Core electron spectroscopy

A study applying core-electron spectroscopy on the addition of HC1 to ethylene, propylene, and isobutylene in the gas phase concludes that a significant portion of the difference between Markovnikov and anti-Markovnikov addition is also... 

Core electron spectroscopy for chemical analysis (ESCA) is perhaps the most definitive technique applied to the differentiation between nonclassical carbocations from equilibrating classical species. The time scale of the measured ionization process is of the order of 10 16 s so that definite species are characterized, regardless of (much slower) intra- and intermolecular exchange reactions—for example, hydride shifts, Wagner-Meerwein rearrangements, proton exchange, and so on. 

Markovnikov s rule The positive portion of the reagent goes to the side of the double or triple bond that has more hydrogens A number of explanations have been suggested for this regioselectivity, but the most probable is that adds to that side that will give the more stable carbocation. This premise has been examined by core electron spectroscopy and by theoretical analysis. Thus, when an alkyl group is present, secondary carbocations are more stable than primary ... 

Bae IT, Scherson DA (1996) Insitu core-electron spectroscopy of carbon monoxide adsorbed on high-area platinum in an acid electrolyte. J Phys Chem 100 19215-19217... 

The one-center expressions given above have been routinely used to analyze the different molecular core electron spectroscopies, and they comply with the notion that different core hole derived spectra map the same set of final states differently according to the localization character of wavefunctions and orbitals, and they thus supply local information of symmetries and densities. Although these local selection rules were stated several decades ago, they have survived as a... 

M. Bucher,/. Phys. Chem., 90, 3411 (1986). Core Electron Spectroscopy of Hydrated Ions. 

Electrons interact with solid surfaces by elastic and inelastic scattering, and these interactions are employed in electron spectroscopy. For example, electrons that elastically scatter will diffract from a single-crystal lattice. The diffraction pattern can be used as a means of stnictural detenuination, as in FEED. Electrons scatter inelastically by inducing electronic and vibrational excitations in the surface region. These losses fonu the basis of electron energy loss spectroscopy (EELS). An incident electron can also knock out an iimer-shell, or core, electron from an atom in the solid that will, in turn, initiate an Auger process. Electrons can also be used to induce stimulated desorption, as described in section Al.7.5.6. 

A popular electron-based teclmique is Auger electron spectroscopy (AES), which is described in section Bl.25.2.2. In AES, a 3-5 keV electron beam is used to knock out iimer-shell, or core, electrons from atoms in the near-surface region of the material. Core holes are unstable, and are soon filled by either fluorescence or Auger decay. In the Auger... 

X-ray photoelectron spectroscopy (XPS), also called electron spectroscopy for chemical analysis (ESCA), is described in section Bl.25,2.1. The most connnonly employed x-rays are the Mg Ka (1253.6 eV) and the A1 Ka (1486.6 eV) lines, which are produced from a standard x-ray tube. Peaks are seen in XPS spectra that correspond to the bound core-level electrons in the material. The intensity of each peak is proportional to the abundance of the emitting atoms in the near-surface region, while the precise binding energy of each peak depends on the chemical oxidation state and local enviromnent of the emitting atoms. The Perkin-Elmer XPS handbook contains sample spectra of each element and bindmg energies for certain compounds [58]. 

Protonated methanes and their homologues and derivatives are experimentally indicated in superacidic chemistry by hydrogen-deuterium exchange experiments, as well as by core electron (ESCA) spectroscopy of their frozen matrixes. Some of their derivatives could even be isolated as crystalline compounds. In recent years, Schmidbaur has pre-... 

The simplest, and perhaps the most important, information derived from photoelectron spectra is the ionization energies for valence and core electrons. Before the development of photoelectron spectroscopy very few of these were known, especially for polyatomic molecules. For core electrons ionization energies were previously unobtainable and illustrate the extent to which core orbitals differ from the pure atomic orbitals pictured in simple valence theory. 

Figure 8.1(c) illustrates schematically the kind of process occurring in Auger electron spectroscopy (AES). The process occurs in two stages. In the first, a high-energy photon ejects an electron from a core orbital of an atom A ... 

Other techniques in which incident photons excite the surface to produce detected electrons are also Hsted in Table 1. X-ray photoelectron Spectroscopy (xps), which is also known as electron spectroscopy for chemical analysis (esca), is based on the use of x-rays which stimulate atomic core level electron ejection for elemental composition information. Ultraviolet photoelectron spectroscopy (ups) is similar but uses ultraviolet photons instead of x-rays to probe atomic valence level electrons. Photons are used to stimulate desorption of ions in photon stimulated ion angular distribution (psd). Inverse photoemission (ip) occurs when electrons incident on a surface result in photon emission which is then detected. 

CEELS Core Electron Energy-Loss Spectroscopy... 

Several UHV techniques which have been developed have not found such wide use in corrosion analysis, despite potential applicability. Ultraviolet photoelectron spectroscopy (UPS) is one of these, operating in a similar fashion to XPS (but using an ultraviolet excitation), and probing the valence electrons, rather than the core electrons of the atoms. Because the energies of the valence electrons are so very sensitive to the precise state of the atom, the technique is in principle very informative however exactly this high sensitivity renders the data difficult to interpret, particularly as a routine... 

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. 

XPS or ESCA (electron spectroscopy for chemical analysis) is a surface sensitive technique that only probes the outer atomic layers of a sample. It is very useful tool to study polymer surfaces [91]. An XPS spectrum is created by focusing a monochromatic beam of soft (low-energy) X-rays onto a surface. The X-rays cause electrons (photoelectrons) with characteristic energies to be ejected from an electronic core level. XPS, which may have a lateral resolution of ca. 1-10 pm, probes about the top 50 A of a surface. 

The nature of the final state depends upon the energy, hv, of the exciting photons. In X-ray photoelectron spectroscopy (XPS) the exciting photons are provided by sources such as A1 Ka (1,486 eV) or Mg Ka (1,253 eV) and excitation of the core electrons of the molecules is observed. In UV photoelectron spectroscopy (UPS), Hel (21.2eV) or Hell (40.8 eV) radiation is used and excitation from the valence region of the neutral molecule is observed. XPS and UPS are surface-sensitive techniques, which are capable of providing extremely useful information on the chemical nature of a surface or interface and, in the case of the XPS, the conformational state of the molecules at the surface [64]. 

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