Assessment of a new approach for the two-electron cumulant in natural-orbital-functional theory.
The Piris natural orbital functional (PNOF) based on a new approach for the two-electron cumulant has been used to predict adiabatic ionization potentials, equilibrium bond distances, and harmonic vibrational frequencies of 18 diatomic molecules. Vertical ionization potentials have been calculated for the same set of diatomic molecules and another set of 20 polyatomic molecules using energy-difference methods as well as the extended Koopman theorem. The PNOF properties compare favorably with the coupled-cluster-doubles results. The calculated PNOF values are in good agreement with the corresponding experimental data, considering the basis sets used (6-31G**).
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Institute of Physical and Theoretical Chemistry, Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstrasse 3, 91058 Erlangen, Germany.
Piris
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