Applications of Synchrotron Radiation High-Resolution Studies of Molecules and Molecular Adsorbates on Surfaces

Applications of synchrotron radiation in physics, chemistry, materials science, and biology has now matured from an exotic experimental field into a well-established area of science. The spectroscopy of molecules and molecular adsorbates on surfaces is one area of science, where, in the past, synchrotron-radiation-related studies had made an impact on understanding the ground-state properties as well as the dynamics. With the new high-brightness synchrotron-radiation sources ahead, this will certainly continue to be a field of very active research. This quasi-monograph reviews the current state of the field for both, the active research scientist, and the new graduate student wishing to become acquainted with this field of research.

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.