Smeared Coulomb potential orbitals for the electron-nucleus mean field configuration interaction method
Résumé
We propose to use the eigenfunctions of a one-electron model Hamiltonian to perform electron-nucleus mean field configuration interaction (EN-MFCI) calculations. The potential energy of our model Hamiltonian corresponds to the Coulomb potential of an infinite wire with charge $Z$ distributed according to a Gaussian function. The time independent \sch equation for this Hamiltonian is solved perturbationally in the limit of small amplitude vibration (Gaussian function width close to zero).
Since the parameter controling the width of the potential factorizes the perturbative corrections to the eigenfunctions, we propose to simply add the latter to standard basis sets, leaving it to molecular orbital calculations to optimize this free parameter. The new functions have been fitted with Gaussian-type orbitals (GTO) with mixed Cartesian prefactors to calculate multicenter integrals efficiently. The BDF code has been modified to accept contracted GTO having such mixed Cartesian prefactors.
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