Theoretical Chemistry Accounts

, Volume 111, Issue 2, pp 345–351

Relativistic atomic natural orbital type basis sets for the alkaline and alkaline-earth atoms applied to the ground-state potentials for the corresponding dimers

  • Björn O. Roos
  • Valera Veryazov
  • Per-Olof Widmark
Article

DOI: 10.1007/s00214-003-0537-0

Cite this article as:
Roos, B., Veryazov, V. & Widmark, PO. Theor Chem Acc (2004) 111: 345. doi:10.1007/s00214-003-0537-0

Abstract.

New basis sets of the atomic natural orbital (ANO) type have been developed for the atoms Li–Fr and Be–Ra. The ANOs have been obtained from the average density matrix of the ground states and the lowest excited states of the atom, the positive ion, and the dimer at its equilibirium geometry. Scalar realtivisitc effects are included through the use of a Douglas–Kroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of the ground-state potentials for the dimers. Computed bond energies are accurate to within 0.05 eV for the alkaline dimers and 0.02 eV for the alkaline-earth dimers (except for Be2).

Keywords

Relativistic basis sets Atomic natural orbitals Douglas-Kroll Complete-active-space self-consistent field/complete-active-space second-order perturbation theory 

Copyright information

© Springer-Verlag Berlin Heidelberg 2003

Authors and Affiliations

  • Björn O. Roos
    • 1
  • Valera Veryazov
    • 1
  • Per-Olof Widmark
    • 1
  1. 1.Department of Theoretical ChemistryLundSweden

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