Contents Chapter 1 Nanotechnology, the Technology of Small Thermodynamic Systems 1 1.1 Introduction 1 1.2 Origins of Nanotechnology 1 1.3 What Nanotechnology Is 4 1.3.1 What Can Nanotechnology Do For Us? 5 1.3.2 Where did the Name Nano Came From? 5 1.3.3 Does Every Nanosystem Have To Be So Small? 6 1.3.4 How and Why do the Properties of Matter Change by Entering the Nano-domain? 7 1.3.5 Has Nanotechnology Been Used Before? 7 1.3.6 Why did it Take us so Long to Realize the Importance of Nanotechnology? 9 1.4 Back to the Science 11 1.5 Large Systems and Small Systems Limits 11 1.6 Scales of Inhomogeneity 14 1.6.1 Thermal Gravitational Scale 14 1.6.2 Capillary Length 14 1.6.3 Tolman Length 15 1.6.4 Line Tension (t) and the (t/s) Ratio 16 1.6.5 Correlation Length (x) 17 1.7 Thermodynamics of Small Systems 19 1.8 Configurational Entropy of Small Systems 21 1.9 Nanophenomena 26 1.9.1 Optical Phenomena 26 1.9.2 Electronic Phenomena 30 RSC Nanoscience & Nanotechnology No. 13 Raman Spectroscopy, Fullerenes and Nanotechnology By Maher S. Amer r Maher S. Amer 2010 Published by the Royal Society of Chemistry, www.rsc.org xi
xii Contents 1.9.3 Thermal Phenomena 35 1.9.4 Mechanical Phenomena 37 References 38 Chapter 2 Raman Spectroscopy; the Diagnostic Tool 43 2.1 Introduction 43 2.2 Raman Phenomenon 44 2.3 General Theory of Raman Scattering 44 2.4 Raman Selection Rules 47 2.4.1 Vibration Modes and the Polarizability Tensor 47 2.5 Symmetry 50 2.5.1 Identity (E) 51 2.5.2 Center of Symmetry (i) 51 2.5.3 Rotation Axes (C n ) 52 2.5.4 Planes of Symmetry (s) (Mirror Planes) 53 2.5.5 Rotation Reflection Axes (S n ) (Improper Rotation) 53 2.5.6 Symmetry Elements and Symmetry Operations 55 2.6 Point Groups 56 2.6.1 Point Groups of Molecules 56 2.6.2 Point Groups of Crystals 60 2.7 Space Groups 62 2.7.1 Screw Axis (n p ) 63 2.7.2 Glide Planes 65 2.7.3 Space Groups in One- and Two-dimensional Space 66 2.8 Character Table 69 2.8.1 Symmetry Operations and Transformation of Directional Properties 69 2.8.2 Degenerate Symmetry Species (Degenerate Representations) 73 2.8.3 Symmetry Species in Linear Molecules 74 2.8.4 Classification of Normal Vibration by Symmetry 74 2.8.5 Raman Overtones and Combination Bands 79 2.8.6 Molecular and Lattice Raman Modes 79 2.9 Raman from an Energy Transfer Viewpoint 81 2.10 Boltzmann Distribution and its Correlation to Raman Lines 83 2.11 Perturbation Effects on Raman Bands 85 2.11.1 Strain Effects 85 2.11.2 Heat Effects 86 2.11.3 Hydrostatic Pressure Effects 88 2.11.4 Structural Imperfections Effects 90 2.11.5 Chemical Potentials Effects 92 2.12 Resonant Raman Effect 95
Contents 2.13 Calculations of Raman Band Positions 95 2.14 Polarized Raman and Band Intensity 96 2.15 Dispersion Effect 99 2.16 Instrumentation 101 Recommended General Reading 106 References 106 xiii Chapter 3 Fullerenes, the Building Blocks 109 3.1 Overview 109 3.2 Introduction 109 3.3 Fullerenes, the Beginnings and Current State 110 3.4 Zero-dimensional Fullerenes: The Structure 117 3.4.1 Structure of the [60] Fullerene Molecule 123 3.4.2 Structure of the [70] Fullerene Molecule 126 3.5 Production Methods of Fullerenes 129 3.5.1 Huffman Kra tschmer Method 129 3.5.2 Benzene Combustion Method 131 3.5.3 Condensation Method 132 3.6 Extraction Methods of Fullerenes 133 3.7 Purification Methods of Fullerene 137 3.8 Fullerene Onions 140 3.9 One-dimensional Fullerene: The Structure 143 3.9.1 Single-walled Carbon Nanotubes (SWCNTs) 143 3.9.2 Multi-walled Carbon Nanotubes (MWCNTs) 155 3.9.3 Production of Carbon Nanotubes 158 3.10 Two-dimensional Fullerenes Graphene 161 References 168 Chapter 4 The Nano-frontier; Properties, Achievements, and Challenges 182 4.1 Introduction 182 4.2 Raman Scattering of Fullerenes 183 4.2.1 Raman Scattering of C 60 Molecules and Crystals 183 4.2.2 Raman Scattering of C 70 189 4.2.3 Raman Scattering of Single-walled Carbon Nanotubes 190 4.2.4 Raman Scattering of Double- and Multi-walled Carbon Nanotubes 197 4.2.5 Raman Scattering of Graphene 201 4.2.6 Thermal Effects on Raman Scattering 208 4.3 Fullerene Solubility and Solvent Interactions 215 4.3.1 Solvent Effects on Fullerenes 221 4.3.2 Fullerene Effects on Solvents 225
xiv Contents 4.4 Fullerenes under Pressure 229 4.5 Overview, Potentials, Challenges, and Concluding Remarks 236 References 240 Appendix 1 Character Tables for Various Point Groups 259 Appendix 2 Appendix 3 General Formula for Calculating the Number of Normal Vibrations in Each Symmetry Species 267 Polarizability Tensors for the 32 Point Groups including the Icosahedral Group 272 Subject Index 276
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