Solids and Surfaces

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.Dieses einzigartige Buch läßt Chemie und Physik im festen Zustand und auf Oberflächen 'zusammentreffen'. In einer lebhaften und anschaulichen Weise bringt es Chemikern die Sprache bei, mit der sie die Elektronenstruktur ausgedehnter Systeme verstehen lernen können. Gleichzeitig zeigt es, wie auch von Seiten der Chemie Modelle über den festen Zustand sowie über Bindungen und Reaktivität von Oberflächen erstellt werden können.

Das Buch bedient sich zunächst der Sprache von Kristallorbitalen, Bandstrukturen und Zustandsdichten. Danach stellt es die Werkzeuge bereit, mit denen der Leser weg von den stark delokalisierten Orbitalen des Festkörpers gelangt, darunter der Zerfall von Zustandsdichten und die Population von Kristallorbital-Overlaps. Mit diesen Werkzeugen schafft es der Autor, detaillierte quantenmechanische Berechnungen mit der chemischen Betrachtungsweise mit Grenzorbitalen zu verknüpfen. Die beschriebenen Anwendungen umfassen eine allgemeine Vorstellung der Chemisorption, Bindungsbildung und -zerfall im festen Zustand, Bindungen im Metall, die Elektronenstruktur ausgewählter leitender und supraleitender Verbindungen sowie die für die Deformation ausgedehnter Systeme verantwortlichen Kräfte. Preface

Introduction

Orbitals and Bands in One Dimension

Bloch Functions, k, Band Structures

Band Width

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-Surface Interactions: Decomposition of the DOS

Where Are the Bonds?

A Solid State Sample Problem: ThCr_2Si_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

Frontiers Orbitals 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

Roald Hoffmann, born in Zloczow, Poland but educated in the US, is the Frank H. T. Rhodes Professor of Humane Letters at Cornell University. One of America's most distinguished chemists, he was awarded the Nobel Prize in Chemistry. A member of the US National Academy of Sciences and the American Academy of Arts and Sciences as well as many foreign academies, Hoffmann has received 26 honorary doctorates together with numerous other honors such as the National Medal of Science. Hoffmann is the only person ever to receive the American Chemical Society's top awards in three sub- disciplines: organic chemistry, inorganic chemistry, and chemical education. For the past dozen years, Hoffmann has simultaneously pursued a literary career. He is the author of three books of poetry, "The Metamict State", "Gaps and Verges", and "Memory Effects". His three non-fiction books deal with the overall theme of the creative and humanistic sparks of chemistry: An art/science/literature collaboration with artist Vivian Torrence, "Chemistry Imagined"; "The Same and Not the Same"; and "Old Wine, New Flasks: Reflections on Science and Jewish Tradition," in collaboration with Shira Leibowitz Schmidt. Hoffmann is also is the presenter of a television course, "The World of Chemistry", which has aired on many PBS Stations and abroad.