona State University J. E. Willard - University of Wisconsin M. Yemen - Michigan State University
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COLLOQUE WEYL IV FINAL PROGRAM (Papers as presented a t the sessions.) SESSION A: Theories and Models of Electrons in Polar Fluids Session Chairman: J. Jortner, Tel Aviv University, Israel
Marshall D. Newton;Chemistry Department, Brookhaven National Laboratory, Upton, N.Y. 11973 The Role of ab Initio Calculations in Elucidating Properties of Hydrated and Ammoniated Electrons Brian Webster, Chemistry Department, University of Glasgow, Glasgow GI2 8QQ , Scotland Ab Initio Studies into the Mechanisms of Formation of the Hydrated Electron Neil R. Kestner and Jean Logan, Chemistry Department, Louisiana State University, Baton Rouge, La. 70803 Theoretical Studies on the Composition of the Absorption Spectrum of the Solvated Electron Sidney Golden, Chemistry Department, Brandeis University, Waltham, Mass. 02154 Model Adiabaticity Effects on Solvation Free-Energies of Electrons Paul D. Schettler, Jr., Lille, France and Juniata College, Pa., and Gerard Lepoutre, Lille, France Interactions between Solvated Electrons. I. Electron-Electron, Electron-Solvent, Solvent-Solvent Interactions in Ammonia. Valence Bond Approximation
* K. Plowman, McGill University, Canada, and J. J. Lagowski, University of Texas at Austin A Vibrational Analysis of the Solvent as It Pertains to the Nature of Metal-Ammonia Solutions
R. R. Dogonadze, E. M. Itskovitch, A. M. Kuznetsov, and M. A. Vorotyntsev, Institute of Electrochemistry of the Academy of Sciences of the USSR, Moscow State University Theory of Light Absorption by Ions in Solution SESSION B: The Electron Localization Process Session Chairman: U. Schindewolf, Karlsruhe, Germany
John W. Hunt and W. John Chase, Ontario Cancer Institute and Department of Medical Biophysics, University of Toronto, Toronto, Ontario, Canada M4X 1K9 Solvation Time of the Electron in Polar Liquids. Water and Alcohols Larry Kevan, Department of Chemistry, Wayne State University, Detroit, Mich. 48202 Pulse Radiolysis Study of Solvated Electrons in Water-Ethanol Glasses a t 76 K. Structure of the First Solvation Shell Around the Electron. J. Belloni, E. Saito, and M. Clerc, Orsay, France Solvation Time of Electrons in Liquid Ammonia
** P. M. Rentzepis, W. Struve, and D. Huppert, Bell Laboratories, Murray Hill, N.J. 07974 Dynamics of the Solvating Electron and the Hole Burning in NH3-Na Solutions by Picosecond Pulses
** P. M. Rentzepis and D. Huppert, Bell Laboratories, Murray Hill, N.J. 07974 Kinetics of Electrons in Methylamine-Sodium Solutions by Picosecond Pulses SESSION C: Electrons in Dense Vapors and Nonpolar Liquids Session Chairman: G. R. Freeman, University of Alberta, Edmonton, Canada
Richard Holroyd, Steven Tames, and Alvin Kennedy, Chemistry Department, Brookhaven National Laboratory, Upton, N.Y. 11973 The Effect of Temperature on Conduction Band Energies and on Reactions of Electrons in Nonpolar Liquids
* S. 0. Nielsen, AECRE, Denmark Localization of Excess Electrons in Liquid Alkanes
J. K. Baird, Oak Ridge National Laboratory, Health Physics Division, Oak Ridge, Tenn. 37830 Continuum Dielectric Model for an Electron in a Nonpolar Fluid Shoji Noda, Larry Kevan, Department of Chemistry, Wayne State University, Detroit, Mich. 48202, and Kenji Fueki,Department of Synthetic Chemistry, Faculty of Engineering, Nagoya University, Na-
goya, Japan Conduction State Energy of Excess Electrons in Condensed Media. Liquid Methane, Ethane, and Argon and Glassy Matrices
* M. Silver and J. P. Hernandez, Physics Department, University of North Carolina, Chapel Hill, N.C. 27514 Electron Transport and 0 2 - Formation in Fluid Helium The Journal of Physical Chemistry, Vol. 79, No. 26, 1975
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D. A. Armstrong and S. S. Nagra, Department of Chemistry, The University of Calgary, Calgary, Alberta, Canada Mechanisms of Thermal Electron Capture by HC1 and HBr J.-P. Dodelet, F.-Y. Jou, and G. R. Freeman, Chemistry Department, University of Alberta, Edmonton, Canada, T6G 2E1 An Electron Mobility Transition in Liquid Ethers
SESSION D: The Metal-Nonmetal Transition in Metal-Ammonia Solutions Session Chairmen: T. Tuttle, Brandeis University, and J. C. Thompson, University of Texas
J. P. Lelieur, P. Damay, and G. Lepoutre, 13 rue de Toul, 49000 Lille, France Magnetic Properties and the Metal-Nonmetal Transition in Metal-Ammonia Solutions Sidney Golden, Chemistry Department, Brandeis University, Waltham, Mass. 02154; Isotope Department, The Weizmann Institute of Science, Rehovot, Israel; and Physical Chemistry Department, The Hebrew University, Jerusalem, Israel. Magnetic Similarities and Differences of Some Chemical Models of Alkali Metal-Ammonia Solutions
* D. N. Knapp and H. D. Bale, University of North Dakota, Grand Forks, N.D. Small Angle X-Ray Scattering from Metal-Ammonia Solutions
P. Chieux, Institut Laue Langevin, Grenoble, France Concentration Fluctuations in the Nonmetal to Metal Transition Range of the 7Li-ND3 System. A Neutron Small Angle Scattering Experiment D. E. Bowen, Physics Department, The University of Texas at El Paso, El Paso, Tex. Ultrasound Absorption Studies in the Critical Region of Lithium-Ammonia Solutions Morrel H. Cohen, The James Franck Institute and Department of Physics, The University of Chicago, Chicago, Ill. 60637, and Joshua Jortner, Department of Chemistry, Tel-Aviv University, Tel-Aviv, Israel Metal-Nonmetal Transition in Metal-Ammonia Solutions via the Inhomogeneous Transport Regime N. F. Mott, Cavendish Laboratory, University of Cambridge, England The Metal-Insulator Transition in Metal-Ammonia Solutions
K. G. Breitschwerdt and H. Radscheit, Institute fur Angewandte Physik, Universitat Heidelberg, Heidelberg, Germany Microwave Electronic Properties of Metal-Ammonia Solutions S. Hahne and U. Schindewolf, Institut fur Physikalische Chemie und Elektrochemie, Universitat Karlsruhe, Germany Temperature- and Pressure-Dependence of the Nonmetal-Metal Transition in Sodium-Ammonia Solutions (Electrical Conductivity and PVT Data up to 150OC and 1000 bars)
Masayuki Katsumoto and Pierre Damay, 13 rue de Toul, 59000 Lille, France Phase Diagram for Liquid-Liquid Coexistence in the Li-ND3 System
* J. C. Thompson, Department of Physics, The University of Texas at Austin, Tex. 78712 Phase Separation of Mixed Solutes in Liquid Ammonia
* B. DeBettignies, Universite des Sciences et Techniques de Lille, F-59650 Villeneuve d’ASCQ, France, and M. G. DeBacker, CNRS ERA 126,13 rue de Toul, F-59046, Lille, France Raman Spectra of Li-4NH3 and Li-4ND3 Solutions Pierre Damay, Lille, France, and Paul Schettler, Lille, France and Juniata College, Juniata Pa. Fluctuations in Metal-Ammonia Solutions
SESSION E: Optical Properties Session Chairman: G. Lepoutre, Lille, France
Ladislav Nemec, Lucille Chia, and Paul Delahay, Department of Chemistry, New York University, 4 Washington Place, Room 514, New York, N.Y. 10003 Photoionization Spectra of Solutions as Obtained by Photoelectron Spectroscopy P. Krebs, Institut fur Physikalische Chemie und Elektrochemie, Universitat Karlsruhe, Germany Continuous Registration of Optical Absorption Spectra of Periodically Produced Solvated Electrons W. Schmitt and U. Schindewolf, Institut fur Physikalische Chemie und Elektrochemie, Universitat Karlsruhe, Germany Absorption Spectra of Excess Electrons in Alkali-Halide Salt Melts The Journal of Physical chemistry, Vol. 79, No. 26, 1975
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* Judith B.Weinstein and R. F.Firestone, Department of Chemistry, The Ohio State University, 60lumbus, Ohio 43210 Dependence of the Thermodynamic Stability of the Solvated Electron in Binary Liquid Solutions on Thermodynamic Solution Stability Prior to Electron Injection T. R. White and W. S.Glaunsinger, Arizona State University Laser Raman Investigation of Dilute Metal-Ammonia Solution
W. F.Love, C.T. Walker, and W. %. Glaunsinger, Arizona State University Brillouin Scattering in Dilute Metal-Ammonia Solutions William Peer and J. 6.Lagowski, The Robert A, Welch Laboratories, The University of Texas a t Austin, Austin, "ex. Metal-Ammonia Solutions. IX. Matrix Rank Analysis as an Indicator of the Number of Species PIesen t James W. Lundeen and William H. Koehler, Department of Chemistry, Texas Christian University, Fort Worth, Tex. 76129 Liquid Ammonia. A Comparative Study of Models via Raman Spectroscopy
G. Rubinstein, Ramapo College of New Jersey, Mahwah, N.J. 07430 Correlation of Optical and Magnetic Data for Na-NHa Solutions
SESSION F: Electrons in Disordered Solids Session Chairman: L. Kevan, Wayne State University
John E. Willard, Department of Chemistry, University of Wisconsin, Madison Wis. 53706 Trapped Electrons in Organic Glasses A. Bernas, D. Grand, and T. B. Truong, Orsay, France Trapped Electrons Studied through Stimulated Neutralization Luminescence A. Namiki, M. Noda, and T. Higashimura, Research Reactor Institute, Kyoto University, Japan Capture of the Trapped Electron in Alcohol Glasses
SESSION G: Properties of Solid Metal-Amines and Related Compounds Session Chairman: M. Sienko, Cornell University
R. F. Marzke and W. S. Glaunsinger, Arizona State University Proton Magnetic Resonance Study of Metal-Ammonia Compounds
W. H. McKnight and J. C. Thompson, The University of Texas at Austin Optical Properties of Concentrated Li-NH3 Solutions and Solid Li(NH3)d Therese David Pfeuty and M. J. Sienko, Baker Laboratory of Chemistry, Cornell University, Ithaca, N.Y. 14853 Electron Band Structure in Solid Hexaamminecalcium(0)
R. B. Von Dreele, W. S. Glaunsinger, Arizona State University, A. L. Bowman, and J. L. Yarnell, Los Alamos Scientific Laboratory Neutron Diffraction Study of Hexaammine-d3-calcium(O) at 75 K P. Chieux, Grenoble, France, M. J. Sienko, Cornell University, and F. DeBaecker, Lille, France Neutron Diffraction Study and Phase Diagram Investigation of the Solid Lithium-Ammonia Compound Pierre Damay, Lille, France, and M. J. Sienko, Cornell University Conduction Electron Spin Resonance of Lithium Tetraammine, Li(NH3)4 J. V. Acrivos, C. Delios, N. Y. Tops@e,and J. R. Salem, San Jose State University, San Jose, Calif. 95194 Insertion of NH3 and NzH4 into Layer Disulfides
R. Catterall and P. P. Edwards, University of Salford, England Electron Spin Resonance Studies of Localized Excess Electron States in Frozen Solutions of Alkali Metals in Hexamethylphosphoramide
R. Catterall and P. P. Edwards, University of Salford, England Electron Spin Resonance Studies of Extended Excess Electron States in Frozen Solutions of Alkali Metals in Hexamethylphosphoramide The Journal of Physical Chemistry, Vol. 79, No. 26, 1975
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SESSION H: Reactions of Electrons Session Chairman: L. Dorfman, Ohio State University
A. K. Pikaev, B. G. Erskov, and I. E. Makarov, Institute of Physical Chemistry of the Academy of Sciences of the USSR, Moscow, USSR Influence of Nature of Matrix on Reactivity of Electrons in Irradiated Systems M. J. Pilling and Stephen A. Rice, Physical Chemistry Laboratory, South Parks Road, Oxford, OX1 3QZ, England The Effect of the Charge of an Electron Scavenger on the Rate of Electron Tunneling in Glasses and Liquids A. M. Koulkes-Pujo, C.N.R.S., France, L. Gilles, and J. Sutton, Cen. Saclay, France Kinetics Study of Selective Solvation of Electrons in Water-Dimethyl Sulfoxide Mixtures Leon M. Dorfman and Bradley Bockrath, Department of Chemistry, The Ohio State University, Columbus, Ohio, 43210 The Solvated Electron as Reducing Species in the Submicrosecond Formation of Reactive Transients. Carbanions in Solution George Bakale, Department of Radiology, Case Western Reserve University, Cleveland, Ohio 44106, U. Sowada, and W. F. Schmidt, Hahn-Meitner-Institut fur Kernforschung Berlin GmbH, Bereich Strahlenchemie, 1Berlin 39, Germany Electron Attachment to SFe in Nonpolar Liquids SESSION I: Kinetics and Thermodynamics of Metal-Ammonia Solutions Session Chairman: L. V. Coulter, Boston University
Robert R. Dewald, Tufts University, Medford, Mass. 02155 Mechanistic Studies of Metal-Ammonia Reductions Pierre Damay, 13 rue de Toul, Lille 59046, France Surface Tension of Metal-Ammonia Solutions Gerard Billaud and Antoine Demortier, 13 rue de Toul, 59000 Lille, France Dielectric Constant of Liquid Ammonia from -35 to +5OoC and Its Influence on the Association between Solvated Electrons and Cations J. W. Fletcher and W. A. Seddon, Physical Chemistry Branch, Atomic Energy of Canada, Limited, Chalk River Nuclear Laboratories, Chalk River, Ontario, KOJ 1J0, Canada Alkali Metal Species in Liquid Amines, Ammonia, and Ethers. Formation by Pulse Radiolysis SESSION J: Alkali Metal Monomers and Anions Session Chairmen: J. J. Lagowski, University of Texas and G. Lepoutre, Lille, France
Bradley Bockrath, James F. Gavlas, and Leon M. Dorfman, Department of Chemistry, The Ohio State University, Columbus, Ohio 43210 Spectra of esol- Coupled with Metal Cations. Lithium in Tetrahydrofuran James L. Dye, Charles W. Andrews, and S. E. Mathews, Department of Chemistry, Michigan State University, East Lansing, Mich. 48824 Strategies for the Preparation of Compounds of Alkali Metal Anions T. R. Tuttle, Jr., Brandeis University The Monomer and Its Paramagnetic Companion in Some Potassium Solutions in Alkylated Amines James L. Dye, Charles W. Andrews, and Joseph M. Ceraso, Department of Chemistry, Michigan State University, East Lansing, Mich. 48824 NMR Studies of Alkali Anions
* S. Nehari and K. Bar-Eli, Department of Chemistry, Tel-Aviv University, Ramat-Aviv, Israel On the Optical, Electrical, and Magnetic Properties of Alkali Metal Amine Solutions
* J. V. Acrivos, Department of Chemistry, San Jose State University, San Jose, California 95194 On the Dilemma of M-NHs Solutions
* Papers marked with a single asterisk were presented for discussion a t the Colloquium but, for various reasons, are not included in this symposium issue. = * These papers have been combined into one paper by D. Huppert, P. M. Rentzepis, and W. S. Struve, Picosecond Dynamics of Localized Electrons in Metal-Ammonia and Metal-Methylamine Solutions
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