Theoretical Chemistry Accounts

, Volume 96, Issue 4, pp 248–255

Atomic ionization potentials and electron affinities with relativistic and mass corrections

Authors

  • Toshikatsu Koga
    • Department of Applied Chemistry, Muroran Institute of Technology, Muroran, Hokkaido 050, Japan
  • Hidenori Aoki
    • Department of Applied Chemistry, Muroran Institute of Technology, Muroran, Hokkaido 050, Japan
  • J. M. Garcia de la Vega
    • Departamento de Química Física Aplicada, Facultad de Ciencias, Universidad Autónoma de Madrid, E-28049 Madrid, Spain
  • Hiroshi Tatewaki
    • Institute of Natural Sciences and Computation Center, Nagoya City University, Nagoya, Aichi 467, Japan

DOI: 10.1007/s002140050227

Cite this article as:
Koga, T., Aoki, H., de la Vega, J. et al. Theor Chem Acta (1997) 96: 248. doi:10.1007/s002140050227

Abstract.

Relativistic corrections to ionization potentials (IPs) and electron affinities (EAs) of atoms with an atomic number Z≤54 are examined based on the first-order perturbation theory with an approximate Schrödinger form of the Dirac-Coulomb-Breit Hamiltonian. Using a Hartree-Fock (HF) wave function from the numerical HF method as the unperturbed function, both the LS-non-splitting and fine-structure corrections are evaluated together with the normal and specific mass corrections. The LS-non-splitting corrections are found to be important for IPs and EAs of transition metal atoms. The fine-structure corrections are generally larger in magnitude than the LS-non-splitting corrections for the atoms of groups 13–18 with Z≥31, and can never be neglected. Comparison of the IPs and EAs presented here and experimental IPs and EAs gives an estimation of the electron correlation correction for these properties. For some light atoms, the estimated values agree with the results directly obtained from correlated calculations.

Key words: Relativistic correctionMass correctionIonization potentialElectron affinityAtoms

Copyright information

© Springer-Verlag Berlin Heidelberg 1997