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



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

Roald Hoffmann

ISBN: 978-0-471-18710-3 January 1989 152 Pages


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.


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