Theoretical Chemistry for Advanced Nanomaterials (eBook)
XVII, 544 Seiten
Springer Singapore (Verlag)
978-981-15-0006-0 (ISBN)
This book collects recent topics of theoretical chemistry for advanced nanomaterials from the points of view of both computational and experimental chemistry. It is written for computational and experimental chemists, including undergraduate students, who are working with advanced nanomaterials, where collaboration and interplay between computation and experiment are essential.
After the general introduction of nanomaterials, several computational approaches are explained in Part II. Each chapter presents not only calculation methods but also concrete calculation results for advanced nanomaterials. Hydride ion conducting nanomaterials, high-k dielectric nanomaterials, and organic electronics are focused on. In Part III, the interplay between computational and experimental approaches is explained. The chapters show calculation results, combined with corresponding experimental data. Dimensionality of nanomaterials, electronic structure of oligomers and nanorods, carbon nanomaterials, and the electronic structure of a nanosized sandwich cluster is looked at carefully. In Part IV, functionality analysis is explained from the point of view of the experimental approach. The emphasis is on the mechanism of photoluminescence and hydrogen generation using silicon nanopowder, the superionic conducting mechanism of glass ceramics, nanoclusters formation on the surface of metal oxides, and the magnetic property of an organic one-dimensional nanochannel. Finally, forthcoming theoretical methods for excited states and quantum dynamics are introduced in Part V.
Taku Onishi is Japanese scientist. He graduated from Faculty of Science, Osaka University, Japan in 1998, and got PhD from Graduate School of Science, Osaka University, Japan in 2003. He got a permanent position at Faculty of Engineering, Mie University, Japan in 2003. He has been a guest researcher of Department of Chemistry, University of Oslo, Norway since 2010. His research covers several scientific fields such as computational chemistry, quantum physics and material science. He has served on international scientific activities: Member of Royal Society of Chemistry; Chair of Computational Chemistry (CC) symposium; Science Committee of International Conference of Computational Methods in Sciences and Engineering (ICCMSE); Editorial Board Member of Journal of Computational Methods in Sciences and Engineering (JCMSE), Cogent Chemistry and Cogent Engineering etc.
This book collects recent topics of theoretical chemistry for advanced nanomaterials from the points of view of both computational and experimental chemistry. It is written for computational and experimental chemists, including undergraduate students, who are working with advanced nanomaterials, where collaboration and interplay between computation and experiment are essential.After the general introduction of nanomaterials, several computational approaches are explained in Part II. Each chapter presents not only calculation methods but also concrete calculation results for advanced nanomaterials. Hydride ion conducting nanomaterials, high-k dielectric nanomaterials, and organic electronics are focused on. In Part III, the interplay between computational and experimental approaches is explained. The chapters show calculation results, combined with corresponding experimental data. Dimensionality of nanomaterials, electronic structure of oligomers and nanorods, carbon nanomaterials, and the electronic structure of a nanosized sandwich cluster is looked at carefully. In Part IV, functionality analysis is explained from the point of view of the experimental approach. The emphasis is on the mechanism of photoluminescence and hydrogen generation using silicon nanopowder, the superionic conducting mechanism of glass ceramics, nanoclusters formation on the surface of metal oxides, and the magnetic property of an organic one-dimensional nanochannel. Finally, forthcoming theoretical methods for excited states and quantum dynamics are introduced in Part V.
Preface 5
Contents 7
About the Editor 9
About the Corresponding Authors 10
Chapters 1 and 2 10
Chapter 3 10
Chapter 4 10
Chapter 5 11
Chapter 6 11
Chapter 7 12
Chapter 8 12
Chapter 9 13
Chapter 10 13
Chapter 11 14
Chapter 12 15
Chapter 13 15
Chapter 14 16
Part I Introduction 17
1 Theoretical Chemistry for Advanced Nanomaterials: Computational and Experimental Approaches 18
1.1 Introduction 18
1.2 Definition of Nanomaterial 19
1.3 Computation and Experiment 20
1.3.1 Computational Approach 20
1.3.2 Experimental Approach 21
1.4 Nanosize Materials 22
1.4.1 Top-Down and Bottom-Up Approaches 22
1.4.2 Organic Nanomaterials 23
1.4.3 Cluster 23
1.4.4 Nanoparticle 24
1.4.5 Plasma Electrolytic Oxidation 24
1.5 Nanoscale Functionality in Perovskite 24
1.5.1 Perovskite for Next Generation Energy 25
1.5.1.1 Light Response Perovskite 25
1.5.1.2 Ion-Conducting Perovskite 26
1.5.1.3 Hydrogen Storage Perovskite 27
1.5.2 Perovskite for Next Generation Electronic Device 29
1.5.2.1 Ferroelectric Perovskite 29
1.5.2.2 Superconductive Perovskite 30
1.5.2.3 Magnetic Perovskite 31
1.6 Challenges 33
1.6.1 Nanospace Chemistry Towards Nanomachine 33
1.6.2 Hydrogen Society and Safety 33
1.6.3 Safety of Lithium Ion Battery 34
1.6.4 Replacement of Lithium: Sodium Ion Battery 36
1.7 Summary 36
References 37
Part II Computational Approach 39
2 Quantum Chemistry in Perovskite Fluoride and Hydride: Nanoscale Hydride Ion Conduction 40
2.1 Introduction 40
2.2 Theoretical Approach: Molecular Orbital Calculation and Chemical Bonding Rule 41
2.3 Hydride Ion Conduction in Perovskite Magnesium Fluoride: KMgF3 42
2.3.1 Calculation Models 42
2.3.2 Fluorine Anion Conduction in Perovskite Magnesium Fluoride 42
2.3.3 Hydride Ion Incorporation in Perovskite Magnesium Fluoride 47
2.3.3.1 Pure Hydride Ion Conduction 47
2.3.3.2 Pure Fluorine Anion Conduction 50
2.3.3.3 Competitive Fluctuation of Fluorine Anion 51
2.3.4 Summary 54
2.4 Hydride Ion Conduction in Perovskite Magnesium Hydride: KMgH3 54
2.4.1 Calculation Models 55
2.4.2 Chemical Bonding Between Magnesium and Hydride Ion 55
2.4.3 Hydride Ion Conduction 57
2.4.4 Summary 61
2.5 Hydride Ion Safety and Outlook 61
2.5.1 Safety of Hydride Ion Conduction 62
2.5.2 Safety of Hydrogen Molecule Production Combined with Hydride Ion Conduction 62
2.5.3 AC Impedance Measurement of Hydride Ion Conduction 63
References 63
3 Local Dielectric Constant Density Analysis of High-k Dielectric Nanomaterial 65
3.1 Introduction 65
3.2 Theory 69
3.3 Local Dielectric Property of Simple Systems 74
3.3.1 Dependence of Local Polarizability on Choice of Basis Set 75
3.3.2 Local Dielectric Property of Molecules XHn (X = C, N, O, F, Si, P, S, Cl, Ge, As, Se, and Br) 78
3.4 Local Dielectric Property of HfLaOx 85
3.5 Summary 94
3.6 Perspective 96
References 98
4 Nanoscale First-Principles Electronic Structure Simulations of Materials Relevant to Organic Electronics 100
4.1 Introduction 101
4.2 Theoretical Investigations on Electronic Properties of Organic Molecular Materials 103
4.2.1 Structural Properties: Crystal Geometry and Intermolecular Configuration 103
4.2.1.1 Crystal Structures Optimized with a Variant of Van der Waal Density Functionals 103
4.2.1.2 Electronic Structures with the GW Approximation 110
4.2.1.3 Effects of the Crystal Geometry and the Molecular Configuration 118
4.2.2 Electronic Properties at Organic-Metal Interfaces: Energy Level Alignment and Emergence of the Image Potential-Like States 123
4.2.3 Theoretical Determination of the Ionization Energy and Electron Affinity 129
4.3 Conclusions and Outlook 132
References 134
Part III Interplay Between Computationaland Experimental Approaches 143
5 Enabling Materials By Dimensionality: From 0D to 3D Carbon-Based Nanostructures 144
5.1 Introduction: The Course of Dimensionality 145
5.2 0D Carbon Materials: The Fullerenes 152
5.2.1 Using 0D Carbon Systems to Synthesize 2D Monolayers 155
5.2.1.1 Experimental Results 158
5.2.1.2 Computational Modelling: Breaking the Fullerene Cage 161
5.3 2D Carbon-Based Materials: Graphene and Its Low-Density Allotropes 164
5.3.1 Structure Search Method 165
5.3.1.1 Graphene and Graphene Daughter 165
5.3.1.2 Tilene Parent and Tilene 165
5.3.1.3 Flakene Parent and Flakene 167
5.3.1.4 Liskene 168
5.3.2 Electronic Properties of 2D All-Carbon-Based Materials 169
5.3.3 Mechanical Properties of Two-Dimensional All-Carbon Materials 172
5.4 Graphene Pseudospheres 177
5.5 1D Carbon-Based Materials 178
5.5.1 The GW Method for CNTs 179
5.5.2 Band Gap of Model CNTs 180
5.6 3D Carbon-Based Structures 183
5.6.1 Two Case Studies: Transport Properties of Diamond and Graphite 184
5.6.1.1 The Dielectric Response of Materials 184
5.6.1.2 Theory of Monte Carlo Simulations 190
5.6.1.3 Monte Carlo Simulations of Energy-Loss Spectra and Secondary Electron Yield 192
5.6.2 Graphite for Armour Technologies 195
5.6.3 Other 3D Carbon Materials: Foams and Graphene Frameworks 196
5.6.3.1 Graphene Foams 196
5.6.3.2 Pillared Graphene 198
5.7 Conclusions and Future Outlook 199
References 203
6 Group 13–15 Needle-Shaped Oligomers and Nanorods: Structures and Electronic Properties 210
6.1 Introduction 211
6.2 13–15 Needle-Shaped Oligomers: Experimental and Computational Studies 213
6.2.1 Synthetic Methods of Production of Needle-Shaped 13–15 Compounds 213
6.2.2 Structural Features and Reactivity of Needle-Shaped Oligomers 217
6.2.2.1 Tetramers 217
6.2.2.2 Heptamers and Decamers 221
6.2.2.3 Higher Oligomers and Polymers 223
6.2.3 Reaction Pathways to 13–15 Needle-Shaped Compounds 226
6.3 Electronic Properties of Ga-N-Based Needle-Shaped Oligomers 229
6.3.1 Background of Ga-N-Based Needle-Shaped Oligomers 229
6.3.2 Analysis of Computational Approaches 233
6.3.2.1 180hoice of the Level of the Theory of the Computational Method 233
6.3.2.2 Band Structure Computation Method 236
6.3.3 Small Open (CH3)3[CH3MNH]9H3 and Closed [CH3MNH]10 Mixed Metal Oligomers (M == Al, Ga, In) 239
6.3.3.1 Structures of Mixed Metal Oligomers 239
6.3.3.2 Effect of Group 13 Metal on the Electronic Structure of Mixed Metal Oligomers 242
6.3.3.3 Excitation Spectra 245
6.3.4 Size Effect: The Elongation of the [RGaNH]n Oligomers 248
6.3.4.1 The Effect of the Rod Termination on the Structural Properties 248
6.3.4.2 Band Structure of [RGaNH]n Polymer and Electronic Structure of Finite Size Oligomers 251
6.3.4.3 Thermodynamic Characteristics of the Oligomer Elongation 256
6.3.5 The Effect of Terminal Substituents on the Electronic Properties of Oligomers 258
6.4 Conclusions 268
6.5 Future Directions 271
References 272
7 Computational and Experimental Analysis of Carbon Functional Nanomaterials 278
7.1 Introduction 278
7.2 Density Functional Theory 281
7.3 Graphene-Based Functional Nanomaterials 282
7.3.1 Active Sites of Graphene-Based Metal-Free Catalysts 283
7.3.2 Oxidation Reactions 285
7.3.3 Oxidative Dehydrogenation 286
7.3.4 Friedel-Crafts Reaction 287
7.3.5 Oxidative Coupling 289
7.3.6 C–H Bond Activation 291
7.3.7 Reduction of Nitro Compounds 293
7.4 Porous Carbon-Based Functional Nanomaterials 295
7.5 DFT Analysis for Structural, Fluorescence, and Sensing Properties of Fluorescent Carbon Nanomaterials 299
7.5.1 Structural and Fluorescence Analysis of Graphene Quantum Dots and Carbon Dots 301
7.5.2 Sensing Analysis of Graphene Quantum Dots and Carbon Dots 308
7.6 Conclusions 310
7.7 Outlook 311
References 312
8 Electronic Properties of Transition Metal-Benzene Sandwich Clusters 321
8.1 Introduction 322
8.2 Preparation and Structures of Transition Metal-Benzene Sandwich Clusters 323
8.2.1 Early Studies on Sandwich Complexes 323
8.2.2 Gas-Phase Synthesis of Organometallic Complexes 325
8.2.3 Mass Spectroscopic Characterization of Transition Metal-Benzene Sandwich Clusters 327
8.3 Electronic and Magnetic Properties of Transition Metal-Benzene Sandwich Clusters 331
8.3.1 Physical Properties of Low-Dimensional Materials 331
8.3.2 Low Dimensionality of Transition Metal-Benzene Sandwich Clusters 332
8.3.3 Laser Spectroscopic Studies of Transition Metal-Benzene Sandwich Clusters 335
8.3.4 Joint Anion Photoelectron and Computational Studies of Vanadium-Benzene Sandwich Clusters and Their Anions 340
8.3.5 Multiple-Decker and Ring Sandwich Formation of Manganese-Benzene Cluster Anions 345
8.4 Conclusions and Outlook 350
References 352
Part IV Experimental Approach 358
9 Si Nanopowder for Photoluminescence and Hydrogen Generation Materials 359
9.1 Photoluminescence From Si Nanostructures 360
9.1.1 Introduction 360
9.1.2 Experiments 361
9.1.3 Results and Discussion 361
9.1.3.1 Structure of Si Nanopowder 361
9.1.3.2 Photoluminescence from Si Nanopowder 362
9.2 Hydrogen Generation from Si Nanopowder by Reaction with Water 374
9.2.1 Introduction 374
9.2.2 Experiments 375
9.2.3 Results and Discussion 376
9.2.3.1 Reaction of Si Nanopowder with Strong Alkaline Solutions 376
9.2.3.2 Reaction of Si Nanopowder with Neutral Water 377
9.3 Conclusion 385
9.4 Outlook 386
References 387
10 New Na+ Superionic Conductor Narpsio Glass-Ceramics 389
10.1 Introduction 390
10.2 Materials 392
10.2.1 Glasses and Glass-Ceramics 392
10.2.2 Characterization 393
10.2.2.1 AC Impedance Measurement 393
10.2.2.2 X-Ray Diffraction 394
10.2.2.3 Scanning Electron Microscope and Transmission Electron Microscope 395
10.2.2.4 Arrhenius Plot and Kissinger Plot 395
10.3 Phase Stability and Transformation 396
10.3.1 Composition Dependence of Precursor and High-Temperature-Stable phases 396
10.3.2 Kinetic Effects of Composition on the Phase Transformation 398
10.4 Effects of Microstructure on Conduction Properties 401
10.4.1 Crystallization and Phase Diagram 401
10.4.2 Conduction Properties of Crystalline Grains 402
10.4.3 Structure and Conduction Properties of Grain Boundaries 404
10.5 Microstructural Control of Glass-Ceramic Narpsio Conductors 405
10.5.1 Preparation of Crack-Free Na5YSi4O12-Type Glass-Ceramics Containing Large Sm3+ Ions: Crystallization Conditions and Ionic Conductivities [15–17] 405
10.5.2 Composition Control of Silicophosphate Glass-Ceramics 408
10.5.2.1 Ionic Conductivities of Nasicon-Type Glass-Ceramic Superionic Conductors in the System Na2O-Y2O3-XO2-SiO2 (X == Ti, Ge, Te) [37] 408
10.5.2.2 Synthesis and Na+ Conduction Properties of Nasicon-Type Glass-Ceramics in the System Na2O-Y2O3-X2O3-SiO2 (X == B, Al, Ga) and Effect of Si Substitution [38] 410
10.5.2.3 Effect of Substitution of Si with V and Mo on Ionic Conductivity of Na5YSi4O12-Type Glass-Ceramics [41] 412
10.5.2.4 Synthesis and Na+ Conduction Properties of Nasicon-Type Glass-Ceramics in the System Na2O-Y2O3-R2O3-P2O5-SiO2 (R == rare earth) and Effect of Y Substitution [42] 413
10.5.3 Ionic Conductivities of Na+ Ion-Implanted Silicophosphate Glass-Ceramics [26] 415
10.5.4 Structure and Conduction Properties of Na5YSi4O12-Type Glass-Ceramics Synthesized by Bias Crystallization of Glass [27] 417
10.6 Concluding Remarks 420
10.7 Future Prospects 421
References 422
11 Surface Characterization of Plasma-Electrolytic Oxidized Coatings by X-Ray Photoelectron Spectroscopy 423
11.1 Introduction 423
11.2 Composition and Electronic State of Surface Metal Oxide Structure 424
11.2.1 Experimental Details 424
11.2.2 Experimental Results 424
11.3 Outlook 427
References 427
12 Inter-spin Interactions of Organic Radical Chains in Organic 1D Nanochannels: An ESR Study of the Molecular Orientations and Dynamics of Guest Radicals 428
12.1 Introduction of Inclusion Compounds 428
12.2 Theoretical Background and ESR Simulation 433
12.2.1 Electron Spin Resonance 433
12.2.2 Nuclear Magnetic Resonance 434
12.2.3 ESR Simulation 435
12.2.3.1 g Tensor and A Tensor 435
12.2.3.2 Calculation Procedure 437
12.2.3.3 Rigid-Limit ESR Spectra 437
12.2.3.4 Anisotropic Rotational Diffusion 441
12.2.4 Van Vleck's Formula for Rigid Spin Lattices 442
12.2.5 Dietz's Method for Determination of ESR Line Profiles and Inter-spin Interactions 444
12.3 Experimental Procedure 445
12.3.1 Sample Preparation and Notation 445
12.3.2 Sample Characterization 445
12.4 ESR Analysis of Molecular Orientations and Dynamics of Organic Radicals in CLPOT Nanochannels 446
12.5 ESR Analysis of Isolated Organic Radical in 1D TPP Nanochannels 451
12.6 1D 4-X-TEMPO Chains Constructed in CLPOT and TPP Nanochannels 457
12.7 Concluding Remarks and Outlook 463
References 464
Part V Forthcoming Theoretical Approach 468
13 If Truncated Wave Functions of Excited State Energy Saddle Points Are Computed as Energy Minima, Where Is the SaddlePoint? 469
13.1 Introductory Remark 470
13.2 Overview 470
13.3 The Construction of Fn 480
13.4 Improving a Ground State Approximant ?0 Via an Accurate ?1 483
13.4.1 Improving ?0 Orthogonally to the Exact 1 (Analysis) 483
13.4.2 Improving ?0 Orthogonally to ?1 484
13.4.3 Further Improvement of ?0 485
13.5 Identifying a Flipped Root Around an Avoided Crossing 486
13.6 Demonstrations 489
13.6.1 Formalism in Hylleraas Coordinates 490
13.6.1.1 Fn Minimization Procedure 492
13.6.1.2 Establishing “Exact” Wave Functions 0, 1 and Truncated Approximants ?0, ?1 492
13.6.1.3 Results 493
13.6.1.4 The Main Orbitals: F1 (and OO) Give 1s2s HUM Gives 1s1s
13.6.1.5 Fulfillment of the Saddle Point Criteria by F1 and Immediate Improvement of 0 500
13.6.1.6 Quick Check of Reasonableness via the Main Orbitals and via 2nd Derivatives 501
13.6.1.7 The Energy of ?1+ (the Closest to 1 Orthogonal to ?0) 504
13.6.1.8 Comparison Between F, HUM, and the Lowest Orthogonal to ?0 (OO) 504
13.6.1.9 Remarks 504
13.6.2 Demonstration of Identifying a “Flipped Root” 506
13.6.3 Application to Conventional Configuration Interaction Treatment 509
13.6.3.1 Results 511
13.6.4 Immediate Improvement of a Lowest State Approximant 513
13.7 Final Remark 514
References 515
14 Simulating Quantum Dynamics in Classical Nanoscale Environments 518
14.1 Introduction 519
14.2 Mixed Quantum-Classical Liouville Dynamics 522
14.2.1 The Quantum-Classical Liouville Equation 522
14.2.2 Representing the QCLE in the Adiabatic Basis 524
14.2.3 The Sequential Short-Time Propagation Algorithm 525
14.2.4 Transition Filtering 528
14.2.5 Eigenvector Sign Correction 530
14.3 Applications 533
14.3.1 Vibrational Energy Transfer in an Alpha-Helical Polypeptide 533
14.3.2 Field-Driven Dynamics of a Plasmonic Metamolecule 537
14.4 Summary and Future Outlook 543
Appendix 544
References 545
| Erscheint lt. Verlag | 3.2.2020 |
|---|---|
| Zusatzinfo | XVII, 544 p. 314 illus., 203 illus. in color. |
| Sprache | englisch |
| Themenwelt | Naturwissenschaften ► Chemie ► Physikalische Chemie |
| Naturwissenschaften ► Physik / Astronomie ► Festkörperphysik | |
| Technik | |
| Schlagworte | Advanced Nanomaterials • Computational chemistry for materials • Forthcoming theoretical approach on materials • Functional Analysis • Interplay between theory and experiment on materials |
| ISBN-10 | 981-15-0006-1 / 9811500061 |
| ISBN-13 | 978-981-15-0006-0 / 9789811500060 |
| Haben Sie eine Frage zum Produkt? |
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