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Multideterminant calculations have been performed on model systems toemphasize the role of many-body effects in the general description of chargequantization experiments. We show numerically and derive analytically that aclosed-shell ansatz, the usual ingredient of mean-field methods, does notproperly describe the step-like electron transfer characteristic in weaklycoupled systems. With the multideterminant results as a benchmark, we haveevaluated the performance of common ab initio mean field techniques, such asHartree Fock (HF) and Density Functional Theory (DFT) with local and hybridexchange correlation functionals, with a special focus on spin-polarizationeffects. For HF and hybrid DFT, a qualitatively correct open-shell solutionwith distinct steps in the electron transfer behaviour can be obtained with aspin-unrestricted (i.e., spin-polarized) ansatz though this solution differsquantitatively from the multideterminant reference. We also discuss therelationship between the electronic eigenvalue gap and the onset of chargetransfer for both HF and DFT and relate our findings to recently proposedpractical schemes for calculating the addition energies in the Coulomb blockaderegime for single molecule junctions from closed-shell DFT within the localdensity approximation.

A multideterminant assessment of mean field methods for the description of electron transfer in the weak coupling regime