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On the accuracy of one-component pseudopotential spin-orbit calculations
Stockholm University, Faculty of Science, Department of Physics.
2005 (English)In: Journal of Chemical Physics, Vol. 123, no 16, 164105-164115 p.Article in journal (Refereed) Published
Abstract [en]

Improvements on current one-component extraction procedures of spin-orbit pseudopotentials are investigated for high accuracy computation of spin-orbit coupling energies. By means of the perturbation-theory formalism we first show that spin-orbit pseudopotentials, extracted at the one-component self-consistent-field level from a reference all-electron Dirac-Coulomb or Dirac-Coulomb-Breit calculation, include valence spin-orbit polarization and relaxation effects. As a consequence the use of these pseudopotentials in uncontracted spin-orbit configuration interaction (CI) with singles from the reference ground-state configuration gives rise to double counting of these spin-orbit effects. Two new methods that avoid such double counting have been investigated. The first, so-called “explicit” method, calculates explicitly, by means of a four-component spin-orbit CI, the double-counted spin-orbit effects and removes them from the pseudopotentials. Due to the nonadditivity of the core and valence spin-orbit effects as well as the so-called “pseudovariational collapse,” this method is shown to be cumbersome. In the second “implicit” method the spin-orbit pseudopotential is extracted at the spin-orbit polarized and relaxed level by means of a single-excitation spin-orbit CI calculation. Atomic tests on iodine demonstrate the ability of the latter method to solve the double-counting problem.

Place, publisher, year, edition, pages
2005. Vol. 123, no 16, 164105-164115 p.
Keyword [en]
National Category
Atom and Molecular Physics and Optics
URN: urn:nbn:se:su:diva-23950DOI: 10.1063/1.2072927OAI: diva2:196081
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18 Last updated: 2010-09-10Bibliographically approved

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