Elsevier S & T

Chemical Bonding at Surfaces and Interfaces

Nilsson, Anders; Pettersson, Lars G.M.; Norskov, Jens

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Table of contents
  • Cover
  • Table of Contentsv
  • Prefacexi
  • Chapter 1 Surface Structure1
  • 1. Why surface structure?1
  • 2. Methods of surface adsorbate structure determination2
  • 2.1. General comments2
  • 2.2. Electron scattering3
  • 2.3. X-ray scattering6
  • 2.4. Ion scattering8
  • 2.5. Spectroscopic methods and scanning probe microscopy9
  • 3. Adsorbate-induced surface reconstruction11
  • 4. Molecular adsorbates – local sites, orientations and intramolecular bondlengths19
  • 4.1. General issues and the case of CO on metals19
  • 4.2. Simple hydrocarbons on metals21
  • 4.3. Carboxylates on metals26
  • 4.4. Other substrates: molecules on Si33
  • 5. Chemisorption bondlengths38
  • 5.1. Metal surfaces38
  • 5.2. Oxide surfaces44
  • 6. Conclusions48
  • Chapter 2 Adsorbate Electronic Structure and Bonding on Metal Surfaces57
  • 1. Introduction57
  • 2. Probing the electronic structure58
  • 3. Adsorbate electronic structure and chemical bonding63
  • 4. Adsorbate systems68
  • 5. Radical atomic adsorption69
  • 5.1. The electronic structure of N on Cu(100)70
  • 5.2. Chemical bonding of atomic adsorbates75
  • 6. Diatomic molecules79
  • 6.1. N2 adsorbed on Ni(100)80
  • 6.2. CO adsorbed on Ni(100)91
  • 6.3. CO adsorbed on Cu(100) and other metals97
  • 6.4. CO adsorbed in different sites99
  • 6.5. Coadsorption of CO and K on Ni(100)101
  • 7. Unsaturated hydrocarbons103
  • 7.1. Ethylene (C2H4) adsorbed on Ni(110) and Cu(110)104
  • 7.2. Benzene on Ni and Cu surfaces111
  • 7.3. Bond energetics and rehybridization from spin-uncoupling113
  • 8. Saturated hydrocarbons119
  • 8.1. n-Octane adsorbed on Cu(110)120
  • 8.2. Difference between octane on Ni and Cu surfaces126
  • 9. Lone pair interactions127
  • 9.1. Water adsorption on Pt and Cu surfaces127
  • 9.2. Adsorption of ammonia and the amino group in glycine on Cu(110)131
  • 10. Summary134
  • Chapter 3 The Dynamics of Making and Breaking Bonds at Surfaces143
  • 1. Introduction143
  • 2. Theoretical background146
  • 2.1. Adiabatic dynamics (Born-Oppenheimer approximation)146
  • 2.2. Generic PES topologies149
  • 2.3. Dynamics vs. kinetics152
  • 2.3.1. Direct dissociation153
  • 2.3.2. Precursor-mediated dissociation156
  • 2.4. Detailed balance157
  • 2.5. Lattice coupling158
  • 2.5.1. Energy transfer in adsorption/scattering159
  • 2.5.2. Lattice coupling in direct molecular dissociation163
  • 2.6. Non-adiabatic dynamics164
  • 2.6.1. Hot electrons from chemistry165
  • 2.6.2. Chemistry from hot electrons169
  • 3. Experimental background172
  • 3.1. Experimental techniques173
  • 3.2. Typical measurements175
  • 3.2.1. Rate measurements175
  • 3.2.2. Adsorption-trapping and sticking176
  • 3.2.3. Desorption179
  • 3.2.4. Scattering180
  • 3.2.5. Initial state preparation181
  • 3.2.6. Photochemistry/femtochemistry181
  • 3.2.7. Single molecule chemistry (STM)182
  • 4. Processes182
  • 4.1. Atomic adsorption/desorption/scattering183
  • 4.1.1. Ar/Pt(111)183
  • 4.1.2. H/Cu(111)186
  • 4.2. Molecular adsorption/desorption/scattering188
  • 4.2.1. NO/Ag(111)188
  • 4.2.2. NO/Pt(111)195
  • 4.3. Direct dissociation/associative desorption198
  • 4.3.1. Activated dissociation198
  • 4.3.2. Weakly activated dissociation214
  • 4.3.3. Non-activated dissociation216
  • 4.4. Precursor-mediated dissociation/associative desorption219
  • 4.4.1. O2/Pt(111)219
  • 4.5. Direct and precursor-mediated dissociation223
  • 4.5.1. N2/W(100)223
  • 4.5.2. NH3/Ru(0001)226
  • 4.6. Langmuir-Hinschelwood chemistry227
  • 4.6.1. (O+CO)/Pt(111)227
  • 4.7. Eley-Rideal/Hot atom chemistry230
  • 4.7.1. H+H/Cu(111)230
  • 4.8. Hot electron chemistry235
  • 4.8.1. Photochemistry/femtochemistry235
  • 4.8.2. Single molecule chemistry240
  • 5. Summary and outlook242
  • Chapter 4 Heterogeneous Catalysis255
  • 1. Introduction255
  • 2. Factors determining the reactivity of a transition metal surface256
  • 3. Trends in adsorption energies on transition metal surfaces257
  • 4. The d-band model259
  • 4.1. One-electron energies and bond energy trends259
  • 4.2. The Newns-Anderson model262
  • 5. Trends in chemisorption energies267
  • 5.1. Variations in adsorption energies from one metal to the next267
  • 5.2. Ligand effects in adsorption – changing the d band center269
  • 5.2.1. Variations due to changes in surface structure270
  • 5.2.2. Variations due to alloying273
  • 5.3. Ensemble effects in adsorption – the interpolation principle275
  • 6. Trends in activation energies for surface reactions278
  • 6.1. Electronic effects in surface reactivity279
  • 6.2. Geometrical effects in surface reactivity281
  • 7. Brønsted-Evans-Polanyi relationships in heterogeneous catalysis283
  • 7.1. Correlations from DFT calculations283
  • 7.2. Universal relationships285
  • 8. Activation barriers and rates287
  • 8.1. Transition state theory288
  • 8.2. Variational transition state theory and recrossings291
  • 8.3. Harmonic transition state theory (HTST)292
  • 9. Variations in catalytic rates – volcano relations297
  • 9.1. Dissociation rate-determined model298
  • 9.2. A Le Chatelier-like principle for heterogeneous catalysis302
  • 9.3. Including molecular precursor adsorption303
  • 9.4. Sabatier analysis305
  • 9.5. A realistic desorption model307
  • 9.6. Database of chemisorption energies311
  • 10. The optimization and design of catalyst through modeling312
  • 10.1. The low-temperature water gas shift (WGS) reaction313
  • 10.2. Methanation313
  • 11. Conclusions and outlook316
  • Chapter 5 Semiconductor Surface Chemistry323
  • 1. Inroduction323
  • 2. Structure of semiconductor surfaces325
  • 2.1. Silicon surface structure326
  • 2.2. Germanium surface structure330
  • 3. Surface oxidation331
  • 3.1. Silicon331
  • 3.2. Germanium333
  • 4. Passivation of semiconductor surfaces334
  • 4.1. Silicon passivation334
  • 4.1.1. Hydride termination of silicon334
  • 4.2. Germanium passivation335
  • 4.2.1. Sulfide passivation of germanium336
  • 4.2.2. Chloride passivation of germanium337
  • 4.2.3. Hydride termination of germanium337
  • 5. Reactions at passivated semiconductor surfaces339
  • 5.1. Organic functionalization of semiconductor surface339
  • 5.2. Reaction with passivated silicon (Si−H and Si−Cl)339
  • 5.2.1. Hydrosilylation339
  • 5.2.2. Grignard reactions on silicon345
  • 5.3. Reaction with passivated germanium (Ge−H and Ge−Cl)346
  • 5.3.1. Grignard reactions on germanium347
  • 5.3.2. Hydrogermylation348
  • 5.3.3. Alkanethiol reactions on germanium349
  • 5.4. Reaction with compound semiconductors350
  • 6. Adsorption of organic molecules under vacuum conditions351
  • 6.1. Silicon surface chemistry352
  • 6.1.1. Cycloaddition reaction on Si(100)–2×1352
  • 6.1.2. Heterocycloadditions361
  • 6.1.3. Nucleophilic/electrophilic reactions362
  • 6.2. Germanium surface chemistry369
  • 6.2.1. Cycloaddition reactions on Ge(100)–2×1370
  • 6.2.2. Heterocycloadditions372
  • 6.2.3. Nucleophilic/electrophilic reactions374
  • 6.2.4. Multiple-layer reactions376
  • 6.3. Summary of concepts in organic functionalization378
  • Chapter 6 Surface Electrochemistry397
  • 1. Introduction397
  • 2. Special features of electrochemical reactions398
  • 2.1. Electrochemical current and potential399
  • 2.2. Electrochemical interfaces404
  • 2.3. Models of electrochemical electron transfer kinetics406
  • 3. Electrochemistry at the molecular scale412
  • 3.1. Surface structure412
  • 3.2. Bonding of ions413
  • 3.3. Bonding of water415
  • 3.4. Experimental aspects of current/voltage properties416
  • 4. Electrocatalytic reaction processes418
  • 4.1. The electrocatalytic reduction of oxygen420
  • 4.1.1. Background420
  • 4.1.2. Mechanistic pathways422
  • 4.1.3. Electroreduction of oxygen on Pt and Pt alloys423
  • 4.1.4. Recent quantum chemical studies of the ORR mechanism425
  • 4.1.5. State-of-the-art ORR electrocatalyst concepts431
  • 4.2. The electrochemical oxidation of small organic molecules435
  • 4.2.1. The electrooxidation of carbon monoxide438
  • 4.2.2. The electrooxidation of formic acid and methanol444
  • 5. Summary and outlook448
  • Chapter 7 Geochemistry of Mineral Surfaces and Factors Affecting Their Chemical Reactivity457
  • 1. Introduction457
  • 2. Environmental interfaces461
  • 2.1. Common minerals in Earth’s crust, soils, and atmosphere, weathering mechanisms and products,461
  • 2.2. Solubilities of Al- and Fe(III)-oxides and Al and Fe(III)-(oxy)hydroxides466
  • 2.3. Dissolution mechanisms at feldspar–water interfaces469
  • 2.4. The nature of metal oxide-aqueous solution interfaces – some basics472
  • 3. Factors affecting the chemical reactivity of mineral surfaces478
  • 3.1. The reaction of water vapor with metal oxide surfaces – surface science and theoretical studi479
  • 3.2. Grazing incidence EXAFS spectroscopic studies of Pb(II)aq adsorption on metal oxide surfaces ??484
  • 3.3. The structure of hydrated metal oxide surfaces from X-ray diffraction studies488
  • 3.4. X-ray standing wave studies of the electrical double layer at solid-aqueous solution interfaces496
  • 3.5. Effect of organic coatings and microbial biofilms on metal oxide surface reactivity – X-ray s499
  • 4. Conclusions504
  • Index511
Book details
  • Vendor Elsevier S & T
  • SKU 9780444528377
  • ISBN-13 9780444528377
  • Author Nilsson, Anders; Pettersson, Lars G.M.; Norskov, Jens
  • Category Science
  • Subject Physical & Theoretical

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Molecular surface science has made enormous progress in the past 30 years. The development can be characterized by a revolution in fundamental knowledge obtained from simple model systems and by an explosion in the number of experimental techniques. The last 10 years has seen an equally rapid development of quantum mechanical modeling of surface processes using Density Functional Theory (DFT).
Chemical Bonding at Surfaces and Interfaces focuses on phenomena and concepts rather than on experimental or theoretical techniques. The aim is to provide the common basis for describing the interaction of atoms and molecules with surfaces and this to be used very broadly in science and technology.
The book begins with an overview of structural information on surface adsorbates and discusses the structure of a number of important chemisorption systems. Chapter 2 describes in detail the chemical bond between atoms or molecules and a metal surface in the observed surface structures. A detailed description of experimental information on the dynamics of bond-formation and bond-breaking at surfaces make up Chapter 3. Followed by an in-depth analysis of aspects of heterogeneous catalysis based on the d-band model. In Chapter 5 adsorption and chemistry on the enormously important Si and Ge semiconductor surfaces are covered. In the remaining two Chapters the book moves on from solid-gas interfaces and looks at solid-liquid interface processes. In the final chapter an overview is given of the environmentally important chemical processes occurring on mineral and oxide surfaces in contact with water and electrolytes.

* Gives examples of how modern theoretical DFT techniques can be used to design heterogeneous catalysts
* This book suits the rapid introduction of methods and concepts from surface science into a broad range of scientific disciplines where the interaction between a solid and the surrounding gas or liquid phase is an essential component
* Shows how insight into chemical bonding at surfaces can be applied to a range of scientific problems in heterogeneous catalysis, electrochemistry, environmental science and semiconductor processing
* Provides both the fundamental perspective and an overview of chemical bonding in terms of structure, electronic structure and dynamics of bond rearrangements at surfaces