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Photoelectron Spectroscopy of the Outer Shells

  • Chapter
Photoelectron and Auger Spectroscopy

Part of the book series: Modern Analytical Chemistry ((MOAC))

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Abstract

In this chapter we shall be concerned with the valence shell or outer shell of the molecule. To give a precise, unambiguous definition of the outer shell is a difficult task. In atoms, the outer shell contains those electrons that make up the highest occupied principal shell. In molecules, the outer shell is made up of those orbitals that are derived from atomic outer shell orbitals. Electrons in the outer shell are characterized by large radii and low binding energies. The outer d orbitals of transition metals and the outer d and f orbitals of the rare earths and actinides are examples of the difficulty of unambiguously characterizing the outer shell, since electrons in these orbitals have low binding energies and are often involved in chemical bonding; yet these orbitals are not part of the outermost principal shell and have radii that are considerably smaller than electrons in this shell. Nevertheless, dividing electron orbitals into inner or outer shells is, for the most part, a useful concept. It is the outer shell which includes those electrons that are involved in chemical bonding, and our interest here lies in the intrinsic nature of the molecular orbitals. These orbitals, unlike core levels, are not characteristic solely of a particular atom but of the overall molecule. Essentially, we desire the complete energy level scheme of the molecule. In principle, one ought to examine all the electrons in a molecule, including even the inner shell or core electrons. The inner shell electrons, however, behave primarily like electrons in a free atom, feeling the chemical environment as a perturbation. Thus, the behavior of the inner shell electrons is more profitably discussed from an entirely different viewpoint, and will be treated in a separate chapter (Chapter 5).

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    Thomas A. Carlson

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Carlson, T.A. (1975). Photoelectron Spectroscopy of the Outer Shells. In: Photoelectron and Auger Spectroscopy. Modern Analytical Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-0118-0_4

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