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1 Chapter 1Figure 1.1 Sodium cluster abundance spectrum, (a) experimental data of Knigh...Figure 1.2 Schematic diagram of an atom and atomic orbitals (left panel) whe...Figure 1.3 Series of mass spectra showing progression of the etching reactio...Figure 1.4 Three‐dimensional periodic table with superatoms mimicking the ch...Figure 1.5 Spin polarized electron orbitals of Al atom (left panel) and the ...

2 Chapter 2Figure 2.1 The periodic table of elements.Figure 2.2 Binding‐energy curves of (Na₁₉)₂ for two different electronic con...Figure 2.3 Binding energy as a function of distance between two Na atoms. Th...Figure 2.4 Ground‐state geometry of Na₂₀.Figure 2.5 Molecular orbitals and energy levels of neutral Na₂₀ cluster. The...Figure 2.6 Reaction between two Na₈ clusters in vacuum. (a) Time evolution o...Figure 2.7 The initial (left) and the final (right) configuration of the col...Figure 2.8 (a) Structure and super atomic‐molecule models of Au₂₀ (TAu4). (b...Figure 2.9 Direct atomic imaging and dynamical fluctuations of the tetrahedr...Figure 2.10 Q(M) versus η (X = F, Cl, Br, I) for (a) MX (M = Al₁₁–Al₁₅,...Figure 2.11 Initial crystal structure for (a) body‐centered‐cubic (bcc), (b)...Figure 2.12 Electron affinity of coinage metal atoms decorated with F.Figure 2.13 Electron affinity (EA) of Au(BO₂) _n as a function of n (black lin...Figure 2.14 Al(BH₄)₃ (left panel) and KAl(BH₄)₄ (right panel).Figure 2.15 (a)–(e) are the globally optimized geometries for M(CN)₄ ^0,1−,2−...Figure 2.16 (a) Isolated (CH₃)₄N⁺Al₁₃ ⁻ cluster. (b) Optimized body‐cen...Figure 2.17 (a)–(c) are the optimized geometries for MAu₁₂ ^0,1−,2−...Figure 2.18 Orbital energies of Pu@Pb₁₂ and Pb₁₂ ²⁻. The latter have be...Figure 2.19 Ground state geometries of neutral and anionic C₆H_{6 − x}...Figure 2.20 Ground state geometries of neutral and anionic C₅BH_{6 − x}...Figure 2.21 Left panel: photoelectron spectra at 355 nm (3.496 eV) for (a) L...Figure 2.22 Geometry of B₁₂H₁₂ ²⁻.Figure 2.23 PES spectrum of Al₄H₆ anion (left panel) and mass spectra of Al₄ Figure 2.24 Optimized structure of (a) Sn₁₂ ⁻, (b) Sn₁₂ ²⁻, and (c...Figure 2.25 Ground state geometries of neutral and anionic C₆H_{6 − x} ...Figure 2.26 Ground state geometries of neutral and anionic C₅BH_{6 − x} ...Figure 2.27 Electron affinities of BC₅H_{6 − x} (CN) _x , x = ...Figure 2.28 Equilibrium geometries of (a) neutral and (b) anionic Mn[BC₅(CN)Figure 2.29 Molecular dynamics simulation of Cr[BC₅(CN)₆]₂ ²⁻ cluster....Figure 2.30 Geometry of B₁₂(CN)₁₂ ²⁻ with I_h symmetry.Figure 2.31 Optimized geometries of (a) B₂C₄H₆ ^0,1−,2−, (b) B₂C₄(...Figure 2.32 BeB₁₁(CN)₁₂ ³⁻ (a) geometry, (b) AIMD simulation as a funct...Figure 2.33 (a) Evaluation of the size (r = 9.09 Å) needed for a stable tetr...

3 Chapter 3Figure 3.1 HOMOs for (MgF₃)⁻, (AlF₄)⁻, (SiF₅)⁻, and (PF₆)⁻...Figure 3.2 The equilibrium structures of neutral BF₄ and AlF₄ superhalogens ...Figure 3.3 Photoelectron spectra of (LiX₂)⁻ anions (left) and (NaX₂)⁻...Figure 3.4 Electron detachment energies for the (NaCl₂)⁻ superhalogen ...Figure 3.5 Equilibrium structures of selected alternative superhalogen anion...Figure 3.6 Equilibrium structure of the (Al(C₆F₅)₄)⁻ anion and its dou...Figure 3.7 The energy profile for the formation of the (Na(OH)₂)⁻ anio...Figure 3.8 The lowest energy isomers of (NaF₃)⁻ (C_2v‐symmetry, VDE = 7...Figure 3.9 The equilibrium structure of neutral Mg(Mg(BH₄)₃)₃ hyperhalogen (...Figure 3.10 The lowest energy structure of the (Mg₃Cl₇)⁻ anion.Figure 3.11 The equilibrium structures of C₃‐symmetry (H₉F₁₀)⁻ and C_3h Figure 3.12 The VDE dependence on the number of central atoms (n) for the (H

4 Chapter 4Figure 4.1 (a) Fullerene isomer of Zr@Si₁₆ and (b) Frank‐Kasper (FK) polyhed...Figure 4.2 Mass spectra of groups 3 (anions), 4 (neutral), and 5 (cations) m...Figure 4.3 Interaction energies (left scale) between TiSi _n and H₂O molecule,...Figure 4.4 Kohn−Sham energy spectra of fullerene type f‐Zr@Si₁₆ and FK‐Ti@SiFigure 4.5 (a) L_2,3 X‐ray absorption spectra of size‐selected [VSi _n ]⁺ cluste...Figure 4.6 (a) M@Si₁₆ (M = Cr, Mo, W) capped fullerene structure, (b) Mo@Si₁...Figure 4.7 (a) Bicapped tetragonal antiprism for Be@X₁₀ (X = Si, Ge, Sn), Ni...Figure 4.8 Photoelectron spectra of M@Ge₁₆ (M = Sc, Y, Lu, Tb, Ti, Zr, Hf, V...Figure 4.9 Relative reactivity of anionic/neutral/cationic MGe _n ^−/0/+ c...Figure 4.10 Photoelectron spectra of (a) ScSn _n , (b) YSn _n , (c) TiSn _n , (d) ZrS...Figure 4.11 Atomic structures of (a) Al₁₃ ⁻ and (b) Au₂₀. (c) and (d) s...Figure 4.12 Atomic structures of (a) W@Au₁₂ (I_h symmetry) (also for Mo@Au₁₂,...Figure 4.13 Structures of small boron clusters. (a) B₉ ⁻, (b) Co@B₈ ⁻...Figure 4.14 Structures of boron cages. (a) Cr@B₂₀, (b) Mo@B₂₂, and (c) Mo@B₂...Figure 4.15 Hydrogenated silicon fullerenes Si₁₆H₁₆ and Si₂₀H₂₀.Figure 4.16 Halide ion templated Si₂₀H₂₀ fullerenes X⁻@Si₂₀H₂₀ with (a...Figure 4.17 Structures of (a) (CdSe)₁₃ and (b) (CdSe)₃₄ core–cage nanopartic...Figure 4.18 Interaction between superatoms. (a) Zr@Si₁₆ fullerenes and (b) F...Figure 4.19 Interaction between two Si₁₂Be clusters leads to the formation o...Figure 4.20 Representative units used for infinite nanotubes of Si _n Be _m . (a) ...Figure 4.21 Structures of Si₂₄M₄ (M = Mn, Fe, Co, and Ni) infinite nanotubes...Figure 4.22 Immobilization of Ta@Si₁₆ nanoclusters onto C₆₀‐terminated surfa...Figure 4.23 (a) A slightly distorted fullerene structure of Ta@Si₁₆, (b) Cl ...

5 Chapter 5Figure 5.1 The Kohn–Sham states of the group 3 clusters of seven atoms are s...

6 Chapter 6Figure 6.1 (a) Electronic shell structure of magic Na₄₀ cluster. (b) EAs of ...Figure 6.2 Annual numbers of crystals datasets for (a) coinage‐metal MPCs, (...Figure 6.3 Schematic representation of size effects on spherical jellium pot...Figure 6.4 Size‐dependent (a) optical absorption profiles and (b) optical ba...Figure 6.5 Schematic representation of the effects of anionic charge on the ...Figure 6.6 Schematic representation of heterometal doping to Au superatom....Figure 6.7 Optimized structures and the corresponding energy diagrams of (a)...Figure 6.8 Schematic representation of jellium potentials before and after d...Figure 6.9 Series of superatomic molecules of Au ₁₁ (7e) and Au ₁₃ (7/8e) wi...Figure 6.10 Energy diagram of the SOs for (a) Au ₂₃ (14e) and (b) Au ₂₀ (14e)....Figure 6.11 CD spectra of (a) [Au₁₁(R/S‐DIOP)₄Cl₂]⁺ and (b) [Au₈(R/S‐BINAP)₃ Figure 6.12 (a) Atomic structure of anisotropic Au ₁₃ (8e) observed in [Au₂₃(SFigure 6.13 Schematic illustration of the preparation and size‐focusing stra...Figure 6.14 (a) Optical spectra of size‐selected Au _x (SG) _y before (0 hour) an...Figure 6.15 (a, b) SEC separation of Au₅₅(SC₁₈H₃₇)₃₂ and Au₃₈(SC₁₈H₃₇)₂₄ in ...Figure 6.16 (a, b) Reverse‐phase HPLC separation of a series of Au _x (SR) _y clu...Figure 6.17 Separation of enantiomers of Au₃₈(PET)₂₄. (a) Chiral HPLC chroma...Figure 6.18 PAGE separation of (a) Au _x (SG) _y , (b) Au _x (SPG) _y , (c) Au _x (mMBA) _y , ...Figure 6.19 (a) Time course of the abundance of each reaction intermediate i...Figure 6.20 (a) A schematic image, (b) mass analysis, (c) HRTEM image, and (...Figure 6.21 (a) Schematic illustration of the synthesis of Au:PVP using a mi...Figure 6.22 Schematic illustration of the four modes of AGRs.Figure 6.23 Formation of hydrogen‐containing Au‐based superatom and its tran...Figure 6.24 Examples of fusion reactions of preformed MPCs. Color codes: yel...Figure 6.25 Luminescent properties in chemically modified Au superatoms depe...Figure 6.26 Examples of LEIST and reversible LEIST of (a) Au MPC and (b) Ag ...Figure 6.27 Hydride‐mediated surface transformation reactions. Color codes: ...

7 Chapter 7Figure 7.1 A schematic representation of the electron states in bulk metal (...Figure 7.2 Shell structure of noninteracting fermions in an infinite spheric...Figure 7.3 Left: Ground‐state densities of electron cluster from two to eigh...Figure 7.4 Visualization of ligand‐stabilized metal nanoclusters composed of...Figure 7.5 Superatom analysis: angular momentum weights for Kohn–Sham orbita...Figure 7.6 The atomic structure of Ag₄₄(SPhF₂)₃₀ ⁴⁻. (a) Full structure...Figure 7.7 (top left): measured PE spectra of Ag₄₄(SPhF₂)₃₀ ⁴⁻ using tw...Figure 7.8 Predicted structure of the Au₁₄₄(SR)₆₀ cluster. (a)–(c) Show the ...Figure 7.9 (a) Projected density of electron states (PDOS) within the Au₁₁₄ ...Figure 7.10 Co‐crystal structure of (AuAg)₂₆₇·(AuAg)₄₅. (a) The total struct...Figure 7.11 (a) Buckyball‐shaped (AuAg)₂₆₇ nanoparticle. (b) Layered ABCAC p...Figure 7.12 Calculated electronic structures of (AuAg)₂₆₇ and (AuAg)₄₅. (a) ...Figure 7.13 Correlation between the binding energy of O₂ to partially protec...Figure 7.14 (a) HOMO and LUMO states of the fully protected Au₁₁(PH₃)₇Cl₃ cl...Figure 7.15 (a) The model structure of Au₁₁L₅(O₂)₃ complex; (b) Solvent‐acce...Figure 7.16 A schematic representation of functionalization of Au₁₀₂(p‐MBA)₄...Figure 7.17 TEM images of enteroviruses. (a) CVB3 incubated with functionali...Figure 7.18 End configurations of directed molecular dynamics (MD) simulatio...Figure 7.19 Atomic structure of the cluster polymer, where the basic unit is...Figure 7.20 DFT‐computed electronic DOS of the cluster polymer crystal. The ...Figure 7.21 (a) A single crystal of (AuAg)₃₄ cluster polymers (top) and the ...

8 Chapter 8Figure 8.1 (a) Cohesive energy per C₆₀ as a function of C₆₀‐C₆₀ inter‐cluste...Figure 8.2 (a) The energetically optimized hexagonal structure of C₆₀ monola...Figure 8.3 (a) The AR‐2PPE obtained energy diagram of the 2D ML‐C₆₀, in whic...Figure 8.4 (a) The building block C₆₀ in the single hexagonal C₆₀ layer (sev...Figure 8.5 The structural models of three 2D C₆₀ polymers with different int...Figure 8.6 The optimized atomic structure of Hexa‐C₂₀ from (a) top and (b) s...Figure 8.7 (a) The optimized atomic structure of C₂₆ cluster. (b) Initial st...Figure 8.8 The optimized structures of (a) C₃₂‐graphene and (b) C₃₆‐filled CFigure 8.9 (a) Geometric structures of fullerene C₃₆, (b) top view of 2D C₃₆ Figure 8.10 STM images recorded at sample voltages between 2 and 2.2 V of C₆...Figure 8.11 (a) STM images of the C₆₀‐ML on the Cu(111) surface. (b) High‐re...Figure 8.12 Atomic structures of the fully optimized V@Si₁₂‐assembled sheets...Figure 8.13 (a) Top and (b) side views of the optimized structure of Zr@Si₁₂ Figure 8.14 The atomic structures of four possible TMSi₁₂ assembled 2D cryst...Figure 8.15 MM variation of the isolated TM atoms, TM@Si₁₂ clusters as well ...Figure 8.16 Optimized self‐assembled 2D hexagonal structures of Ta@Si₁₆. (a)...Figure 8.17 Stable immobilization of Ta@Si₁₆ clusters onto C₆₀‐terminated su...Figure 8.18 Ta@Si₁₆/C₆₀ structures: (a) dot‐contact structure [dot‐C₆₀‐2D (t...Figure 8.19 Schematic diagram of (a) optical absorption spectra and (b) work...Figure 8.20 Initial and optimized geometries of Cd₆Se₆ cluster assembly, for...Figure 8.21 Dynamical and thermal stability of Cd₆Se₆ cluster assembly for t...Figure 8.22 (a) Total DOS and (b) PDOS of type‐2 Cd₆Se₆ cluster‐assembled bi...Figure 8.23 (a) The atomic structure of 2D graphene‐like sheet assembled by ...Figure 8.24 The atomic structure of 2D Mg₇ monolayer. (a) The corresponding ...Figure 8.25 Structure of 2D (a) Pt₉, (b) Au₉, and (c) Au₁₈Pt₁₈. Black box in...Figure 8.26 Spin‐resolved PDOSs of (a) red‐circled Pt atom in 2D‐Pt₉ and (b)...Figure 8.27 (a) Optimized structure of the hexameric species [Ge₉R]₆ ⁶⁻ Figure 8.28 (a) Atomic structure and (b) electronic band structure of 2D Na₂ Figure 8.29 Crystal structure and exfoliation of the 2D vdW solid Re₆Se₈Cl₂....Figure 8.30 (a) AFM image of monolayers drop‐cast on a sapphire substrate. (...Figure 8.31 Structure of Tet _2D from SCXRD: square sheets in the crystalline ...

9 Chapter 9Figure 9.1 FE switching of hydroxylized (a) transition‐metal molecular SNWs,...Figure 9.2 FE switching pathway of (a) isolated M@C₆₀ fixed on the substrate...Figure 9.3 Geometric structures of super‐cations and FE switching of (a) (H₅ Figure 9.4 (a) ZB structure, superalkali cations, and superhalogen anions; (...Figure 9.5 (a) FE switching of NH₄MX₄/PH₄MX₄. (b) Triferroic switching of PH

10 Chapter 10Figure 10.1 (a) Geometry of C₆₀ fullerene. (b) Geometry of fcc‐C₆₀ solid....Figure 10.2 The HOMO and LUMO (c.a. 2 eV above) of neutral C₆₀ (Left) and tw...Figure 10.3 (a) Calculated band structures of fcc‐C₆₀ using (a) GW and (b) n...Figure 10.4 Experimental phase diagram for fcc A₃C₆₀ (A = K, Rb, Cs). Copyri...Figure 10.5 TaSi₁₆ superatom monolayer on C₆₀‐terminated surface.Figure 10.6 Ball and stick model of K⁺MnO₄ ⁻ crystal.Figure 10.7 Efficiency of different solar cells.Figure 10.8 Crystal structure of CH₃NH₃PbX₃ perovskites (X = I, Br, and/or C...Figure 10.9 Degradation mechanism of CH₃NH₃PbI₃ exposed to moisture. The bal...Figure 10.10 Ionic radius ratio and the bandgaps of hybrid perovskites again...Figure 10.11 Crystal structures of (a) BA₂MI₄ and (b) BA₂M(BH₄)₄ (M = Ge, Sn...Figure 10.12 (a) Cluster model of 2D hybrid perovskite. The organic chains o...Figure 10.13 Optimized geometries of anions of four potential candidates for...Figure 10.14 (a) Unit cell of the optimized ground state of Li₃O(BH₄). The g...Figure 10.15 (a) Optimized unit cell of Li₃SBF₄, with Li in blue, S in yello...Figure 10.16 Optimized pesudocubic structures of Na₃O(AlH₄), Na₃O(BF₄), and ...Figure 10.17 Snapshots of (a) Na₃S(BCl₄) and (b) Na₃S(BCl₄)0.5I_0.5 containin...Figure 10.18 Adsorption of hydrogen on substrates, (a) physisorption, (b) ch...Figure 10.19 Geometries of Li⁺(H₂) _n clusters with n ≤ 6. The bond lengths ar...Figure 10.20 (a) Optimized atomic structures of C₆₀[ScH₂(H₂)₄]₁₂, (b) C₄₈B₁₂ Figure 10.21 (a) Initial and (b) optimized geometries of Li₁₂C₆₀(H₂)₆₀.Figure 10.22 Geometries of negative ion components of intermediate phases in...Figure 10.23 Screening study results of NaAlH₄/carbon mixtures. These values...Figure 10.24 Correlation of the carbon substrate EA and the hydrogen removal...Figure 10.25 Optimized structures of (a–d) neutral and (e–g) anionic ZnX₃ (X...Figure 10.26 (a) Fragmentation reaction that yields the electrophilic anion ...

11 Chapter 11Figure 11.1 (a) Seebeck effect: Two TE materials joined at hot and cold junc...Figure 11.2 Schematic diagram showing how ZT and its related parameters (ele...Figure 11.3 The pseudocubic band‐convergence scheme. (a) Crystal structure a...Figure 11.4 Schematic representation of (a) undoped semiconductor and (b) mo...Figure 11.5 Perspective representation of the crystal structure of Ag₆Ge₁₀P₁...Figure 11.6 (a) Crystal structure and (b) the primitive cell for cubic Ag₉Ga...Figure 11.7 (a) Molecular structure of the superatoms [Co₆E₈] and C₆₀. Hydro...Figure 11.8 Thermal conductivity of SACs as a function of temperature.Figure 11.9 Measured thermal conductivities for the fullerene derivative fil...Figure 11.10 Schematic representation of the formation of the Mo₉Se₁₁Se₆ clu...Figure 11.11 Projection of the crystal structure of the Ag _x Mo₉Se₁₁ compounds...Figure 11.12 DFT dispersion curves of the (a) Ag₄Mo₉Se₁₁ and (b) Ag₃Mo₉Se₁₁....Figure 11.13 (a) Temperature dependence of the electrical resistivity ρ Figure 11.14 (a) The total thermal conductivity κ and (b) the lattice t...Figure 11.15 Temperature dependence of ZT of the Ag _x Mo₉Se₁₁ compounds.Figure 11.16 Views of crystal structures of (a) RB₆₆[70a], (b) YB₄₄Si₂ along...Figure 11.17 Temperature dependence of the electrical resistivity ρ of ...Figure 11.18 Temperature dependence of the Seebeck coefficient of YbB₆₆ with...Figure 11.19 Temperature dependence of the power factor of YbB₆₆ with SmB₆₆[...Figure 11.20 Temperature dependence of the thermal conductivity κ of Yb...Figure 11.21 Temperature dependence of the dimensionless figure of merit ZT ...Figure 11.22 Temperature‐dependent Seebeck coefficient (a), resistivity (b),...Figure 11.23 Temperature‐dependent figure of merit (ZT) for Ag₉Ga(S_1−x

12 Chapter 12Figure 12.1 Calculated structures of Au⁻(CO₂), AuCO₂ ⁻, Ag⁻ Figure 12.2 Optimized geometries (left panel) and natural bond orbital (NBO0...Figure 12.3 Equilibrium structures of superalkali–CO₂ complexes with bond le...Figure 12.4 The SOMOs (isovalue = 0.02 a.u.) and spin density surfaces (isov...Figure 12.5 Calculated CBS‐QB3 potential energy surface of the Li₃F₂ with COFigure 12.6 The SOMOs for Li₃F₂; Li₃F₂/CO₂ (1), (2), and (3); and Li₃F₂/N₂ (Figure 12.7 Equilibrium structure of C₆Li₆–nCO₂ complexes for n = 1–6 obtai...Figure 12.8 Optimized structures of graphene … Li₃F₂ … CO₂ (a, c) and graphe...Figure 12.9 (a) Optimized structure of Li₃O@BNNT with an adsorbed CO₂ molecu...Figure 12.10 Structures of optimized ground state Al₅M … CO₂ complexes with ...Figure 12.11 Configurations of CO₂ adsorptions on ZrAl _n (a–d), HfAl _n (e–h), Figure 12.12 Experimental results and DFT modeling of the Au₂₅–CO₂ couple. (...Figure 12.13 Free energy diagram for electrochemical reduction of CO₂ to CO ...Figure 12.14 The catalytic carboxylation of terminal alkyne with CO₂ over Au...Figure 12.15 (a) DFT‐optimized geometries for the adsorption products of [CHFigure 12.16 Reaction scheme for CO₂ electroreduction on Cu₃₂H₂₀L₁₂ to form ...Figure 12.17 Overall mechanism of HCOOH formation from CO₂ reduction on Cu₃₂ Figure 12.18 Most stable structures and adsorption energies for CO₂ on clust...Figure 12.19 Activation energy for the CO₂* dissociation into CO* + O*.Figure 12.20 Atomic structures of reactants and products for the elemental s...Figure 12.21 Reaction pathway and free energy diagram for CO₂ hydrogenation ...