Relativistic Corrections to the Exchange-Correlation Energy Functional

  • E. Engel
  • S. Keller
  • R. M. Dreizler


During recent years the development of fully relativistic methods for electronic structure calculations has been a major trend both in atomic physics and computational quantum chemistry (see e.g.[1–5]). Looking at Gold as the prime candidate for relativistic effects this trend is easy to understand: When going from a nonrelativistic to a relativistic treatment the ionization potential of Au increases by 30% [6], the bond length of AuH is contracted by 13% and its dissociation energy increases by about 50% [6]. The differences are even more dramatic for the electron affinity: For Au a nonrelativistic CI-calculation [7] gives a value of 1.02 eV compared with 2.28 eV obtained with a fully relativistic Coupled-Cluster calculation [4]. Moreover, the fact that the relativistic Hartree-Fock (RHF) approach leads to 7.48 eV [4] for the electron affinity of Au while the nonrelativistic HF value is 0.10 eV, clearly demonstrates that relativistic and exchange-correlation (xc) effects are nonadditive.


Ground State Energy Correlation Energy Relativistic Correction Transverse Part Photon Propagator 
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Copyright information

© Springer Science+Business Media New York 1998

Authors and Affiliations

  • E. Engel
    • 1
  • S. Keller
    • 1
  • R. M. Dreizler
    • 1
  1. 1.Institut für Theoretische PhysikUniversität FrankfurtFrankfurt/MainGermany

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