Table Of ContentElectrons in Fluids
The Nature
of Metal-Ammonia Solutions
Edited by
J. J ortner and N. R. Kestner
With 271 Figures
Springer-Verlag
Berlin . Heidelberg . N ew York 1973
Professor Dr. JOSHUA JORTNER
Institute of Chemistry, Tel-Aviv University,
Ramat Aviv, Tel-Aviv, Israel
Professor Dr. NEIL R. KESTNER
Department of Chemistry, Louisiana State University,
Baton Rouge, LA 70803, USA
ISBN 13: 978-3-642-61964-9 e-ISBN 13: 978-3-642-61962-5
DOl: 10.1007/978-3-642-61962-5
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is
concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction
by photocopying machine or similar means, and storage in data banks.
Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is
payable to the publisher, the amount of the fee to be determined by agreement with the publisher.
© by Springer·Verlag, Berlin· Heidelberg 1973. Library of Congress Catalog Card Number 73·8484.
Softcover reprint of the hardcover 1st edition 1973
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence
of a specific statement. that such names are exempt from the relevant protective laws and regulations
and therefore free for general use.
Typesetting, Printing and Binding: Briihlsche Universitatsdruckerei Gie8en.
Electrons in Fluids
The Nature
of Metal-Ammonia Solutions
Edited by
J. J ortner and N. R. Kestner
With 271 Figures
Springer-Verlag
N ew York . Heidelberg . Berlin 1973
Professor Dr. JOSHUA JORTNER
Institute of Chemistry, Tel-Aviv University,
Ramat Aviv, Tel-Aviv, Israel
Professor Dr. NEIL R. KESTNER
Department of Chemistry, Louisiana State University,
Baton Rouge, LA 70803, USA
ISBN 13: 978-3-642-61964-9 e-ISBN 13: 978-3-642-61962-5
DOl: 10.1007/978-3-642-61962-5
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is
concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction
by photocopying machine or similar means, and storage in data banks.
Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is
payable to the publisher, the amount of the fee to be determined by agreement with the publisher.
© by Springer·Verlag, Berlin· Heidelberg 1973. Library of Congress Catalog Card Number 73·8484.
Softcover reprint of the hardcover 1st edition 1973
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence
of a specific statement. that such names are exempt from the relevant protective laws and regulations
and therefore free for general use.
Typesetting, Printing and Binding: Briihlsche Universitatsdruckerei Gie8en.
Preface
Colloque Weyl I was convened in June 1963 at the Catholic University of Lille
to commemorate one hundred years of the study of metal-ammonia solutions.
This memorable event, which involved a "single-particle excitation", inspired
Gerard Lepoutre to assemble an international group of physicists and chemists
to discuss the nature of metal-ammonia solutions. Colloque Weyl II, which took
place at Cornell Universtiy, Ithaca, N.Y. in June 1969, was initiated as a
"cooperative interaction" between M. J. Sienko, J. L. Dye, J. J. Lagowski,
G. Lepoutre and J. C. Thompson. That meeting made it clear that Colloque
Weyl should be continued in order to promote the fruitful exchange of ideas set
in motion at Lille and at Cornell.
Colloque Weyl III came into being as the result of a resolution passed at the
Cornell meeting, Tel-Aviv University being the suggested site. The Organizing
Committee consisted ofE. D. Bergmann, J. Jortner, J. J. Lagowski, G. Lepoutre,
U. Schindewolf and M. J. Sienko, reflecting the international and interdisciplinary
aspects of the field.
The original aim of the Colloque Weyl was to contribute to the understanding
of metal-ammonia solutions. Colloque Weyl III extended the scope of the
meetings to include related work on electrons in polar and non-polar liquids
and in dense fluids, the electronic states of disordered systems, and the metal-in
sulator transition, thus the chemical and physical properties of electrons in
fluids from a general point of view. The interdisciplinary nature of the field and
of related areas was emphasized by an intensive exchange of ideas between
chemists and physicists, experimentalists and theoreticians.
This volume provides a record of the lectures, communications and discussions
that took place during the week of Colloque Weyl III. The contributions are not
necessarily presented in chronological order. Some changes have been made to
afford a more coherent presentation of certain subjects.
Colloque Weyl III was held at Kibbutz Hanita, Upper Galilee, Israel on
June 19-23, 1972. The conference was organized by Tel-Aviv University and
sponsored by the Israeli Academy of Sciences and Humanities, the Israeli
Foundation for Research Grants, the Israeli National Council for Research
and Development, Tel-Aviv University as well as the U. S. Army European
Research Office. We are very grateful to these agencies for their support and
cooperation in making this a truely international conference.
JOSHUA JORTNER
NEIL R. KESTNER
Tel-Aviv, June 1973
Contents*
Theory of Electrons in Polar Fluids. N. R. KESTNER. With 9 Figures 1
Discussion .................... 25
Metal-Ammonia Solutions: The Dilute Region. J. J. LAGOWSKI.
With 2 Figures . . . . . . . . . . . . . . . . . . . 29
Discussion .................... 36
The Effect of Electrolytes on the Hydrogen-Bonded Structure of Liquid
Ammonia. J. H. ROBERTS and J. J. LAGOWSKI. With 15 Figures . . . 39
Discussion .......................... 54
Magnetic Relaxation Properties of Dilute Solutions of Sodium in Liquid
Ammonia. C. LAMBERT. With 4 Figures ... . . . . . . . . 57
Chemical Equilibria between Anions and the Ammoniated Electron.
J. BELLONI and E. SAITO 71
Discussion 74
Metal Solutions in Amines and Ethers. J. L. DYE. With 7 Figures 77
Discussion ...................... . 92
Extinction Coefficients of Solutions of Alkali Metals in Amines. S. NEHARI
and K. BAR-ELI. With 4 Figures . . . . . . . . . .. 97
Discussion ................... . 100
Ultrafast Optical Processes. P. M. RENTZEPIS. With 19 Figures 103
Discussion ................... . 127
Quasi-Free Electrons in Polar Liquids. P. DELAHAY. With 3 Figures 131
Discussion .....................;. 136
Spectra of the Ammoniated Electron in the Presence of Amide. E. SAITO.
With 4 Figures . . . . . . . . . . . 139
Discussion ................ . 144
Raman Spectroscopy of Metal-Ammonia Solutions. B. L. SMITH and
W. H. KOEHLER. With 15 Figures ................ . 145
Raman Spectra of Dilute Metal-Ammonia Solutions. M. G. DEBACKER,
P. F. RUSCH, B. DEBETTIGNIES, and G. LEPOUTRE. With 2 Figures 161
* Plenary discussions appear in heavy type.
VIII Contents
General Discussion of Papers by SMITH/KoEHLER and DEBACKER et al. 167
Metal-Ammonia Solutions VIII. Infrared Spectroscopy of the Solvent.
P. F. RUSCH and J. J. LAGOWSKI. With 7 Figures 169
Discussion .......................... 179
Metal-Ammonia Solutions: Transition Range. G. LEPOUTRE. With 10 Figures 181
Appendix. A Percolation Process for Metal to Nonmetal Transition in
Metal-Ammonia Systems. P. CHIEUX and G. LEPOUTRE . . . . . . . . 193
Thermodynamics and Critical Phenomena in Metal-Ammonia Solutions.
P. DAMAY. With 3 Figures . . . . . . . . . . . . . . . . . ... 195
Transport Properties of Lithium-Ammonia Solutions in the Intermediate
Concentration Range. J. P. LELIEUR, P. DAMA Y, and G. LEPOUTRE. With
4 Figures ......................... 203
General Discussion of Papers by LEPOUTRE, DAMAY and LELIEUR et al. .. 210
NMR Measurements of Self-Diffusion in Lithium-Ammonia and Sodium
Ammonia Solutions. A. N. GARROWAY and R. M. COTTS. With 7 Figures 213
Discussion .......................... 228
Cell e.mJ.'s in Metal-Ammonia Solutions. K. IcHIKAWA and J. C.
THOMPSON. With 7 Figures 231
Discussion ........... . 238
Impedence Behavior of Metal-Ammonia Solid Metal Interface. P. D.
SCHETTLER, C. L., VAN ANTWERP, J. A. HAMILTON, J. E. THILLY, and J. D.
SPEAR. With 5 Figures 239
Discussion .................. . 245
Absorption of Ultrasound in Metal-Ammonia Solutions. D. E. BOWEN.
With 8 Figures . . . . . . . . . . 247
Discussion .......... . 254
The Electronic Structures of Disordered Materials. M. H. COHEN. With
24 Figures 257
Discussion 284
Concentrated M-NH3 Solutions: A Review. J. C. THOMPSON. With 14 Figures 287
Discussion .......................... 302
Nuclear Magnetic Resonance Studies of Cesium-Ammonia Solutions. J. P.
LELIEUR. With 10 Figures . . . . . . . . . . . . . . . . . . . . 305
Conductivity of Concentrated Metal-Ammonia Solutions in the Frequency
Range 0-70 GHz. K. G. BREITSCHWERDT and H. RADSCHEIT. With
3 Figures 315
Discussion 321
Contents IX
Strange Magnetic Behavior and Phase Relations of Metal-Ammonia Com
pounds. T. DAVID, W. GLAUNSINGER, S. ZOLOTOV, and M. J. SIENKO.
With 11 Figures . . . . . . . . . . . . .. ..... . 323
Discussion ................ ..... . 338
On Superconducting Metal-Ammonia Complexes. J. V. ACRIVOS, S. F.
MEYER, and T. H. GEBALLE. With 4 Figures 341
Discussion ............ . 353
Metallic Vapors. F. HENSEL. With 8 Figures 355
Metal-Nonmetal Transition in Expanded Liquid Mercury. U. EVEN and
J. JORTNER. With 11 Figures . . . . . . . . . . . . . . 363
General Discussion of Papers by HENSEL, and EVEN/JORTNER 382
Metal-Nonmetal Transition and Exciton Screening. A. GEDANKEN, B. RAZ,
U. EVEN, and J. JORTNER. With 2 Figures . . . . . . . . . . . 385
Discussion ......................... . 392
Mobility Studies of Excess Electrons in Nonpolar Hydrocarbons. H. T.
DAVIS, L. D. SCHMIDT, and R. G. BROWN. With 6 Figures . . . . . . 393
Discussion ......................... . 410
Excitons in Liquids and the Energy of the Quasi-Free Electron State. B. RAZ
and J. JORTNER. With 9 Figures ................ . 413
Discussion ......................... . 422
Electron Localization in Dense He Gas. I. WEBMAN and J. JORTNER. With
6 Figures 423
Discussion 427
Excess Electron States in Dense Polar Vapors. A. GAATHON and J. JORTNER.
With 14 Figures ................. ...... . 429
Discussion ......................... . 446
Optical Absorption Spectrum of the Solvated Electron in Ethers and in Binary
Liquid Systems. L. M. DORFMAN and F. Y. Jou. With 9 Figures . . . . 447
Discussion ............... . . . . . . . . 457
Radiolytic and Photolytic Formation of Stable e';;" in Amide Solutions
J. BELLONI and E. SAITO. With 5 Figures . . . . . . . . . . 461
Kinetic Studies of Reactions Involving the Ammoniated Electron. R. R.
DEWALD, R. L. JONES, and H. BOLL ............... 473
Comments on Electron Transfer Reactions. N. R. KESTNER and J. LOGAN 479
Discussion .................... 481
'Spin Ofr of Solvated Electron Research. U. SCHINDEWOLF 483
Subject Index . 487
Color Plates . 491
