Applications of Synchrotron Radiation: High-Resolution Studies of Molecules and Molecular Adsorbates on Surfaces (Springer Series in Surface Sciences)

The reader of this monograph will learn about the application of synchrotron radiation to the study of the ground state and dynamics of molecules and molecular adsorbates on surfaces. This is a comprehensive review of techniques to determine the structure, electronic, and vibrational properties of molecular adsorbates. A summary of the current development of spectroscopic methods with synchrotron radiation is given. It also gives a comprehensive review of the state of the art technique development and current understanding of the ground state structure, electronic structure, and dynamic behavior of small chemisorbed molecules.

1. Introduction.- References.- 2. Band-Structure Determination of Adsorbates.- 2.1 Historical Introduction.- 2.2 CO Adsorbates.- 2.2.1 Symmetry Considerations and CO-Substrate Interactions.- 2.2.2 Ordered Overlayers.- 2.3 Ethylene Adsorbates.- 2.3.1 Symmetry Consideration and Ethylene-Substrate Interaction.- 2.3.2 Ordered Ethylene Overlayers.- 2.4 Benzene Adsorbates.- 2.5 Co-Adsorbates.- 2.6 Synopsis.- References.- 3. High-Resolution Core-Level Photoelectron Spectroscopy of Surfaces and Adsorbates.- 3.1 Background.- 3.2 Instrumentation.- 3.3 Core-Level Shifts.- 3.3.1 Initial and Final State Effects.- 3.3.2 Equivalent Core or Z + 1 Approximation.- 3.4 Adsorbate Core-Level Shifts.- 3.4.1 Final State Effects.- 3.4.2 Chemical Shifts Between Inequivalent Atoms.- 3.4.3 Adsorption Site-Dependent Shift in CO.- 3.4.4 Molecular Orientation and Site-Dependent Shifts in NO.- 3.4.5 Physisorption-Induced Shifts in O2.- 3.5 Surface Core-Level Shifts.- 3.5.1 Clean Metals.- 3.5.2 Adsorbate-Induced Shifts.- 3.6 Core-Level Line Shapes.- 3.7 Vibrational Effects.- 3.7.1 The Franck-Condon Principle.- 3.7.2 Vibrational Broadening in Adsorbates.- 3.8 Shake-up Satellites.- 3.8.1 General Aspects.- 3.8.2 Substrate Excitations for Adsorbed Argon.- 3.8.3 Local Excitations in Strongly Chemisorbed Atoms.- 3.8.4 Chemisorption-Induced Excitations in Adsorbed CO and N2.- References.- 4. Structure Determination of Molecular Adsorbates Using Photoelectron Diffraction.- 4.1 Introductory Comments.- 4.2 Basis of the Technique and Its Potential.- 4.3 Examples.- 4.3.1 Forward-Scattering Photoelectron Diffraction (XPD): CO on Ni (110).- 4.3.2 Experimental Methodology and Qualitative Site Sensitivity in PhD.- 4.3.3 Quantitative Structural Analysis with PhD.- 4.3.4 Chemical-Shift Photoelectron Diffraction.- 4.4 Concluding Remarks.- References.- 5. Near Edge X-Ray Absorption and Decay Dynamics of Adsorbed Molecules.- 5.1 Background.- 5.2 X-Ray Absorption.- 5.2.1 Physisorbed Molecules.- 5.2.2 Chemisorbed Molecules.- 5.3 Decay Dynamics.- 5.3.1 Physisorbed Molecules.- 5.3.2 Chemisorbed Molecules.- 5.4 Desorption and Dissociation.- 5.5 Conclusions.- References.- 6. Spectroscopy and Dynamics of the Electronic Decay of Core Electron Excitations in Isolated and Chemisorbed Molecules.- 6.1 Deexcitation Electron Spectroscopy.- 6.1.1 Historical Development.- 6.1.2 Development of an Empirical Assignment.- 6.1.3 Relationship Between Photoemission and DES.- 6.2 Probing the Local Electronic Structure and Response.- 6.2.1 Deexcitation.- 6.2.2 Basic Parameters of the Spectator Shift.- 6.3 A Detailed Probe of Electron Correlation.- 6.3.1 The Difference Between n*; and Rydberg Excitations in N2.- 6.3.2 Threshold Behaviour in CO2:‘There is No Threshold at the XPS-Threshold’.- 6.3.3 Identification of the Primary Excitation Through the Decay Spectra (O2).- 6.4 Dynamics of Core-Electron-Excited States.- 6.4.1 Coherence and Interference.- 6.4.2 Theoretical Description of the Interference Profiles.- 6.4.3 Vibrational Resolution in Excitation and Decay (N2).- 6.4.4 Time Development of the Eigenstates on the FS Time Scale (O2).- 6.5 Direct Observation of Charge Transfer and Screening Processes.- 6.5.1 Deexcitation of Transition Metal Carbonyls and CO Chemisorbed on Surfaces.- 6.6 Summary and Outlook.- References.- 7. Synchrotron Radiation in the Far Infrared: Infrared Reflection Absorption Spectroscopy.- 7.1 IR Spectroscopy at Surfaces.- 7.2 Synchrotron Radiation in the Far Infrared.- 7.3 Examples.- 7.3.1 Resonant Adsorbate-Substrate Interactions for CO Adsorbed on Cu(100).- 7.3.2 Potassium - Oxygen Bond Formation.- 7.4 Conclusion - Outlook.- References.- Index of Molecules and Adsorbate Systems.