Theoretica chimica acta

, Volume 90, Issue 5–6, pp 421–439 | Cite as

Orbital connections for perturbation-dependent basis sets

  • Jeppe Olsen
  • Keld L. Bak
  • Kenneth Ruud
  • Trygve Helgaker
  • Poul Jørgensen
Article

Summary

The use of perturbation-dependent basis sets is analysed with emphasis on the connection between the basis sets at different values of the perturbation strength. A particular connection, the natural connection, that minimizes the change of the basis set orbitals is devised and the second quantization realization of this connection is introduced. It is shown that the natural connection is important for the efficient evaluation of molecular properties and for the physical interpretation of the terms entering the calculated properties. For example, in molecular Hessian calculations the natural connection reduces the size of the relaxation term, leading to faster convergence of the response equations. The physical separation of the terms also means that first-order non-adiabatic coupling matrix elements can be obtained in a very simple way from a molecular Hessian calculation.

Key words

Perturbation-dependent basis sets Atomic orbitals Molecular orbitals 

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Copyright information

© Springer-Verlag 1995

Authors and Affiliations

  • Jeppe Olsen
    • 1
  • Keld L. Bak
    • 2
  • Kenneth Ruud
    • 3
  • Trygve Helgaker
    • 3
  • Poul Jørgensen
    • 4
  1. 1.Theoretical Chemistry, Chemical CentreUniversity of LundLundSweden
  2. 2.Department of Physical ChemistryUniversity of CopenhagenKøbenhavn ØDenmark
  3. 3.Department of ChemistryUniversity of OsloOsloNorway
  4. 4.Department of ChemistryAarhus UniversityAarhus, CDenmark

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