Atomic Clusters (eBook)

Cover 1
Preface 12
Contents 14
Chapter 1. Size effects in the chemistry of small clusters 24
1. Introduction 24
2. CO Oxidation on Small Gold Clusters 28
3. The CO Chemistry of Supported PdN Clusters 44
4. The Polymerization of Acetylene on Supported Clusters 60
5. Size-Selected, Supported Clusters: Exciting New Model Systems for Electrocatalysis 68
6. Conclusion 70
Note 70
References 70
Chapter 2. Chemical reactivity and catalytic properties of size-selected gas-phase metal clusters 76
1. Introduction 76
2. Experimental Techniques in Cluster Ion Chemistry 78
3. Concepts in Cluster Ion Chemistry 87
4. Catalytic Activity of Gas-Phase Clusters 88
5. Concluding Remarks 109
References 110
Chapter 3. Probing the unique size-dependent properties of small au clusters, au alloy clusters, and Co-chemisorbed au clusters in the gas phase 114
1. Introduction 114
2. Experimental Method 116
3. Electronic and Structural Properties of Elemental Gold Clusters 118
4. Novel Gold Alloy Clusters 134
5. Gold as Hydrogen in Si–Au and B–Au Clusters 145
6. CO Chemisorption on Au Clusters: Implications for Nanogold Catalysis 161
7. Concluding Remarks 168
Note Added in Proof 169
Acknowledgments 169
References 169
Chapter 4. Aun and Agn (=1–8) nanocluster catalysts: gas-phase reactivity to deposited structures 174
1. Introduction 174
2. Experimental Methods 175
3. Interactions Between Aun and Agn Cluster Ions and Small Alkenes 182
4. Aun+ and Agn+ Deposited on TiO2(110) Surfaces Under Soft-Landing Conditions 201
References 220
Chapter 5. Oxide-supported metal clusters 224
1. Introduction 224
2. Alumina-Supported Metal Clusters 225
3. Magnesium Oxide-Supported Metal Clusters 237
4. Silica-Supported Metal Clusters 248
5. Titania-Supported Metal Clusters 260
6. Conclusions 280
Acknowledgments 280
References 281
Chapter 6. Magic numbers for shells of electrons and shells of atoms in binary clusters 294
1. Introduction 294
2. Production of Binary Clusters 297
3. Phenomenological Modelling of the Many Body Problem for Doped Metal Clusters 299
4. A Selection of Doped Metal Cluster Systems 302
5. Summary and Outlook 316
References 316
Chapter 7. Computational electron spectroscopy of gas-phase metal clusters 322
1. Introduction 322
2. Converting Kohn–Sham Eigenenergies into Electron Binding Energies 324
3. Computational Methodology 329
4. Magnesium Clusters: Results and Discussion 330
5. Aluminum Clusters: Results and Discussion 345
6. Summary 348
Acknowledgments 348
References 348
Chapter 8. Vibrational spectroscopy of gas-phase clusters and complexes 350
1. Introduction 350
2. Methods 351
3. Experimental Section 355
4. Results 360
5. Summary and Conclusions 393
Note 394
Acknowledgments 394
References 394
Chapter 9. Trapped ion electron diffraction: structural evolution of silver and gold clusters 400
1. Introduction 400
2. Methods of Trapped ion Electron Diffraction 402
3. Structural Transitions in Metal Clusters 411
4. Outlook 427
Acknowledgments 428
References 428
Chapter 10. Superatoms: building blocks of new materials 432
1. Introduction 432
2. Jellium: Tenets, Electron Counts and Energetic Stability 434
3. Cluster Stability, Electronic Markers and Superatoms 434
4. Adding a Third Dimension to the Periodic Table 436
5. Influencing Properties: Creation of Active Sites and Effects on Reactivity 441
6. Establishing the Concept of Employing Superatoms in Producing Nanoscale Materials Formation 442
7. Implications of Cluster Science to Material and Surface Properties 444
Acknowledgments 447
References 447
Chapter 11. Magnetic properties of 2D islands on single-crystal metal surfaces 450
1. Introduction 450
2. Magnetization vs. Temperature 452
3. Co Islands on Pt(111): MAE and Reversal Mechanism 456
4. Superlattices of Uniaxial Monodomain Islands 468
5. MAE and Magnetic Moment of Single Atoms 477
6. Spatially Resolved Measurements of Spin Polarization of Magnetic Islands 482
7. Conclusions and Outlook 488
References 489
Chapter 12. Electronic structure and magnetic properties of small deposited transition metal clusters 494
1. Introduction 494
2. Discussion 495
3. Summary 506
Acknowledgments 507
References 507
Chapter 13. Magnetic properties of deposited and embedded clusters 510
1. Introduction 510
2. Deposited Clusters 514
3. Embedded Nanoparticle Assemblies 528
4. Applications of Cluster-Assembled Films 546
5. Conclusions and Summary 552
References 553
Chapter 14. Theory of magnetic clusters and nanostructures at surfaces 558
1. Introduction 558
2. Ground-State Theory 559
3. Free and Embedded Clusters 565
4. Binary Alloy Clusters 573
5. Ferromagnetic Clusters on Highly Polarizable Substrates 578
6. Finite-Temperature Magnetic Properties 584
7. Electron Correlation Effects in Magnetic Clusters 595
8. Conclusion 606
Acknowledgments 607
References 607
Chapter 15. Modelling the structure and dynamics of metal nanoclusters deposited on graphite. 612
1. Introduction 612
2. Ab Initio Calculations of the Interaction of Small Metal Clusters with Graphite 614
3. Interaction Potentials 624
4. The Determination of Cluster Geometries 625
5. Molecular Dynamics Methodology 627
6. Pinning Clusters on Surfaces 628
7. Low-Energy Cluster Implantation 632
8. Conclusion and Future Prospects 637
References 638
Index 640