Photoelectron spectroscopy chemical shift

Cattania, M.G. et al.. An experimental correlation between points of zero charge and X-ray photoelectron spectroscopy chemical shifts of oxides. Colloids Surf. A. 76, 233, 1993. 

Delamar, M., Correlation between the isoelectic point of solid surfaces of metal oxides and X-ray photoelectron spectroscopy chemical shifts, J. Electron Spectrosc., 53, Cll, 1990. 

Note that in core-level photoelectron spectroscopy, it is often found that the surface atoms have a different binding energy than the bulk atoms. These are called surface core-level shifts (SCLS), and should not be confiised with intrinsic surface states. Au SCLS is observed because the atom is in a chemically different enviromuent than the bulk atoms, but the core-level state that is being monitored is one that is present in all of the atoms in the material. A surface state, on the other hand, exists only at the particular surface. 

X-ray photoelectron spectroscopy (XPS), which is synonymous with ESCA (Electron Spectroscopy for Chemical Analysis), is one of the most powerful surface science techniques as it allows not only for qualitative and quantitative analysis of surfaces (more precisely of the top 3-5 monolayers at a surface) but also provides additional information on the chemical environment of species via the observed core level electron shifts. The basic principle is shown schematically in Fig. 5.34. 

X-ray photoelectron spectroscopy also provides information on the chemical composition of a surface. An incoming photon causes electrons to be emitted from atomic core levels, which are then analyzed as a function of kinetic energy. The shifts of these core-level energies provide information about the chemical environment surrounding the excited atom. This information also includes changes in the oxidation state of the sample. 

Photoelectron spectroscopy of Ag(enbisbig)(C104)3 gave binding energy chemical shifts for... 

Data Analysis. Data analysis is, of course, directly related to data acquisition. However, not all good data is or can be completely analyzed. For example, McIntyre (J5) has observed that "a broad base in chemical shift data has been slow in developing" for XPS data. Until such a data base existed, it was difficult for both expert and non-expert to interpret spectra from corrosion products, particularly on complex alloys. The Handbook of X-Ray Photoelectron Spectroscopy (27) and collections of Auger parameter data (32 ) are examples of data compilations very useful to a researcher trying to interpret measurements of corrosion products. 

X-ray photoelectron spectroscopy of atomic core levels (XPS or ESCA) is a very powerful tool for characterization of the chemical surrounding of atoms in molecules. In particular, since the method is very surface sensitive, it is possible to monitor the first stages of the interface formation, i.e., in our case the interaction between individual metal atoms and the polymer. Standard core level bonding energies are well known for common materials. However, in our case, we are studying new combinations of atoms and new types of structures for which there are no reference data available. In order to interpret the experimental chemical shifts it is useful to compare with theoretical estimates of the shifts. 

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