Preface xi

1 Surface Structure 1

1 Why surface structure? 1

2 Methods of surface adsorbate structure determination 2

3 Adsorbate-induced surface reconstruction 11

4 Molecular adsorbates local sites, orientations and intramolecular bondlengths 19

5 Chemisorption bondlengths 38

6 Conclusions 48

2 Adsorbate Electronic Structure and Bonding on Metal Surfaces 57

1 Introduction 57

2 Probing the electronic structure 58

3 Adsorbate electronic structure and chemical bonding 63

4 Adsorbate systems 68

5 Radical atomic adsorption 69

6 Diatomic molecules 79

7 Unsaturated hydrocarbons 103

8 Saturated hydrocarbons 119

9 Lone pair interactions 127

10 Summary 134

3 The Dynamics of Making and Breaking Bonds at Surfaces 143

1 Introduction 143

2 Theoretical background 146

3 Experimental background 172

4 Processes 182

5 Summary and outlook 242

4 Heterogeneous Catalysis 255

1 Introduction 255

2 Factors determining the reactivity of a transition metal surface 256

3 Trends in adsorption energies on transition metal surfaces 257

4 The d-band model 259

5 Trends in chemisorption energies 267

6 Trends in activation energies for surface reactions 278

7 Brønsted-Evans-Polanyi relationships in heterogeneous catalysis 283

8 Activation barriers and rates 287

9 Variations in catalytic rates volcano relations 297

10 The optimization and design of catalyst through modeling 312

11 Conclusions and outlook 316

5 Semiconductor Surface Chemistry 323

1 Introduction 323

2 Structure of semiconductor surfaces 325

3 Surface oxidation 331

4 Passivation of semiconductor surfaces 334

5 Reactions at passivated semiconductor surfaces 339

6 Adsorption of organic molecules under vacuum conditions 351

6 Surface Electrochemistry 397

1 Introduction 397

2 Special features of electrochemical reactions 398

3 Electrochemistry at the molecular scale 412

4 Electrocatalytic reaction processes 418

5 Summary and outlook 448

7 Geochemistry of Mineral Surfaces and Factors Affecting Their Chemical Reactivity 457

1 Introduction 457

2 Environmental interfaces 461

3 Factors affecting the chemical reactivity of mineral surfaces 478

4 Conclusions 504

Index 511