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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
This unique book shows how chemistry and physics come together in the solid state and on surfaces. Using a lively, graphic, descriptive approach, it teaches chemists the language that is necessary to understand the electronic structure of extended systems. And, at the same time, it demonstrates how a chemical, frontier-orbital, approach to solid state and surface bonding and reactivity may be constructed. The book begins with the language of crystal orbitals, band structures and densities of states. The tools for moving back from the highly delocalized orbitals of the solid are then built up in a transparent manner; they include decompositions of the densities of states and crystal orbital overlap populations. Using these tools, the book shapes a meeting ground between detailed quantum mechanical calculations and a chemical frontier orbital perspec- tive. Applications include a general picture of chemisorption, bond-breaking and making in the solid state, bonding in metals, the electronic structure of selected conducting and supercon- ducting structures, dissociation, migration and coupling on surfaces and the forces controlling deformation of extended systems.
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Veröffentlichungsjahr: 2021
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Table of Contents
COVER
TITLE PAGE
COPYRIGHT PAGE
DEDICATION PAGE
PREFACE AND ACKNOWLEDGMENTS
INTRODUCTION
ORBITALS AND BANDS IN ONE DIMENSION
BLOCH FUNCTIONS,
k,
BAND STRUCTURES
BANDWIDTH
SEE HOW THEY RUN
AN ECLIPSED STACK OF Pt(II) SQUARE PLANAR COMPLEXES
THE FERMI LEVEL
MORE DIMENSIONS, AT LEAST TWO
SETTING UP A SURFACE PROBLEM
DENSITY OF STATES
WHERE ARE THE ELECTRONS?
THE DETECTIVE WORK OF TRACING MOLECULE-SUREACE INTERACTIONS: DECOMPOSITION OF THE DOS
WHERE ARE THE BONDS?
A SOLID STATE SAMPLE PROBLEM: THE ThCr
2
Si
2
STRUCTURE
THE FRONTIER ORBITAL PERSPECTIVE
ORBITAL INTERACTION ON A SURFACE
A CASE STUDY: CO ON Ni(100)
BARRIERS TO CHEMISORPTION
CHEMISORPTION IS A COMPROMISE
FRONTIER ORBITAIS IN THREE-DIMENSIONAL EXTENDED STRUCTURES
MORE THAN ONE ELECTRONIC UNIT IN THE UNIT CELL. FOLDING BANDS
MAKING BONDS IN A CRYSTAL
THE PEIERLS DISTORTION
A BRIEF EXCURSION INTO THE THIRD DIMENSION
QUALITATIVE REASONING ABOUT ORBITAL INTERACTIONS ON SURFACES
THE FERMI LEVEL MATTERS
ANOTHER METHODOLOGY AND SOME CREDITS
WHAT’S NEW IN THE SOLID?
REFERENCES
INDEX
END USER LICENSE AGREEMENT
List of Illustrations
c01
Figure 1 The band structure of a chain of hydrogen atoms spaced 3, 2, and 1 ...
Figure 2 Molecular orbital derivation of the frontier orbitals of a square p...
Figure 3 Computed band structure of an eclipsed PtH
4
2–
stack, spaced ...
Figure 4 The band structure of a square lattice of H atoms, H–H separation 2...
Figure 5 Schematic band structure of a planar square lattice of atoms bearin...
Figure 6 Band structures of square monolayers of CO at two separations: (a) ...
Figure 7 The band structure of a four-layer Ni slab that serves as a model f...
Figure 8 Band structure and density of states for an eclipsed PtΗ
4
2−
...
Figure 9 The density of states (right) corresponding to the band structure (...
Figure 10 Band structure and density of states for rutile, TiO
2
.
Figure 12 Contributions of Ti and O to the total DOS of rutile, TiO
2
are sho...
Figure 13 z
2
and z contributions to the total DOS of an eclipsed PtH
4
2−
...
Figure 14 The total density of states of a model
c
(2 × 2)CO–Ni(100) system (...
Figure 15 For the
c
(2 × 2)CO–Ni(100) model this shows the 5
σ
and 2
π
...
Figure 16 Interaction diagrams for 5
σ
and 2
π
* of
c
(2 × 2)C)–Ni...
Figure 17 From left to right: contributions of
π
,
π
σ
,
π
...
Figure 18 That part of the total DOS (dashed line) which is in the H
2
σ
...
Figure 19 The orbitals of N
2
(left) and a “solid state way” to plot the DOS ...
Figure 20 Total density of states (left), and Pt–H (middle) and Pt–Pt (right...
Figure 21 DOS and Ti–O COOP for rutile.
Figure 22 Total DOS (dashed line) and 4s and 4p contributions to it in bulk ...
Figure 23 The total DOS and nearest neighbor Ni–Ni COOP in bulk Ni.
Figure 24 Crystal orbital overlap population for CO, on top, in a
c
(2 × 2)CO...
Figure 25 COOP curve for the α–carbon–Pt
1
bond in the one-fold (left) and th...
Figure 26 A schematic picture of the Mn
2
P
2
2−
layer band structure as ...
Figure 27 Band structure and DOS of a single Mn
2
P
2
2−
layer.
Figure 28 Total DOS of the composite Mn
2
P
2
2−
layer lattice (dashed li...
Figure 29 Crystal orbital overlap population curves for the Mn–Mn bonds (sol...
Figure 30 Total DOS of the P sublattice (left), the Mn sublattice (middle), ...
Figure 31 Phosphorus 3p
z
orbital contribution (dark area) to the total DOS (...
Figure 32 Phosphorus 3p
z
orbital contribution (dark area) to the total DOS (...
Figure 33 Schematic drawing showing how the interactions of levels (bottom) ...
Figure 34 The frontier orbitals of an M
o6
S
8
4−
cluster, with some sele...
Figure 35 The band structure of a staggered PtH
4
2−
stack (left), comp...
Figure 36 A comparison of the DOS of staggered (left) and eclipsed (right) P...
Figure 37 The band structure for VS in the NiAs structure (left), together w...
Figure 38 The evolution of the contribution of methyl lone pairs to the DOS ...
Figure 39 Some calculated characteristics of H
2
on Mg(0001), after Ref. 87. ...
Guide
Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures
Cover
Title Page
Copyright Page
Dedication Page
Preface and Acknowledgments
Table of Contents
Begin Reading
References
Index
WILEY END USER LICENSE AGREEMENT
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Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures
Roald Hoffmann
A NOTE TO THE READER:
This book has been electronically reproduced from digital information stored at John Wiley & Sons, Inc. We are pleased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.
Copyright © 1988 by Wiley-VCH Inc. All rights reserved.
Originally published as ISBN 0-89573-709-4
Published simultaneously in Canada.
No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 and 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012. (212) 850-6011, fax (212) 850-6008, E-mail: PERMREQ@WILEY.COM.
Library of Congress Cataloging-in-Publication Data
Hoffmann,Roald.
Solids and Surfaces: A Chemist’s View on Bonding in Extended Structures.
p. cm.
Bibliography: p.
Includes index.
ISBN 0-471-18710-0
1. Chemical Bonds 2. Surface Chemistry. 3. Solid state chemistry
I. Title.
QD471.H83 1988
541.2’24 -- dc 20
88-14288
CIP
for
Earl Muetterties
and
Mike Sienko
Preface and Acknowledgments
The material in this book has been published in two articles in Angewandte Chemic and Reviews of Modern Physics, and I express my gratitude to the editors of these journals for their encouragement and assistance. The construction of the book based on those articles was suggested by my friend M. V. Basilevsky.
My graduate students, postdoctoral associates, and senior visitors to the group are responsible for both teaching me solid state physics and implementing the algorithms and computer programs that have made this work possible. While in my usual way I’ve suppressed the computations in favor of explanations, little understanding would have come without those computations. An early contribution to our work was made by Chien-Chuen Wan, but the real computational and interpretational advances came through the work of Myung-Hwan Whangbo, Charles Wilker, Miklos Kertesz, Tim Hughbanks, Sunil Wijeyesekera, and Chong Zheng. This book very much reflects their ingenuity and perseverance. Several crucial ideas were borrowed early on from Jeremy Burdett, such as using special k-point sets for properties.
Al Anderson was instrumental in getting me started in thinking about applying extended Hückel calculations to surfaces. A coupling of the band approach to an interaction diagram and frontier orbital way of thinking evolved from the study Jean-Yves Saillard carried out of molecular and surface C–H activation. We learned a lot together. A subsequent collaboration with Jérome Silvestre helped to focus many of the ideas in this book. Important contributions were also made by Christian Minot, Dennis Underwood, Shen-shu Sung, Georges Trinquier, Santiago Alvarez, Joel Bernstein, Yitzhak Apeloig, Daniel Zeroka, Douglas Keszler, William Bleam, Ralph Wheeler, Marja Zonnevylle, Susan Jansen, Wolfgang Tremel, Dragan Vučkovič, and Jing Li.
An important factor in the early stages of this work was my renewed collaboration with R. B. Woodward, prompted by our joint interest in organic conductors. Our collaboration was unfortunately cut short by his death in 1979- Thor Rhodin was mainly responsible for introducing me to the riches of surface chemistry and physics, and I am grateful to him and his students. It was always instructive to try to provoke John Wilkins.
Over the years my research has been steadily supported by the National Science Foundation’s Chemistry Division. I owe Bill Cramer and his fellow program directors thanks for their continued support. A special role in my group’s research on extended structures was played by the Materials Science Center (MSC) at Cornell University, supported by the Materials Research Division of the National Science Foundation. MSC furnished an interdisciplinary setting, which facilitated an interaction among researchers in the surface science and solid state areas that was very effective in introducing a novice to the important work in the field. I am grateful to Robert E. Hughes, Herbert H. Johnson, and Robert H. Silsbee, the MSC directors, for providing that supporting structure. In the last five years my surface-related research has been generously supported by the Office of Naval Research. That support is in the form of a joint research program with John Wilkins.
One reason it is easy to cross disciplines at Cornell is the existence of the Physical Sciences Library, with its broad coverage of chemistry and physics. I would like to thank Ellen Thomas and her staff for her contributions in that regard. Our drawings, a critical part of the way our research is presented, have been beautifully prepared over the years by Jane Jorgensen and Elisabeth Fields. I’d like to thank Eleanor Stagg, Linda Kapitany, and Lorraine Seager for their typing and secretarial assistance.
This manuscript was written while I held the Tage Erlander Professorship of the Swedish Science Research Council, NFR. The hospitality of Professor Per Siegbahn and the staff of the Institute of Theoretical Physics of the University of Stockholm and of Professor Sten Andersson and his crew at the Department of Inorganic Chemistry at the Technical University of Lund is gratefully acknowledged.
Finally, this book is dedicated to two men, colleagues of mine at Cornell in their time. They are no longer with us. Earl Muetterties played an important role in introducing me to inorganic and organometallic chemistry. Our interest in surfaces grew together. Mike Sienko and his students offered gentle encouragement by showing us the interesting structures on which they worked; Mike also taught me something about the relationship between research and teaching. This book is for them—both Earl Muetterties and Mike Sienko—who were so important and dear to me.
