Chapter

Relativistic Methods for Chemists

Volume 10 of the series Challenges and Advances in Computational Chemistry and Physics pp 215-277

Date:

Relativistic Pseudopotentials

  • Xiaoyan CaoAffiliated withInstitut für Theoretische Chemie, Universität zu Köln Email author 
  • , Michael DolgAffiliated withInstitut für Theoretische Chemie, Universität zu Köln

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Abstract

A brief overview over the foundations and modern variants of the relativistic effective core potential method, i.e., energy-consistent and shape-consistent ab initio pseudopotentials as well as ab initio model potentials, is given. The energy-consistent ab initio pseudopotential approach is discussed in more detail, focussing on the uranium atom as an example. The selection of appropriate relativistic reference data, the choice of the core and the fitting procedure are discussed. Results of atomic and molecular test calculations, e.g., for the low-lying electronic states of uranium hydride, are summarized. Whereas the 5f-in-core large-core approximation provides an efficient approximate treatment of larger actinide systems without having to struggle with complexities arising from the open 5f shell, the 5f-in-valence small-core approach allows to reach a similar accuracy as the best available relativistic all-electron calculations.

Keyword

Effective core potentials Model potentials Pseudopotentials Pseudo-valence orbitals Core-polarization potentials Dirac–Coulomb–Hamiltonian Breit interaction Wood–Boring–Hamiltonian Frozen-core errors Uranium Uranium hydride Electronic structure Excited states Calibration