Purusottam (Puru) Jena is Distinguished Professor of Physics at Virginia Commonwealth University, USA. He originated the idea of superatoms and co-authored the first paper in the field in 1992. He has since published numerous papers and review articles on superatom clusters as materials building blocks. He has worked extensively on superhalogens and superalkalis.Qiang Sun is Professor at Peking University, China and Visiting Professor at Virginia Commonwealth University, USA. His research focus is on nanostructure physics, including 2D materials and clusters, and the physics of energy materials.

• Preface xiList of Contributors xiii1 Introduction 1Puru Jena and Qiang SunReferences 72 Rational Design of Superatoms Using Electron-Counting Rules 15Puru Jena, Hong Fang, and Qiang Sun2.1 Introduction 152.2 Electron-Counting Rules 172.3 Stabilizing Negative Ions Using Multiple Electron-Counting Rules 372.4 Conclusions 46References 463 Superhalogens – Enormously Strong Electron Acceptors 53Piotr Skurski3.1 Superhalogen Concept 533.2 Alternative Superhalogens 613.3 Polynuclear Systems and the Search for EA and VDE Limits 703.4 Superhalogens’ Applications at a Glance 773.5 Final Remarks 78Acknowledgements 79References 794 Endohedrally Doped Superatoms and Assemblies 85Vijay Kumar4.1 Introduction 854.2 Magic Clusters and Their Electronic Stability 884.3 Discovery of Silicon Fullerenes and Other Polyhedral Forms 894.4 Endohedral Superatoms of Ge, Sn, and Pb 974.5 Magnetic Superatoms 1014.6 Endohedral Clusters of Group 11 Elements 1014.7 Endohedral Clusters of B, Al, and Ga 1044.8 Hydrogenated Silicon Fullerenes 1074.9 Compound Superatoms and Other Systems 1084.10 Assemblies of Superatoms 1104.11 Concluding Remarks 117Acknowledgements 117References 1185 Magnetic Superatoms 129Nicola Gaston5.1 Introduction 1295.2 The Arrival of the Magnetic Superatom 1305.3 Tunable Superatoms 1335.4 The Delocalisation of d-electrons 1345.5 Prospects for Nanostructured Magnetic Material Design 137References 1386 Atomically Precise Synthesis of Chemically Modified Superatoms 141Shinjiro Takano and Tatsuya Tsukuda6.1 Introduction 1416.2 Electronic Structures of Chemically Modified Superatoms 1476.3 Atomically Precise Synthesis of Chemically Modified Superatoms 1606.4 Summary 176References 1777 Atomically Precise Noble Metals in the Nanoscale, Stabilized by Ligands 183Hannu Häkkinen7.1 Introduction 1837.2 Fundamentals 1847.3 Applications 1947.4 Summary and Outlook 205References 2068 Superatoms as Building Blocks of 2D Materials 209Zhifeng Liu8.1 Introduction 2098.2 Fullerene-Assembled 2D Materials 2118.3 Si-Based Cluster Assembled 2D Materials 2238.4 Binary Semiconductor Cluster Assembled 2D Materials 2318.5 Simple and Noble Metal Cluster-assembled 2D Materials 2368.6 Zintl-ion Cluster-assembled 2D Materials 2408.7 Chevrel Cluster-Assembled 2D Materials 2438.8 Summary and Future Perspectives 247References 2499 Superatom-Based Ferroelectrics 257Menghao Wu and Puru Jena9.1 Introduction 2579.2 Organic Ferroelectrics 2589.3 Hybrid Organic-Inorganic Perovskites 2629.4 Supersalts 2669.5 Conclusion 270References 27010 Cluster-based Materials for Energy Harvesting and Storage 277Puru Jena, Hong Fang, and Qiang Sun10.1 Introduction 27710.2 Cluster-Based Materials for Moisture-resistant Hybrid Perovskite Solar Cells 28310.3 Cluster-Based Materials for Optoelectronic Devices 28710.4 Cluster-Based Materials for Solid-state Electrolytes in Li-and Na-ion Batteries 28710.5 Cluster-Based Materials for Hydrogen Storage 30010.6 Clusters Promoting Unusual Reactions 30510.7 Conclusions 310References 31111 Thermal and Thermoelectric Properties of Cluster-based Materials 317Tingwei Li, Qiang Sun, and Puru Jena11.1 Introduction 31711.2 Basic Theory 31811.3 Low Lattice Thermal Conductivity of Cluster-based Materials 32311.4 Thermoelectric Properties of some Selected Cluster-based Materials 33011.5 Conclusion 341References 34212 Clusters for CO2 Activation and Conversion 349Haoming Shen, Qiang Sun, and Puru Jena12.1 Introduction 34912.2 Superalkali Catalysts 35112.3 Al-Based Clusters for CO2 Capture 35912.4 Ligand-Protected Au25 Clusters for CO2 Conversion 36112.5 M@Ag24 Clusters for CO2 Conversion 36412.6 Cu-Based Clusters for CO2 Conversion 36712.7 Metal Encapsulated Silicon Nanocages for CO2 Conversion 37012.8 Summary and Perspectives 370References 37213 Conclusions and Future Outlook 375Puru Jena and Qiang SunIndex 379

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