Table Of ContentELECTRONIC STRUCTURE
AND PROPERTIES OF
HYDROGEN IN METALS
NATO CONFERENCE SERIES
I Ecology
II Systems Science
III Human Factors
IV Marine Sciences
V Air-Sea Interactions
VI Materials Science
VI MATERIALS SCIENCE
Volume 1 Molecular Metals
Edited by William E. Hatfield
Volume 2 Materials for Advanced Batteries
Edited by D. W. Murphy, J. Broadhead, and B. C. H. Steele
Volume 3 Adhesion in Cellulosic and Wood-Based Composites
Edited by John F. Oliver
Volume 4 Adhesion Problems in the Recycling of Concrete
Edited by Pieter C. Kreijger
Volume 5 Atomistics of Fracture
Edited by R. M. Latanision and J. R. Pickens
Volume 6 Electronic Structure and Properties of Hydrogen in Metals
Edited by P. Jena and C. B. Satterthwaite
ELECTRONIC STRUCTURE
AND PROPERTIES OF
HYDROGEN IN METALS
Edited by
P. Jena
and
C. B. Satterthwaite
Virginia Commonwealth University
Richmond, Virginia
Published in cooperation with NATO Scientific Affairs Division
PLENUM PRESS· NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
NATO International Symposium on the Electronic Structure and Properties of Hydrogen
in Metals (1982: Richmond, Va.)
Electronic structure and properties of hydrogen in metals.
(NATO conference series. VI, Materials science; v. 6)
"Proceedings of a NATO International Symposium on the Electronic Structure and
Properties of Hydrogen in Metals, held March 4-6, 1982, in Richmond, Virginia"
Verso t.p.
Includes bibliographical references and index.
1. Metals-Hydrogen content-Congresses. 2. Electronic structure-Congresses. 1.
Jena, P. II. Satterthwaite, C. S., 1920- . III. North Atlantic Treaty Organization.
Scientific Affairs Division. IV. Title. V. Series.
TN689.2.N36 1983 669/.94 82·16569
ISBN 978-1-4684-7632-3 ISBN 978-1-4684-7630-9 (eBook)
DOI 10.1007/978-1-4684-7630-9
Proceedings of a NATO International Symposium on the Electronic Structure and
Properties of Hydrogen in Metals, held March 4-6, 1982, in Richmond, Virginia
© 1983 Plenum Press, New York
Softcover reprint of the hardcover 1s t edition 1983
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
AII rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
PREFACE
Hydrogen is the smallest impurity atom that can be implanted
in a metallic host. Its small mass and strong interaction with the
host electrons and nuclei are responsible for many anomalous and
interesting solid state effects. In addition, hydrogen in metals
gives rise to a number of technological problems such as hydrogen
embrittlement, hydrogen storage, radiation hardening, first wall
problems associated with nuclear fusion reactors, and degradation
of the fuel cladding in fission reactors. Both the fundamental
effects and applied problems have stimulated a great deal of inter
est in the study of metal hydrogen systems in recent years. This
is evident from a growing list of publications as well as several
international conferences held in this field during the past decade.
It is clear that a fundamental understanding of these problems re
quires a firm knowledge of the basic interactions between hydrogen,
host metal atoms, intrinsic lattice defects and electrons. This
understanding is made particularly difficult by hyrogen's small
mass and by the large lattice distortions that accompany the
hydrogenation process.
The purpose of the "International Symposium on the Electronic
Structure and Properties of Hydrogen in Metals" held in Richmond,
Virginia, March 4-6, 1982 was to increase our fundamental under
standing of hydrogen in metals. Such knowledge is essential in
solving technologically important questions. The symposium con
sisted of twenty-two invited papers and seventy-two contributed
poster presentations and attracted nearly 150 participants from
thirteen countries. The proceedings of this symposium constitute
this book.
The discussions and presentations included a number of topics:
phase diagrams, spinodals, order-disorder transformations, thermo
dynamics, neutron scattering, elastic interactions, electronic
structure, magnetic and hyperfine properties, superconductivity,
diffusion, interaction with lattice defects, chemisorption, and
catalysis. A variety of experimental and theoretical techniques
were discussed and the complimentarity of these techniques in
probing the electronic structure and properties of metal-hydrogen
systems was emphasized.
v
vi PREFACE
The structure, phase diagrams; phase transitions, stabilities,
stoichiometries and site occupancies were presented from an experi
mental viewpoint and discussed theoretically in terms of electronic
and elastic interactions. The electronic structure and properties
were studied with de Haas van Alphen effect, XPS/UPS and energy loss
spectroscopy, M6ssbauer effect, perturbed angular correlation, muon
spin rotation, and electron and nuclear spin resonance techniques.
The results were analyzed theoretically using conventional jellium,
cluster, and band structure models. The mechanism of trapping of
hydrogen by impurities and imperfections and the effects of trapping
on diffusion entered the discussion. New work on superconductivity
and the status of the theory were presented. Throughout much of
the program isotope effects and quantum solid effects associated
with the small hydrogen mass played a role. The present under
standing of hydrogen chemisorption and catalysis was reviewed. Be
cause of the limited time available for the conference, many impor
tant areas of hydrogen in metals had to be left out.
We wish to thank the conferees for the high quality of their
participation in the invited and poster presentations and exchange
of ideas. We thank the members of the international steering
committee: Professors G. Alefeld, B. Baranowski, H. K. Birnbaum,
J. P. Burger, J. Friedel, F. D. Manchester, D. T. Peterson, J. M.
Rowe, K. S. Singwi, A. M. Stoneham, W. E. Wallace and T. Yamazaki
for their advice in the choice of scientific topics and organiza
tion of the symposium. We owe special gratitude to the local
organizing committee: Professors C. T. Butler, T. D. Doiron, D. W.
Hartman, W. J. Kossler, H. E. Schone, J. Ruvalds, C. E. Stronach,
and K. R. Squire for their help during the one and half year this
symposium was being planned. We are grateful to the faculty and
staff of the Physics Department of Virginia Commonwealth University,
in particular Professor R. H. Gowdy, Prof. G. B. Taggart, Mr. James
Spivey, Ms. Kim Hulce, and Miss Belinda Ashmore for their individual
help and advice.
This symposium was made possible by a generous grant from the
Special Program Panel on Materials Science of the North Atlantic
Treaty Organization. The symposium was hosted by the Virginia
Commonwealth University. We also acknowledge with thanks the finan
cial support of the Virginia Commonwealth University, the National
Science Foundation, the Exxon Corporation, and Philip Morris, U.S.A.
P. Jena
C. B. Satterthwaite
Richmond, Virginia
May, 1982
CONTENTS
PHASE DIAGRAMS, SPINODALS, AND THERMODESORPTION
Metal-Hydrogen Phase Diagrams . . . . . . . . . . . . . . 1
T. Schober
A Review of the Statistical Theory of the Phase-Change
Behavior of Hydrogen in Metals . . . . . . . 11
Carol K. Hall
Spinodals and Spinodal Mechanisms in M-H Systems 25
F.D. Manchester
What is the Relevance of Thermal Fluctuations for the
Spinodal Decomposition in a Coherent Metal-
Hydrogen System? .. . . . . . . . . . . . . . . . .. 43
Joseph W. Haus and Harald King
Enthalpy of Metal-Hydrogen Systems: A Pair-Bond Model 49
P. S. Rudman
Thermal Desorption Spectra of PdH System (O<x<O.9) in
Different Samples: a Powdef, a Foil, and a Wire 55
A. Stern, A. Resnik, D. Shaltiel, and S.R. Kreitzman
Fundamental Aspects of Thermodesorption Spectra in
Bulk Hydride Systems ......... . 61
S.R. Kreitzman, A. Stern, and D. Shaltiel
Thermal Desorption Spectroscopy (TDS) of Hydrogen from
Niobium . • . . . . . .. .... 67
V.J. Ghosh, M.A. Pick, D.O. Welch, and G.J. Dienes
The Concentration Profile of Hydrogen near the Surface
of Niobium . . .. ........•.•. 73
M.A. Pick, A. Hanson, K.W. Jones, and A.N. Goland
vii
viii CONTENTS
Theory of Hydrogen Absorption in Metal Hydrides 79
Tomoyasu Tanaka and Daniel E. Azofeifa
STRUCTURAL PROPERTIES, SITE OCCUPANCIES,
AND ELASTIC INTERACTIONS
Stabilities, Stoichiometries, and Site Occupancies in
Hydrides of Intermeta11ic Compounds . • . • . • . . . • . 85
D.G. Westlake
Octahedral Site Occupation in Lanthanum Dihydride . • . . • • • 97
E.L. Venturini
Thermodynamic and Structural Properties of the Rare-Earth
C03 Hydrides • • • • . • • • . . . • . . • . • . • . . . 103
Henry A. Kierstead
Measurement of Three Dimensional Distributions of Hydrogen
in Thin Samples using the 15N Hydrogen Profiling
Method • • • • • . • • • . . . . • . . . . • . · 109
W.A. Lanford and C. Burman
Strain Effects in the X-ray Determination of Lattice
Parameters in Pd-H. .•..• • 115
x
P.A. Hardy, I.S. Ba1baa, and F.D. Manchester
Lattice Distortions and Phase Transitions of Hydrogen in
Niobium · 117
H. Peis1
Forces, Dipole Force Tensor, and Elastic Binding Energy in
a-Palladium Hydrides • • • • • • • • • • • • • . • 119
J. Kha1ifeh, G. Moraitis, and C. Demangeat
Relaxation, Electronic, and Volume Expansion Contributions
to the Elastic Constant Changes Induced by Hydrogen
and Deuterium in Nb • • • • • • • • • • • • . • • • • • 125
F.M. Mazzo1ai and H.K. Birnbaum
Low Temperature Ultrasonic Attenuation in Rapidly Cooled
Niobium Containing Oxygen and Hydrogen • • • . · 133
K.F. Huang, A.V. Granato, and H.K. Birnbaum
Ultrasonic Attenuation Measurements in Single Crystal PdH 65. . 139
T. Kanashiro, D.K. Hsu, R.G. Leisure, and P.C. Riedi .
Contribution of Optical Phonons to the Elastic Moduli of
PdH and PdD ••••••••••••••••.•• • 145
B.M. G~erken, R~ Griessen, L.M. Huisman, and E. Walker
CONTENTS ix
NEUTRON SCATTERING
Neutron Spectroscopic Studies of Dilute Hydrogen in Pure
and Defected Metals . . . . . . . . . . . . . · 151
J.J. Rush
Structure and Phase Transitions in V2D and V2H · 153
S.C. Moss
Hydrogen Vibrations in Nickel Hydride . . . . . . . . . . . · 165
J. Eckert, C.F. Majkrzak, L. Passell, W.B. Daniels, and
T.A. Kitchens
Localized Vibrations of H in Nb and Ta at High Concentration
and Low Temperatures • . . . . . · 167
J. Eckert, J.A. Goldstone, and D. Richter
Tetrahedral and Octahedral Site Occupancy and Optic Mode
Vibrations of Hydrogen in Yttrium . . . . . . 169
J.A. Goldstone, J. Eckert, E.L. Venturini, and P.M.
Richards
Influence of Substitutional and Interstitial Impurities on
Local Hydrogen Modes in Nb ..•... . ..... 171
A. Magerl, J.J. Rush, J.M. Rowe, D. Richter, and H. Wipf
Quasielastic Neutron Scattering in Metal Hydrides: Effects
of the Quantum Mechanical Motion of Interstitial
Hydrogen Atoms •. .. •.•••......•.•.. 177
D.W. Brown and V.M. Kenkre
A Study of Hydrogen Site Occupation in the Yttrium-Hydrogen
Solid Solution Phase Using Inelastic Neutron
Scattering • . • • . . . . . . . . ....•..• 183
J.E. Bonnet, S.K.P. Wilson, and D.K. Ross
Neutron Scattering Studies of the Low Temperature Transition
in ex' PdD . . . . . . . • . • . . • . • • . . . . .• . 189
R.A. Bond, I.S. Anderson, B.S. Bowerman, C.J. Carlile,
D.J. Picton, D.K. Ross, D.G. Witchell, and J.K. Kjems
Properties of Vanadium-Alloy Dihydrides • . . . . . . . . 197
H.G. Severin and E. Wicke
Temperature Dependence of Intrinsic Disorder in LaH and
YH . • . . .. . ..•...•••..•x .•..•. 205
PeterxM. Richards
x CONTENTS
ELECTRONIC STRUCTURE
Electronic Structure of Metal Hydrides: A Review of
Experimental and Theoretical Progress • . · 207
J.H. Weaver, D.J. Peterman and D.T. Peterson
The Electronic Structure of PdH Studied with Photoemission
and Electron Energy Loss Spectroscopy . . • . . . . . · 223
P. Bennett and J.C. Fuggle
XPS/UPS Study of the Electronic Structure of PdHO.6 ...... 229
L. Schlapbach and J.P. Burger
Electronic Structure of Metal Hydrides and Deuterides from
de Haas van Alphen Measurements • . . . . • . . · 235
R. Griessen and L.M. Huisman
Electronic Structure of Non-Stoichiometric Transition Metal
Hydrides . . .• ......... . . . . · 249
A. Bansil, R. Prasad and L. Schwartz
A Simple Tight Binding Description of the Electronic Structure
of a Single and a Pair of Hydrogen Atoms in fcc Transi-
tion Metals . • . . • . . . . . . • . . . . . . . . . . • 265
M.A. Khan, J.C. Parlebas, and C. Demangeat
Theoretical Studies of Dilute Hydrogen Impurities in
Palladium . ••.. . • . . . . . . .. ..... 277
Barry M. Klein and Warren E. Pickett
Electronic Structure of Interstitial Hydrogen in Aluminum . . . 283
Raju P. Gupta
Calculation of the Ground State Energy of Hydrogen at
Interstitial Sites in a Lithium Cluster . . • . . . • • . 291
D.D. Schillady, T. Nguyen, and P. Jena
Parametrization of the Self-consistently Calculated Electronic
Densities Around a Proton in Jellium • • . • . . • . • . 299
S. Estreicher and P.F. Meier
Electronic Structure of Vanadium-Hydrogen Clusters . • • • . . 307
G. Bambakidis, M.P. Guse, and G.C. Abell
SUPERCONDUCTIVITY
Superconductivity in Metal-Hydrogen Systems • • • • • • . . • . 309
B. Stritzker
