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Negative energy states in relativistic quantum chemistry

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Abstract

The role of the negative energy states in relativistic quantum chemistry is shortly discussed. They must be included in a sum over states formula that arises for second-order properties. Relativistic calculations for the electric dipole polarizability and the diamagnetic susceptibility (with on-center and displaced gauge origins) for hydrogen-like ions are presented to illustrate the problem. Relativistic electron correlation calculations mostly use a configuration space Dirac-Coulomb operator together with the no-pair approximation, which excludes the negative energy states from the correlation treatment. Despite all efforts, no consistent theoretical description between this and a full QED treatment seems to exist.

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  1. Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße, 67663, Kaiserslautern, Germany

    Christoph van Wüllen

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  1. Christoph van Wüllen
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Correspondence to Christoph van Wüllen.

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van Wüllen, C. Negative energy states in relativistic quantum chemistry. Theor Chem Acc 131, 1082 (2012). https://doi.org/10.1007/s00214-011-1082-x

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