Nanotechnology, the Technology of Small Thermodynamic Systems 1

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1 Contents Chapter 1 Nanotechnology, the Technology of Small Thermodynamic Systems Introduction Origins of Nanotechnology What Nanotechnology Is What Can Nanotechnology Do For Us? Where did the Name Nano Came From? Does Every Nanosystem Have To Be So Small? How and Why do the Properties of Matter Change by Entering the Nano-domain? Has Nanotechnology Been Used Before? Why did it Take us so Long to Realize the Importance of Nanotechnology? Back to the Science Large Systems and Small Systems Limits Scales of Inhomogeneity Thermal Gravitational Scale Capillary Length Tolman Length Line Tension (t) and the (t/s) Ratio Correlation Length (x) Thermodynamics of Small Systems Configurational Entropy of Small Systems Nanophenomena Optical Phenomena 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, xi

2 xii Contents Thermal Phenomena Mechanical Phenomena 37 References 38 Chapter 2 Raman Spectroscopy; the Diagnostic Tool Introduction Raman Phenomenon General Theory of Raman Scattering Raman Selection Rules Vibration Modes and the Polarizability Tensor Symmetry Identity (E) Center of Symmetry (i) Rotation Axes (C n ) Planes of Symmetry (s) (Mirror Planes) Rotation Reflection Axes (S n ) (Improper Rotation) Symmetry Elements and Symmetry Operations Point Groups Point Groups of Molecules Point Groups of Crystals Space Groups Screw Axis (n p ) Glide Planes Space Groups in One- and Two-dimensional Space Character Table Symmetry Operations and Transformation of Directional Properties Degenerate Symmetry Species (Degenerate Representations) Symmetry Species in Linear Molecules Classification of Normal Vibration by Symmetry Raman Overtones and Combination Bands Molecular and Lattice Raman Modes Raman from an Energy Transfer Viewpoint Boltzmann Distribution and its Correlation to Raman Lines Perturbation Effects on Raman Bands Strain Effects Heat Effects Hydrostatic Pressure Effects Structural Imperfections Effects Chemical Potentials Effects Resonant Raman Effect 95

3 Contents 2.13 Calculations of Raman Band Positions Polarized Raman and Band Intensity Dispersion Effect Instrumentation 101 Recommended General Reading 106 References 106 xiii Chapter 3 Fullerenes, the Building Blocks Overview Introduction Fullerenes, the Beginnings and Current State Zero-dimensional Fullerenes: The Structure Structure of the [60] Fullerene Molecule Structure of the [70] Fullerene Molecule Production Methods of Fullerenes Huffman Kra tschmer Method Benzene Combustion Method Condensation Method Extraction Methods of Fullerenes Purification Methods of Fullerene Fullerene Onions One-dimensional Fullerene: The Structure Single-walled Carbon Nanotubes (SWCNTs) Multi-walled Carbon Nanotubes (MWCNTs) Production of Carbon Nanotubes Two-dimensional Fullerenes Graphene 161 References 168 Chapter 4 The Nano-frontier; Properties, Achievements, and Challenges Introduction Raman Scattering of Fullerenes Raman Scattering of C 60 Molecules and Crystals Raman Scattering of C Raman Scattering of Single-walled Carbon Nanotubes Raman Scattering of Double- and Multi-walled Carbon Nanotubes Raman Scattering of Graphene Thermal Effects on Raman Scattering Fullerene Solubility and Solvent Interactions Solvent Effects on Fullerenes Fullerene Effects on Solvents 225

4 xiv Contents 4.4 Fullerenes under Pressure 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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