Interpair electron correlation by second-order perturbative corrections to PNOF5.
An antisymmetrized product of strongly orthogonal geminals with the expansion coefficients explicitly expressed by the occupation numbers is used to generate the Piris natural orbital functional 5 (PNOF5). Second-order corrections to PNOF5 are derived and implemented using the multiconfigurational perturbation theory size consistent at second-order (SC2-MCPT). A modified version of the SC2-MCPT including only doubly excited determinants from different geminals is proposed to describe the dispersion interaction in the helium dimer, and to avoid the breakdown of curves in homolytic dissociations of FH, CO, and N2. Comparisons of calculated properties to experimental data are included to verify the accuracy of the formulation.
Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), P.K. 1072, 20080 Donostia, Spain.
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Piris