Inner-shell

B1.6.3.2 INNER-SHELL-ELECTRON ENERGY-LOSS SPECTROSCOPY... 

Used effects Phonon excitation (20 meV-1 eV) Plasmon and interband excitations (1-50 eV) Inner-shell ionization (A = ionization energy loss) Emission of x-ray (continuous/characteristic, analytical EM)... 

Figure Bl.24.14. A schematic diagram of x-ray generation by energetic particle excitation, (a) A beam of energetic ions is used to eject inner-shell electrons from atoms in a sample, (b) These vacancies are filled by outer-shell electrons and the electrons make a transition in energy in moving from one level to another this energy is released in the fomi of characteristic x-rays, the energy of which identifies that particular atom. The x-rays that are emitted from the sample are measured witli an energy dispersive detector.

In the 6-3IG basis, the inner shell of carbon is represented by 6 primitives and the 4 valence shell orbitals are represented by 2 contracted orbitals each consisting of 4 primitives, 3 contracted and 1 uncontracted (hence the designation 6-31). That gives... 

HyperChem supports MP2 (second order Mpller-Plesset) correlation energy calculationsusing afe mi/io methods with anyavailable basis set. In order to save main memory and disk space, the HyperChem MP2 electron correlation calculation normally uses a so called frozen-core approximation, i.e. the inner shell (core) orbitals are omitted. A setting in CHEM.INI allows excitations from the core orbitals to be included if necessary (melted core). Only the single point calculation is available for this option. 

Calculations at the 6-31G and 6-31G level provide, in many cases, quantitative results considerably superior to those at the lower STO-3G and 3-21G levels. Even these basis sets, however, have deficiencies that can only be remedied by going to triple zeta (6-31IG basis sets in HyperChem) or quadruple zeta, adding more than one set of polarization functions, adding f-type functions to heavy atoms and d-type functions to hydrogen, improving the basis function descriptions of inner shell electrons, etc. As technology improves, it will be possible to use more and more accurate basis sets. 

Most simple empirical or semi-empirical molecular orbital methods, including all of those used in HyperChem, neglect inner shell orbitals and electrons and use a minimal basis set of valence Slater orbitals. 

Thus for H and He, the basis set consists of one orbital, a Is atomic orbital. For atomsLi to Ne the 2 inner-shell electrons are combined with the nucleus and the basis set consists of 4 orbitals, the 2s, 2p, ... 

The distinction between and 1, and Mm, etc., is an important one. These labels are commonly used by those studying inner shell electron processes. 

Shorter-wavelength radiation promotes transitions between electronic orbitals in atoms and molecules. Valence electrons are excited in the near-uv or visible. At higher energies, in the vacuum uv (vuv), inner-shell transitions begin to occur. Both regions are important to laboratory spectroscopy, but strong absorption by make the vuv unsuitable for atmospheric monitoring. Electronic transitions in molecules are accompanied by stmcture... 

Although x-rays probe inner rather than valence electrons, in light elements the chemical state of the emitting atom may affect inner-shell energies enough to be detected at high resolution. Thus the K d lines of sulfur at 0.537 nm shift by 0.3 pm between the oxidation states and. ... 

Certain rotory dryers moy be a combinoHon of irtdirect ond direct types e.g., hot goses first hoot on inner shell arnl then poss between on inner ond outer shell in contact with the wet solid. 

---