Roald Hoffmann - Solids and Surfaces

1 COVER

2 TITLE PAGE Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures Roald Hoffmann

3 COPYRIGHT PAGE 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

4 DEDICATION PAGE for Earl Muetterties and Mike Sienko

5 PREFACE AND ACKNOWLEDGMENTS

6 INTRODUCTION

7 ORBITALS AND BANDS IN ONE DIMENSION

8 BLOCH FUNCTIONS, k, BAND STRUCTURES

9 BANDWIDTH

10 SEE HOW THEY RUN

11 AN ECLIPSED STACK OF Pt(II) SQUARE PLANAR COMPLEXES

12 THE FERMI LEVEL

13 MORE DIMENSIONS, AT LEAST TWO

14 SETTING UP A SURFACE PROBLEM

15 DENSITY OF STATES

16 WHERE ARE THE ELECTRONS?

17 THE DETECTIVE WORK OF TRACING MOLECULE-SUREACE INTERACTIONS: DECOMPOSITION OF THE DOS

18 WHERE ARE THE BONDS?

19 A SOLID STATE SAMPLE PROBLEM: THE ThCr 2Si 2STRUCTURE

20 THE FRONTIER ORBITAL PERSPECTIVE

21 ORBITAL INTERACTION ON A SURFACE

22 A CASE STUDY: CO ON Ni(100)

23 BARRIERS TO CHEMISORPTION

24 CHEMISORPTION IS A COMPROMISE

25 FRONTIER ORBITAIS IN THREE-DIMENSIONAL EXTENDED STRUCTURES

26 MORE THAN ONE ELECTRONIC UNIT IN THE UNIT CELL. FOLDING BANDS

27 MAKING BONDS IN A CRYSTAL

28 THE PEIERLS DISTORTION

29 A BRIEF EXCURSION INTO THE THIRD DIMENSION

30 QUALITATIVE REASONING ABOUT ORBITAL INTERACTIONS ON SURFACES

31 THE FERMI LEVEL MATTERS

32 ANOTHER METHODOLOGY AND SOME CREDITS

33 WHAT’S NEW IN THE SOLID?

34 REFERENCES

35 INDEX

36 END USER LICENSE AGREEMENT

1 c01Figure 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 2are sho...Figure 13 z 2and 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 , πσ , 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 1bond in the one-fold (left) and th...Figure 26 A schematic picture of the Mn 2P 2 2−layer band structure as ...Figure 27 Band structure and DOS of a single Mn 2P 2 2−layer.Figure 28 Total DOS of the composite Mn 2P 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 zorbital contribution (dark area) to the total DOS (...Figure 32 Phosphorus 3p zorbital 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 o6S 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 2on Mg(0001), after Ref. 87. ...

1 Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures

2 Cover

3 Title Page

4 Copyright Page

5 Dedication Page

6 Preface and Acknowledgments

7 Table of Contents

8 Begin Reading

9 References

10 Index

11 WILEY END USER LICENSE AGREEMENT

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