Front Cover
Atomic Clusters with Unusual Structure, Bonding and Reactivity: Theoretical Approaches, Computational Assessment and Appli ...
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Contents
Contributors
Chapter 1: Describing chemical bonding in exotic systems through AdNDP analysis
1. Introduction
1.1. AdNDP implementation
2. Boron hydrides
2.1. Chemical bonding scheme in B3Hy- complexes
2.2. Isostructural relationships in BnHn series
2.3. Electronic transmutation
2.4. Chemical bonding in deltahedral BnHn2- systems
3. Boron nanowheels
3.1. Dynamic behavior in small boron clusters
3.2. Boron wheels members of Wankel motor family
3.3. Design of sandwich structures
3.4. Dynamic behavior of B36 cluster
4. Summary
References
Chapter 2: Electron delocalization in clusters
1. Introduction
2. Electron delocalization in flat clusters
3. Electron delocalization in (pseudo)spherical clusters
4. Conclusions
Acknowledgments
References
Chapter 3: Bimetallic clusters
1. Introduction
2. Computational methods
2.1. Energy calculator
2.1.1. Density-functional tight binding
2.1.2. Embedded-atom model
2.2. Global structure optimization methods
2.2.1. Basin-hopping algorithm
2.2.2. Genetic algorithm
3. Structural properties of bimetallic clusters
4. Conclusions
Acknowledgments
References
Chapter 4: Unusual bonding between second row main group elements
1. Introduction
2. Low-valent state of main group elements
3. LEL complexes
3.1. Carbones: Divalent C(0) systems
3.1.1. Synthesis
3.1.2. Bonding analysis
3.1.3. Chemical reactivity
3.1.4. Catalytic applications
3.2. Borylenes: Monovalent B(I) systems
3.2.1. Synthesis
3.2.2. Bonding analysis
3.2.3. Chemical reactivity and applications
3.3. Nitreones: Divalent N(I) systems
3.3.1. Tautomeric preference in nitreones
3.3.2. Synthesis
3.3.3. Bonding analysis
3.3.4. Chemical reactivity and stability
3.3.5. Applications of nitreones
As phase transfer catalysts
Nitreone framework in medicinally important molecules: new perspective of protonated biguanide
4. Debates on the bond representation
5. Summary
References
Chapter 5: Conceptual density functional theory and all metal aromaticity
1. Introduction
2. History and descriptors of aromaticity
2.1. Relative aromaticity indices (X)
3. Aromaticity in the context of metallic systems
3.1. Alkali and alkaline earth metal
3.2. Transition metal
4. Conclusion
Acknowledgments
References
Chapter 6: Structural evolution, stability, and spectra of small silver and gold clusters: A view from the electron shell ...
1. Introduction
2. Equilibrium structures and growth mechanism
3. Thermodynamic stabilities
4. Phenomenological shell model (PSM)
5. Electronic absorption spectra
6. Concluding remarks
Funding information
References
Chapter 7: Optical response properties of some metal cluster supported host-guest systems
1. Introduction
2. Computational details
3. Results and discussion
3.1. Geometrical structures and thermodynamic feasibility of obtaining the corresponding host-guest moieties
3.2. Optical and electronic properties of the selected metal cluster-host complexes
3.3. AIM analysis
3.4. EDA study
3.5. TDDFT analysis of the guestOA complexes
4. Conclusion
References
Chapter 8: Group III-V hexagonal pnictide clusters and their promise for graphene-like materials
1. Introduction
2. Computational details
3. Benzene and its group III-V pnictide cluster analogues
3.1. Structural properties
3.2. Electronic properties
4. Polymeric growth of benzene and its III-V analogues
4.1. Structural properties
4.2. Electronic properties
5. Group III-V graphene-like materials from potential cluster units
5.1. Monolayer indium nitride for thermoelectrics
5.2. Mono- and multilayer thallium nitride for thermoelectrics
5.3. Other two-dimensional group III-V materials
6. Conclusions
Acknowledgments
References
Chapter 9: M(L)8 complexes (M=Ca, Sr, Ba; L=PH3, PF3, N2, CO): Act of an alkaline-earth metal as a conventional transitio ...
1. Introduction
2. Computational details
3. Structure and stability of M(L)8 complex
4. MOs and correlation diagram
5. Energy decomposition analysis
6. M(Bz)3: 20-electron complex
7. Conclusions
Acknowledgments
References
Chapter 10: Structures, reactivity, and properties of low ionization energy species doped fullerenes and their complexes ...
1. Introduction
2. Computational techniques
3. Low IE species doped endofullerenes
3.1. LiC60 vs SAC60 endofullerene (SA=FLi2, OLi3, and NLi4)
3.2. LiC60 vs LrC60 endofullerene
4. Endofullerene-superhalogen complexes
4.1. LiC60-PF6 endofullerene complex
4.2. SAC60BF4 endofullerene complex
5. Conclusions and perspectives
Acknowledgments
Conflict of interests
References
Chapter 11: Generation of global minimum energy structures of small molecular clusters using machine learning technique
1. Introduction
2. Our proposed methodology and algorithm (parallel implementation)
2.1. Particle swarm optimization
2.2. Firefly algorithm
2.2.1. Performance improvement of FA over the basic approach
2.3. ADMP-CNN-PSO approach
2.3.1. CNN architecture
2.3.2. Postprocessing
3. Computational details
4. Experimental setup
4.1. PSO, FA, and ADMP-CNN-PSO
5. Results and discussion
5.1. PSO: Boron clusters, Bn (n=5, 6)
5.1.1. B5 cluster
5.1.2. B6 clusters
5.1.3. Carbon clusters, Cn (n=3-6, 10)
5.1.4. N42- clusters and N64- clusters
5.1.5. Aun (n=2-8) and AunAgm (2(nΒ±m)8) clusters
5.2. CNN and PSO: N42-, N64-, Aun (n=2-8) and AunAgm (2n+m8) clusters
5.2.1. C5 clusters
5.3. Firefly algorithm with density functional theory
5.3.1. Effect of planarity
5.3.2. Energy vs. aromaticity profiles of planar Al42- structures
6. Conclusion
Acknowledgments
Conflict of interest
References
Chapter 12: Studies on hydrogen storage in molecules, cages, clusters, and materials: A DFT study
1. Introduction
2. H-storage in various motifs-The road map representation
2.1. H-storage in small molecules
2.1.1. Cubane (cub)
2.1.2. Cyclohexane (Cyc)
2.1.3. Adamantane (Adm)
2.2. Hydrogen storage in molecular cages
2.2.1. H-storage in boranes- and Alanes-based cages
2.2.2. Energetics of nH2BXY cages
2.2.3. Energetics of nH2AlXY cages
2.3. H-storage in molecular clusters
2.3.1. BA nanoclusters
2.3.2. H-storage in boric acid pentamer (BA)5
2.3.3. H-storage in boric acid hexamer (BA)6
2.4. H-storage in materials
2.4.1. Small molecules incorporated MOP-9
2.4.2. Icosahedral (Ih) cages incorporated MOF-5
2.4.3. Boric acid cluster (BA20) incorporated fullerene-based material
3. Conclusions
Acknowledgments
References
Chapter 13: A density functional theory study of H3+ and Li3+ clusters: Similar structures with different bonding, aromat ...
1. Introduction
2. Methodology
3. Results and discussion
4. Conclusions
Acknowledgments
References
Chapter 14: Designing nanoclusters for catalytic activation of small molecules: A theoretical endeavor
1. Introduction
2. N2 activation
3. H2 activation
4. Activation and reduction of CO2
4.1. Specific role of metal hydride for the reduction of CO2
5. Activation of O2 and oxidation of CO on Aun nanoclusters
5.1. Effect of doping in Aun nanoclusters
5.2. Aln- anionic nanoclusters: Effect of electron spin
6. H2O activation
7. C-X and C-H bonds activation
7.1. C-X bond activation on Aln nanoclusters
7.2. Competitive H-X elimination on alumina nanoclusters
7.3. Selectivity of alumina nanoclusters during elimination
7.4. Selective C-H bond activation
8. Summary and future outlook
Acknowledgments
References
Chapter 15: Molecular electrides: An overview of their structure, bonding, and reactivity
1. Introduction
1.1. Electrides
1.2. Confinement of the electron
1.3. Development of organic electrides
1.4. Development of inorganic electrides
1.5. Toward the molecular electride
2. Norms and conditions of being a molecular electride
3. Computational methodology
4. Examples of molecular electrides
4.1. Alkali metal-doped electrides
4.2. Mg2EP, molecular electride and small molecule activation
4.3. Bonding in [Mg4(HDippL)2]2- complex and its electride nature
4.4. Mg2C60 and its electride characteristics
4.5. Binuclear Sandwich complexes of alkaline earth metals as electrides
4.6. Li3Cg (Cg=B40 and C60) and their electride nature
5. Conclusion
Acknowledgments
Authors note
References
Chapter 16: Hydrogen trapping potential of a few novel molecular clusters and ions
1. Introduction
2. Theoretical background
3. Computational details
4. Atomic and molecular clusters
4.1. Mg and Ca clusters
4.2. B2Li and B2Li2 moieties
4.3. C12N12 cage
5. Ionic clusters
5.1. N4Li2 and N6Ca2 clusters
5.2. Li3+ and Na3+ ions
5.3. B2Li+ and B2Li2+ ions
5.4. M5Li7+ (M=C, Si, Ge) clusters
6. Conclusion
Acknowledgments
References
Chapter 17: Polarizability of atoms and atomic clusters
1. Introduction
2. Basics of response properties and polarizability
3. DFT-based approach to calculation of polarizability
4. Polarizability of spherically symmetric systems: Atoms and atomic clusters within the jellium model
5. Chemical reactivity indices-based route to polarizability
6. Discussion on polarizability values of atomic clusters
7. Concluding remarks
Acknowledgments
References
Chapter 18: Advances in cluster bonding: Bridging superatomic building blocks via intercluster bonds
1. Introduction
2. Intercluster bonding of gold clusters
3. Intercluster bonding of Zintl clusters
4. Extended networks
5. Conclusions
Acknowledgments
References
Chapter 19: Zintl cluster as a building block of superalkali, superhalogen, and superatom
1. Introduction
2. Computational details
3. Zintl superalkali
4. Zintl superhalogens
5. Zintl superatom
6. Concluding remarks
References
Chapter 20: Metallic clusters for realizing planar hypercoordinate second-row main group elements and multiple bonded species
1. Introduction
2. Planar hypercoordinate main group elements
3. Planar pentacoordinate nitrogen
4. Metal cluster supported multiple bonded second-row main group element
5. Conclusions and future aspects
Acknowledgment
References
Chapter 21: Planar hypercoordinate carbon
1. Introduction
2. Planar tetracoordinate carbon (ptC)
3. Planar pentacoordinate carbon (ppC)
4. Planar hexacoordinate carbon (phC)
5. Higher coordinate carbon
6. Conclusion
Acknowledgments
References
Chapter 22: Transformation of nanoclusters without co-reagent
1. Introduction
2. Co-reactant-free transformations
2.1. pH-induced transformation
2.2. Solvent-induced transformation
2.3. Photo-induced transformation
2.4. Temperature-induced transformation
3. Perspectives and conclusions
References
Chapter 23: Application of frustrated Lewis pairs in small molecule activation and associated transformations
1. Introduction
2. The chemistry of Lewis acids and bases
3. Identification of FLP reactivity
4. Mechanism of H2 activation by FLPs
5. Thermodynamics on H2 activation by FLP
6. Activation of other small molecules
7. Aromaticity-enhanced small molecule activation
8. Catalytic hydrogenation
9. Boron-ligand cooperation
10. Polymerization reaction
11. Summary and outlook
References
Chapter 24: Ligand-protected clusters
1. Introduction
2. Representative examples of theoretical studies
3. Diphosphine-ligated gold clusters
3.1. Jellium models and core shapes
3.2. Geometric studies
3.3. Electronic studies
3.4. Effects of ligands on geometric and electronic structures
4. Conclusion
References
Index
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