Iterative partial equalization of orbital electronegativity – a rapid access to atomic charges

1 Introduction.- 1. History.- 2. Scope of Present Book and Review of Past Books.- 3. Name-Calling.- 4. Areas Related to Electron Spectroscopy Not to be Discussed in Detail.- 4.1. Electron-Impact Spectroscopy.- 4.2. Photoemission.- 4.3. Penning Ionization Spectroscopy.- 4.4. Ion Neutralization Spectroscopy.- 5. Fields Related to Electron Spectroscopy.- 2 Instrumentation and Experimental Procedures.- 1. Source Volume.- 1.1. Excitation Devices.- 1.1.1. Electron Gun.- 1.1.2. X-Ray Tube.- 1.1.3. Synchrotron Radiation.- 1.1.4. Vacuum-UV Sources.- 1.2. Target Sample.- 1.2.1. Gases.- 1.2.2. Solids.- 1.2.3. Condensed Vapors, Liquids, and Targets at Other Than Room Temperature.- 1.3. Chamber for Angular Distribution Studies.- 1.4. Preacceleration and Deceleration.- 2. Analyzer.- 2.1. Cancellation of Magnetic Fields.- 2.1.1. Helmholtz Coils.- 2.1.2. Magnetic Shielding.- 2.2. Types of Analyzers.- 2.2.1. Retarding Grid.- 2.2.2. Dispersion.- 3. Detector Systems and Data Analysis.- 3.1. Single-Channel Detector.- 3.2. Position-Sensitive Detector.- 3.3. Scanning the Spectrum.- 3.4. Data Analysis.- 4. New Developments.- 5. Review of Commercial Instruments.- 5.1. AEI.- 5.2. Du Pont.- 5.3. Hewlett-Packard.- 5.4. McPherson.- 5.5. Perkin-Elmer.- 5.6. Physical Electronics.- 5.7. McCrone-RCI.- 5.8. Vacuum Generators, Inc..- 5.9. Varian.- 5.10. Others.- 3 Fundamental Concepts.- 1. Photoelectric Effect.- 2. Binding Energy.- 3. Final States and the Sudden Approximation.- 3.1. Spin-Orbit Splitting.- 3.2. Multiplet Splitting.- 3.3. Jahn-Teller Splitting.- 3.4. Electron Shakeoff and Shakeup.- 3.5. Configuration Interaction.- 3.6. Koopmans' Theorem and the Sudden Approximation.- 3.7. Vibrational and Rotational Final States.- 4. Atomic Wave Functions.- 5. Molecular Orbital Theory.- 5.1. Theoretical Models.- 5.1.1. Ab Initio Calculations.- 5.1.2. Semiempirical Calculations.- 5.2. Basis Set Extension and MO Mixing.- 5.3. Atomic and Molecular Orbital Nomenclature.- 5.3.1. Atoms.- 5.3.2. Molecules.- 4 Photoelectron Spectroscopy of the Outer Shells.- 1. Introduction.- 2. Energy Level Scheme.- 2.1. Binding Energy.- 2.2. Final States.- 2.2.1. Spin-Orbit Splitting.- 2.2.2. Multiplet Splitting due to Spin Coupling.- 2.2.3. Jahn-Teller Effect.- 2.2.4. Electron Shakeoff and Shakeup.- 2.2.5. Configuration Interaction.- 2.2.6. Resonance Absorption.- 2.2.7. Collision Peaks.- 3. Identification of the Orbital.- 3.1. Ionization Potentials.- 3.1.1. Characteristic Ionization Bands.- 3.1.2. Effects of Substituents.- 3.1.3. Sum Rule.- 3.1.4. The Perfluoro Effect.- 3.1.5. Dependence on Steric Effects.- 3.2. Identification of Orbitals by Vibrational Structure.- 3.3. Identification of Molecular Orbitals from Intensities of Ionization Bands.- 3.4. Identification of Molecular Orbitals by Angular Distribution.- 4. Comparison of PESOS with Other Experimental Data.- 4.1. Optical Spectroscopy.- 4.2. Mass Spectroscopy.- 5. Survey of the Literature on PESOS.- 5.1. Atoms.- 5.2. Diatomic Molecules.- 5.2.1. H2.- 5.2.2. N2 and CO.- 5.2.3. O2 and NO.- 5.2.4. Diatomic Molecules Containing Halogen.- 5.3. Triatomic Molecules.- 5.3.1. Linear Triatomic Molecules.- 5.3.2. Bent Triatomic Molecules.- 5.4. Organic Molecules.- 5.4.1. Methane, Alkanes, and Tetrahedral Symmetry.- 5.4.2. Unsaturated Aliphatics.- 5.4.3. Ring Compounds.- 5.4.4. Multiring Compounds.- 5.4.5. Organic Halides.- 5.4.6. Miscellaneous Organic Compounds Containing Oxygen, Nitrogen, Sulfur, and Phosphorus.- 5.5. Organometallics and Miscellaneous Inorganic Polyatomic Molecules.- 5.6. Ions, Transient Species, and Other Special Studies in PESOS.- 6. Studies on Solids.- 7. Analytical Applications of PESOS.- 5 Photoelectron Spectroscopy of the Inner Shells.- 1. Atomic Structure.- 2. Theoretical Basis of Chemical Shifts of Core Electrons.- 2.1. Valence Shell Potential Model.- 2.2. Effect of Neighboring Atoms.- 2.3. Calculation of Net Charge from Electronegativity.- 2.4. Calculation of Net Charge from Semiempirical MO.- 2.5. Use of Ab Initio Calculations for Chemical Shifts.- 2.6. Correlation of Chemical Shift with Thermochemical Data.- 3. Summary of Data on Chemical Shifts as a Function of the Periodic Table.- 3.1. Carbon.- 3.2. Nitrogen and Phosphorus.- 3.3. Sulfur and Oxygen.- 3.4. Group IIIA, IVA, VA, and VIA Elements.- 3.4.1. Group IIIA: B, Al, Ga, In, and Tl.- 3.4.2. Group IVA: C, Si, Ge, Sn, and Pb.- 3.4.3. Group VA: N, P, As, Sb, and Bi.- 3.4.4. Group VIA: O, S, Se, and Te.- 3.5. Halides and Rare Gases.- 3.6. Alkali Metals and Alkaline Earths.- 3.7. Transition Metals.- 3.7.1. First Transition Metal Series: Sc, Ti, V, Cr, Mn, Fe, Co, Ni.- 3.7.2. Second Transition Metal Series: Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd.- 3.7.3. Third Transition Metal Series: Hf, Ta, W, Re, Os, Ir, Pt.- 3.8. Groups IB and IIB: Cu, Ag, Au, Zn, Cd, Hg.- 3.9. Rare Earths and Actinides.- 4. Special Topics on Shifts in Core Binding Energies.- 4.1. Experimental and Interpretive Problems in PESIS.- 4.1.1. Comparative Problems in the Gas and Solid Phases.- 4.1.2. Charging.- 4.1.3. Definition of Binding Energy for Insulators.- 4.1.4. Binding Energy of Surface Atoms.- 4.1.5. Radiation Effects.- 4.1.6. Linewidths.- 4.2. Inorganic Compounds.- 4.2.1. Multiple Chemical Environment.- 4.2.2. Coordination Complexes.- 4.3. Organic Compounds.- 4.3.1. Resonance.- 4.3.2. Substituent Effects.- 4.3.3. Group Analysis.- 4.3.4. Specific Studies on Organic Molecules.- 4.4. Comparison of Core Electron Binding Energy Shifts with Other Physical Quantities.- 4.4.1. Mossbauer Isomer Shift.- 4.4.2. NMR.- 4.4.3. Other Physical Data.- 5. Other Applications of PESIS.- 5.1. Multicomponent Structure.- 5.1.1. Multiplet or Exchange Splitting.- 5.1.2. Electron Shakeoff and Shakeup.- 5.1.3. Configuration Interaction.- 5.1.4. Characteristic Energy Losses.- 5.1.5. Determining the Nature of Multicomponent Structure.- 5.2. PESIS for Surface Studies.- 5.3. Angular Studies with PESIS.- 6. Use of PESIS for Applied Research.- 6.1. PESIS as an Analytical Tool.- 6.2. Biological Systems.- 6.3. Geology.- 6.4. Environmental Studies.- 6.5. Surface Studies.- 6.6. Polymers and Alloys.- 6.7. Radiation Studies.- 6.8. Industrial Uses.- 6 Auger Electron Spectroscopy.- 1. Theory of the Auger Process.- 2. Comparison of the Auger Phenomenon with the Photoelectric Effect and X-Ray Emission.- 3. Use of Auger Spectroscopy for Gases.- 3.1. Atoms.- 3.2. Molecules.- 3.3. Study of Ionization Phenomena by Auger Spectroscopy.- 3.4. Autoionization.- 3.5. Auger Spectroscopy for Use in Gas Analysis.- 4. Use of Auger Spectroscopy in the Study of Solids.- 4.1. Special Problems Encountered on Using AES with Solids.- 4.1.1. Variables Concerned with Production of Auger Electrons.- 4.1.2. High-Energy Satellite Lines.- 4.1.3. Characteristic Energy Losses.- 4.1.4. Charging in Nonconducting Samples.- 4.2. High-Resolution Auger Spectroscopy with Solids.- 4.3. General Analytical Use of Auger Spectroscopy.- 4.4. Use of Auger Spectroscopy in the Study of Surfaces.- 4.4.1. General Considerations.- 4.4.2. Literature Survey of Surface Applications.- 4.5. Other Methods for Surface Analysis.- 4.5.1. Comparison of PESIS and Auger Spectroscopy for Surface Studies.- 4.5.2. Methods of Surface Analysis Other than AES and PESIS.- Appendixes.- 1. Atomic Binding Energies for Each Subshell for Elements Z = 1-106.- 3. Compilation of Data on Shifts in Core Binding Energies.- 4. Acronyms and Definitions of Special Interest in Electron Spectroscopy.- References.

Photoelectron and Auger Spectroscopy

Highly active and low-cost catalysts for electrochemical reactions such as the hydrogen evolution reaction (HER) are crucial for the development of efficient energy conversion and storage technologies. Theoretical simulations have been instrumental in revealing the correlations between the electronic structure of materials and their catalytic activity, and guide the prediction and development of improved catalysts. However, difficulties in accurately engineering the desired atomic sites lead to challenges in making direct comparisons between experimental and theoretical results. In MoS2, the Mo-edge has been demonstrated to be active for HER whereas the S-edge is inert. Using a computational descriptor-based approach, we predict that by incorporating transition metal atoms (Fe, Co, Ni, or Cu) the S-edge site should also become HER active. Vertically standing, edge-terminated MoS2 nanofilms provide a well-defined model system for verifying these predictions. The transition metal doped MoS2 nanofilms show an increase in exchange current densities by at least two-fold, in agreement with the theoretical calculations. This work opens up further opportunities for improving electrochemical catalysts by incorporating promoters into particular atomic sites, and for using well-defined systems in order to understand the origin of the promotion effects.

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Transition-metal Doped Edge Sites in Vertically Aligned MoS2 Catalysts for Enhanced Hydrogen Evolution

Surface spectroscopic characterization of Cu/Al2O3 catalysts

James C. Carver

Papers

A surface study of cobalt-molybdena-alumina catalysts using x-ray photoelectron spectroscopy

An ESCA study of organosilicon compounds

Electron spectroscopy (ESCA). Use for trace analysis

Remote inductive effects evaluated by x-ray photoelectron spectroscopy (ESCA)

Electron spectroscopy. X-ray and electron excitation