Edited by. C'unter. and David S. Moore. Gauglitz. Handbook of Spectroscopy. Second, Enlarged Edition. Volume 4. WlLEY-VCH. VerlagCmbH & Co.

Transcription

1 Edited by C'unter Gauglitz and David S. Moore Handbook of Spectroscopy Second, Enlarged Edition Volume 4 WlLEY-VCH VerlagCmbH & Co. KGaA

2 IX Volume 4 Section XII Applications 6: Spectroscopy at Surfaces Optical Spectroscopy at Surfaces 1441 Georgeta Salvan and Dietrich R. T. Zahn 42.1 Introduction Experimental Methods and Theoretical Calculations Properties of Perylene Derivatives Sample Preparation Reflection Anisotropy Spectroscopy Raman Spectroscopy Initial Adsorption of Molecules on Inorganic Semiconductor Surface Reflection Anisotropy Spectroscopy Investigations Raman Investigations Metals on Organic Layers 2473 References NEXAFS Studies at Surfaces 1485 Maria Benedetta Casu and Thomas Chasse 43.1 Introduction Near-Edge X-Ray Absorption Fine Structure: Basic Principles NEXAFS Measurements and Data Analysis Applications NEXAFS as a Fingerprint in Oxides Molecular Orientation, Interaction with the Substrate, and Intermolecular Interaction of an Organic Absorbate: Copper Phthalocyanine Thin Films on a Polycrystalline Gold Substrate Molecular Orientation and Growth Modes Thickness Dependence of the Electronic Structure and Local Geometry in MnO: Differences between Bulk and Thin Film Properties Charge Transfer Between Metal 3d Electrons and Metal Surfaces in Transition-Metal Phthalocyanine/Metal Interfaces X-Ray Magnetic Circular Dichroism Conclusions and Future 2503 References 2504

3 X 44 The X-Ray Standing Wave Technique 1507 Alexander Gerlach and Frank Schreiber 44.1 Introduction Theory Wave Fields in Crystals Standing Waves The Photo Yield Experiment 1514 AAA Examples: Organic Adsorbates PTCDA/Ag(lll), Cu(lll),and Au(lll) NTCDA/Ag(lll) Fi6CuPc/Ag(lll) andcu(lll) SnPc/Ag(lll) PEN/Cu(lll) and PFP/Cu(lll) Other Systems 1519 Acknowledgments 1519 References Photoelectron Spectroscopy Applications to Materials Science 1523 Maria Benedetta Casu and Thomas Chasse 45.1 Introduction Photoelectron Spectroscopy. Basic Principles UPS Regime XPS Regime Photoemission Measurements and Data Analysis Applications Ultraviolet Photoelectron Spectroscopy: Basic Research and Its Relevance in Technology XPS as a Tool to Investigate Buried Interfaces XPS as a Tool to Investigate Growth Modes Laterally Resolved XPS as a Tool to Reveal New Aspects in Physics and Chemistry of Thin Film X-Ray Photoelectron Diffraction (XPD) as a Tool to Investigate Structural Properties Molecular Orbital Densities from Photoemission Spectra of Organic Molecules Conclusions and Future 1551 References 1553 Section XIII Applications 7: Nano-Optics Miniaturized Optical Sensors for Medical Diagnostics 1559 Seong-Soo Kim and Boris Mizaikoff 46.1 Introduction UV/Vis/NIR Plasmonic Sensors 1561

4 XI 46.3 Mid-Infrared Optical Sensors Terahertz Optical Sensors Conclusions and Outlook 1578 References Tip-Enhanced Near-Field Optical Microscopy 2585 Achim Hartschuh 47.1 Introduction Principles of Near-Field Optics Field Enhancement at a Metal Tip Tip-Enhancement of Optical Signals Enhancement of Raman Scattering Enhancement of Fluorescence Experimental Realization Near-Field Microscopes Far-Field Background Tip-Enhanced Fluorescence (TEF) Single-Molecule Fluorescence Enhancement Imaging of Fluorescently Labelled Biosurfaces Tip-Enhanced Raman Scattering (TERS) Signal Enhancement and Detection Sensitivity Chemical Analysis of Surfaces Biopolymers and Biosurfaces Stress Imaging in Semiconductors Nanoscale Optoelectronic Probing Summary 1603 References Optical Waveguide Spectroscopy James S. Wilkinson 48.1 Introduction Integrated Optical Waveguides Optimization of Dielectric Optical Waveguides for Evanescent Spectroscopy Optimization for Bulk Analyte Spectroscopy Optimization for Thin-Film Spectroscopy Absorption Spectroscopy Waveguide Spectroelectrochemistry Fluorescence Spectroscopy Waveguide Raman Spectroscopy Instrumentation Conclusions 2635 Acknowledgments 2635 References 1636

5 XII I Section XIV Hyphenated Techniques Mass Spectral Detection 1645 John C. Fetzer 49.1 Introduction Mass Spectrometers Ionization Approaches for LC-ESI versus APCI Application Examples Acknowledgment 1653 References 1653 for GC-MS and LC-MS Optical Detection 1657 John C. Fetzer 50.1 UV Detection Fluorescence Detection Infrared Detection Applications 1663 References Atomic Spectral Detection 1667 John C. Fetzer 51.1 Introduction Atomization and Plasmas Spectrometric Detection MIP for GC Detection ICP for LC Detection Application oflc-icp MS 1672 Acknowledgments 1675 References NMR as a Chromatography Detector 1679 Klaus Albert 52.1 Structural Assignment Techniques NMR in a Flowing Liquid Design of Continuous-Flow NMR Probes Continuous-Flow!H NMR Probe for LC-NMR Solenoidal NMR Microprobe for Capillary HPLC-NMR and GC-NMR On-Line HPLC-NMR Solvent Signal Suppression LC-SPE-NMR Capillary HPLC-NMR Coupling GPC-NMR Coupling SFC-NMR GC-NMR 1701

6 Quality Examples XIII CE-NMR and CEC-NMR Current Developments Conclusion 1708 Acknowledgment 2708 References 1708 Section XV General Data Treatment: Databases/Spectral Libraries Optical Spectroscopy 1719 Steffen Thiele and Reiner Salzer 53.1 Introduction Basic Operations Centering Standardization (Autoscaling) Evaluation of Spectra Introduction Qualitative Evaluation of Spectra Quantitative Evaluation of Spectra Spectral Imaging 1742 References Nuclear Magnetic Resonance Spectroscopy 2749 Wolfgang Robien 54.1 Introduction Comparison of NMR Spectroscopy 54.3 Methods in NMR Spectroscopy Spectral Similarity Search Techniques Spectrum Estimation Techniques Spectrum Prediction Spectrum Prediction and Quality Control Spectrum Interpretation with IR and MS 2750 Consideration and Isomer Generation Utilization of 2D-NMR Data Examples of Isomer Generator Programs Ranking of Candidate Structures NMR Data Collections on the Internet Conclusions 2765 References Mass Spectrometry 2769 Wolfgang Werther 55.1 Introduction Databases Databases of Electron Impact (EI) Mass Spectra Databases for Mass Spectra from LC-MS 2775

7 XIV j Fragmentation Databases Protein Databases Library Search/Database Retrieval Search Algorithms for EI Mass Spectra Search Algorithms for MS/MS Spectra Search Strategies for Proteins Fragmentation Pathway Prediction Rule-Based Approaches Combinatorial Approaches Determination of the Element Composition Elemental Composition from Accurate Mass Mass Defect Plots and Mass Defect Filtering Elemental Composition from Isotope Peak Pattern Combined Algorithms for Element Composition Deconvolution and Detection of Components GC-MS Deconvolution LC-MS Deconvolution Factor Analysis Methods Multivariate Data Analysis (MVDA) of Mass Spectra Distance and Similarity Dimensionality Reduction Mass Spectral Features Exploratory Data Analysis Mass Spectral Classifiers 1803 References Raman Spectroscopy Fundamentals 1813 David Moore 56.1 Theory Qualitative Analysis Experimental Details Fluorescence Interference Imaging Fiber Optic Probes Raman Data Treatment and Calibration Raman Spectral Databases Database Searching Extensible Markup Language (XML) Data Model 1827 References 1828 index 1831