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Some may object to using the term "expectation value" in this context, since it is usually reserved for describing the eigenvalue of an operator, or equivalently, a matrix element. We justify its use here because [apart from S(-2)] the S(p) are matrix elements, multiplied by constants. Other terms, such as "expected value" or "anticipated value" fall short of conveying the intended meaning.
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The broad, dominant feature at ∼ 20-22 eV has been described as a plasmon (or plasma resonance) in numerous publications. To the uniniated chemist, it may take on the character of a new phenomenon. However, the calculation of this "resonance" is based on a model, originally applied to metals, in which the plasma frequency is a function of the electron density. The more traditional molecular orbital approach should explain this strong feature equally well. Indeed, such calculations have been reported by H. Deutsch, K. Becker, J. Pittner, V. Bonacic-Koutecky, S. Matt, and T. D. Märk, J. Phys. B 29, 5175 (1996). They reveal a large concentration of orbitals with binding energies between ∼13-35 eV, containing ∼200 of the 240 valence electrons. To our knowledge, the transition probabilities from these orbitals to the ionization continuum have not yet been calculated, but presumably they would generate a superposition of many transitions composing this "resonance."
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