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Jeppe Olsen

ORBITAL CONNECTIONS FOR PERTURBATION-DEPENDENT BASIS-SETS

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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.

Original languageEnglish
JournalTheoretica chimica acta
Volume90
Issue5-6
Pages (from-to)421-439
Number of pages19
ISSN0040-5744
Publication statusPublished - Mar 1995

    Research areas

  • PERTURBATION-DEPENDENT BASIS SETS, ATOMIC ORBITALS, MOLECULAR ORBITALS

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