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Excited States in Quantum Chemistry pp 143–182Cite as

Many-Body Theory of Photoabsorption in Atoms and Molecules

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Part of the book series: NATO Advanced Study Institutes Series ((ASIC,volume 46))

Abstract

We present an approach to the calculation of photoexcitation and photoionization transition probabilities which first derives, consistently, the important correlation effects and then computes them efficiently and accurately. The emphasis is on the correct evaluation of the transition matrix element and not of the exact Schrödinger equation for initial and final wave-functions. The theory is implemented through Configuration-Interaction techniques which allows the practical consideration of any type of state. Both initial and final states are treated at the same level of approximation due to the similarity of restrictions imposed upon them. The basic conceptual and computational characteristics of the theory are simple: The zeroth order vectors for initial and final states are the Fermi-Sea (FS) wave-functions. The transition operator is then applied to the FS vectors and selects the additional correlation effects in initial and final states which contribute to the transition amplitude the most. These correlations are expressed in terms of Hartree-Fock and variationally optimized virtual orbitals for each state. The resulting very small wave-functions are then employed for the calculation of the transition probabilities. This First Order Theory of Oscillator Strengths (FOTOS) is applicable to any system with a shell structure and symmetry (including nuclear transitions). Its application to a variety of atomic transitions has yielded accurate results, some of which are presented here. Also presented are brief discussions on the question of which form of the electric dipole operator is the appropriate one to use in computations, nonorthonormality, extraordinary absorption properties of certain systems, polarizability calculations within FOTOS and the extension of FOTOS to the relativistic domain.

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Authors and Affiliations

  1. Theoretical Chemistry Institute, National Hellenic Research Foundation, 48 Vas. Constantinou Ave., Athens 501/1, Greece

    Cleanthes A. Nicolaides & Donald R. Beck

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  1. Cleanthes A. Nicolaides
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  2. Donald R. Beck
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  1. Theoretical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece

    Cleanthes A. Nicolaides  & Donald R. Beck  & 

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© 1978 D. Reidel Publishing Company, Dordrecht, Holland

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Nicolaides, C.A., Beck, D.R. (1978). Many-Body Theory of Photoabsorption in Atoms and Molecules. In: Nicolaides, C.A., Beck, D.R. (eds) Excited States in Quantum Chemistry. NATO Advanced Study Institutes Series, vol 46. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-9902-2_7

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  • DOI: https://doi.org/10.1007/978-94-009-9902-2_7

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