Surface Science -- Contents -- Acknowledgements -- Introduction -- I.1 Heterogeneous catalysis -- I.2 Why surfaces? -- I.3 Where are heterogeneous reactions important? -- I.3.1 Haber-Bosch process -- I.3.2 Fischer-Tropsch chemistry -- I.3.3 Three-way catalyst -- I.4 Semiconductor processing and nanotechnology -- I.5 Other areas of relevance -- I.6 Structure of the book -- References -- 1 Surface and Adsorbate Structure -- 1.1 Clean surface structure -- 1.1.1 Ideal flat surfaces -- 1.1.2 High index and vicinal planes -- 1.1.3 Faceted surfaces -- 1.1.4 Bimetallic surfaces -- 1.1.5 Oxide and compound semiconductor surfaces -- 1.1.6 The carbon family: Diamond, graphite, graphene, fullerenes and carbon nanotubes -- 1.1.7 Porous solids -- 1.2 Reconstruction and adsorbate structure -- 1.2.1 Implications of surface heterogeneity for adsorbates -- 1.2.2 Clean surface reconstructions -- 1.2.3 Adsorbate induced reconstructions -- 1.2.4 Islands -- 1.2.5 Chiral surfaces -- 1.3 Band structure of solids -- 1.3.1 Bulk electronic states -- 1.3.2 Metals, semiconductors and insulators -- 1.3.3 Energy levels at metal interfaces -- 1.3.4 Energy levels at metal-semiconductor interfaces -- 1.3.5 Surface electronic states -- 1.3.6 Size effects in nanoscale systems -- 1.4 The vibrations of solids -- 1.4.1 Bulk systems -- 1.4.2 Nanoscale systems -- 1.5 Summary of important concepts -- 1.6 Frontiers and challenges -- 1.7 Further reading -- 1.8 Exercises -- References -- 2 Experimental Probes and Techniques -- 2.1 Ultrahigh vacuum -- 2.1.1 The need for UHV -- 2.1.2 Attaining UHV -- 2.2 Light and electron sources -- 2.2.1 Types of lasers -- 2.2.2 Atomic lamps -- 2.2.3 Synchrotrons -- 2.2.4 Free electron laser (FEL) -- 2.2.5 Electron guns -- 2.3 Molecular beams -- 2.3.1 Knudsen molecular beams -- 2.3.2 Free Jets -- 2.3.3 Comparison of Knudsen and supersonic beams.

2.4 Scanning probe techniques -- 2.4.1 Scanning tunnelling microscopy (STM) -- 2.4.2 Scanning tunnelling spectroscopy (STS) -- 2.4.3 Atomic force microscopy (AFM) -- 2.4.4 Near-field scanning optical microscopy (NSOM) -- 2.5 Low energy electron diffraction (LEED) -- Advanced Topic: LEED structure determination -- 2.6 Electron spectroscopy -- 2.6.1 X-ray photoelectron spectroscopy (XPS) -- 2.6.2 Ultraviolet photoelectron spectroscopy (UPS) -- Advanced Topic: Multiphoton photoemission (MPPE) -- 2.6.3 Auger electron spectroscopy (AES) -- 2.6.4 Photoelectron microscopy -- 2.7 Vibrational spectroscopy -- 2.7.1 IR spectroscopy -- 2.7.2 Electron energy loss spectroscopy (EELS) -- 2.8 Second harmonic and sum frequency generation -- 2.9 Other surface analytical techniques -- 2.10 Summary of important concepts -- 2.11 Frontiers and challenges -- 2.12 Further reading -- 2.13 Exercises -- References -- 3 Chemisorption, Physisorption and Dynamics -- 3.1 Types of interactions -- 3.2 Binding sites and diffusion -- 3.3 Physisorption -- Advanced Topic: Theoretical Description of Physisorption -- 3.4 Non-dissociative chemisorption -- 3.4.1 Theoretical treatment of chemisorption -- 3.4.2 The Blyholder model of CO chemisorption on a metal -- 3.4.3 Molecular oxygen chemisorption -- 3.4.4 The binding of ethene -- 3.5 Dissociative chemisorption: H2 on a simple metal -- 3.6 What determines the reactivity of metals? -- 3.7 Atoms and molecules incident on a surface -- 3.7.1 Scattering channels -- 3.7.2 Non-activated adsorption -- 3.7.3 Hard cube model -- 3.7.4 Activated adsorption -- 3.7.5 Direct versus precursor mediated adsorption -- 3.8 Microscopic reversibility in Ad/Desorption phenomena -- 3.9 The influence of individual degrees of freedom on adsorption and desorption -- 3.9.1 Energy exchange -- 3.9.2 PES topography and the relative efficacy of energetic components.

3.10 Translations, corrugation, surface atom motions -- 3.10.1 Effects on adsorption -- 3.10.2 Connecting adsorption and desorption with microscopic reversibility -- 3.10.3 Normal energy scaling -- 3.11 Rotations and adsorption -- 3.11.1 Non-activated adsorption -- 3.11.2 Activated adsorption -- 3.12 Vibrations and adsorption -- 3.13 Competitive adsorption and collision induced processes -- Advanced Topic: High Energy Collisions -- 3.14 Classification of reaction mechanisms -- 3.14.1 Langmuir-Hinshelwood mechanism -- 3.14.2 Eley-Rideal mechanism -- 3.14.3 Hot atom mechanism -- 3.15 Measurement of sticking coefficients -- 3.16 Summary of important concepts -- 3.17 Frontiers and challenges -- 3.18 Further reading -- 3.19 Exercises -- References -- 4 Thermodynamics and Kinetics of Adsorption and Desorption -- 4.1 Thermodynamics of Ad/Desorption -- 4.1.1 Binding energies and activation barriers -- 4.1.2 Thermodynamic quantities -- 4.1.3 Some definitions -- 4.1.4 The heat of adsorption -- 4.2 Adsorption isotherms from thermodynamics -- 4.3 Lateral interactions -- 4.4 Rate of desorption -- 4.4.1 First-order desorption -- 4.4.2 Transition state theory treatment of first-order desorption -- 4.4.3 Thermodynamic treatment of first-order desorption -- 4.4.4 Non-first-order desorption -- 4.5 Kinetics of adsorption -- 4.5.1 CTST approach to adsorption kinetics -- 4.5.2 Langmuirian adsorption: Non-dissociative adsorption -- 4.5.3 Langmuirian adsorption: Dissociative adsorption -- 4.5.4 Dissociative Langmuirian adsorption with lateral interactions -- 4.5.5 Precursor mediated adsorption -- 4.6 Adsorption isotherms from kinetics -- 4.6.1 Langmuir isotherm -- 4.6.2 Classification of adsorption isotherms -- 4.6.3 Thermodynamic measurements via isotherms -- 4.7 Temperature programmed desorption (TPD) -- 4.7.1 The basis of TPD -- 4.7.2 Qualitative analysis of TPD spectra.

4.7.3 Quantitative analysis of TPD spectra -- 4.8 Summary of important concepts -- 4.9 Frontiers and challenges -- 4.10 Further reading -- 4.11 Exercises -- References -- 5 Liquid Interfaces -- 5.1 Structure of the liquid/solid interface -- 5.1.1 The structure of the water/solid interface -- 5.2 Surface energy and surface tension -- 5.2.1 Liquid surfaces -- 5.2.2 Curved interfaces -- 5.2.3 Capillary waves -- 5.3 Liquid films -- 5.3.1 Liquid-on-solid films -- 5.4 Langmuir films -- 5.5 Langmuir-Blodgett films -- 5.5.1 Capillary condensation and meniscus formation -- 5.5.2 Vertical deposition -- 5.5.3 Horizontal lifting (Shaefer's method) -- 5.6 Self assembled monolayers (SAMs) -- 5.6.1 Thermodynamics of self-assembly -- 5.6.2 Amphiphiles and bonding interactions -- 5.6.3 Mechanism of SAM formation -- Advanced Topic: Chemistry with Self Assembled Monolayers -- 5.7 Thermodynamics of liquid interfaces -- 5.7.1 The Gibbs model -- 5.7.2 Surface excess -- 5.7.3 Interfacial enthalpy and internal, Helmholtz and Gibbs surface energies -- 5.7.4 Gibbs adsorption isotherm -- 5.8 Electrified and charged interfaces -- 5.8.1 Surface charge and potential -- 5.8.2 Relating work functions to the electrochemical series -- 5.9 Summary of important concepts -- 5.10 Frontiers and challenges -- 5.11 Further reading -- 5.12 Exercises -- References -- 6 Heterogeneous Catalysis -- 6.1 The prominence of heterogeneous reactions -- 6.2 Measurement of surface kinetics and reaction mechanisms -- 6.3 Haber-Bosch process -- 6.4 From microscopic kinetics to catalysis -- 6.4.1 Reaction kinetics -- 6.4.2 Kinetic analysis using De Donder relations -- 6.4.3 Definition of the rate determining step (RDS) -- 6.4.4 Microkinetic analysis of ammonia synthesis -- 6.5 Fischer-Tropsch synthesis and related chemistry -- 6.6 The three-way automotive catalyst -- 6.7 Promoters -- 6.8 Poisons.

6.9 Bimetallic and bifunctional catalysts -- 6.10 Rate oscillations and spatiotemporal pattern formation -- Advanced Topic: Cluster assembled catalysts -- 6.11 Sabatier analysis and optimal catalyst selection -- 6.12 Summary of important concepts -- 6.13 Frontiers and challenges -- 6.14 Further reading -- 6.15 Exercises -- References -- 7 Growth and Epitaxy -- 7.1 Stress and strain -- 7.2 Types of interfaces -- 7.2.1 Strain relief -- 7.3 Surface energy, surface tension and strain energy -- 7.4 Growth modes -- 7.4.1 Solid-on-solid growth -- 7.4.2 Strain in solid-on-solid growth -- 7.4.3 Ostwald ripening -- 7.4.4 Equilibrium overlayer structure and growth mode -- 7.5 Nucleation theory -- 7.6 Growth away from equilibrium -- 7.6.1 Thermodynamics versus dynamics -- 7.6.2 Non-equilibrium growth modes -- 7.7 Techniques for growing layers -- 7.7.1 Molecular beam epitaxy (MBE) -- 7.7.2 Chemical vapour deposition (CVD) -- 7.7.3 Ablation techniques -- 7.8 Catalytic growth of nanotubes and nanowires -- 7.9 Etching -- 7.9.1 Classification of etching -- 7.9.2 Etch morphologies -- 7.9.3 Porous solid formation -- 7.9.4 Silicon etching in aqueous fluoride solutions -- 7.9.5 Coal gasification and graphite etching -- 7.9.6 Selective area growth and etching -- Advanced Topic: Si Pillar Formation -- 7.10 Summary of important concepts -- 7.11 Frontiers and challenges -- 7.12 Further reading -- 7.13 Exercises -- References -- 8 Laser and Non-Thermal Chemistry: Photon and Electron Stimulated Chemistry and Atom Manipulation -- 8.1 Photon excitation of surfaces -- 8.1.1 Light absorption by condensed matter -- 8.1.2 Lattice heating -- Advanced Topic: Temporal evolution of electronic excitations -- 8.1.3 Summary of laser excitations -- 8.2 Mechanisms of electron and photon stimulated processes -- 8.2.1 Direct versus substrate mediated processes -- 8.2.2 Gas phase photochemistry.

8.2.3 Gas phase electron stimulated chemistry.