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

Abstract

Multideterminant calculations have been performed on model systems to emphasize the role of many-body effects in the general description of charge quantization experiments. We show numerically and derive analytically that a closed-shell ansatz, the usual ingredient of mean-field methods, does not properly describe the step-like electron transfer characteristic in weakly coupled systems. With the multideterminant results as a benchmark, we have evaluated the performance of common ab initio mean field techniques, such as Hartree Fock (HF) and Density Functional Theory (DFT) with local and hybrid exchange correlation functionals, with a special focus on spin-polarization effects. For HF and hybrid DFT, a qualitatively correct open-shell solution with distinct steps in the electron transfer behaviour can be obtained with a spin-unrestricted (i.e., spin-polarized) ansatz though this solution differs quantitatively from the multideterminant reference. We also discuss the relationship between the electronic eigenvalue gap and the onset of charge transfer for both HF and DFT and relate our findings to recently proposed practical schemes for calculating the addition energies in the Coulomb blockade regime for single molecule junctions from closed-shell DFT within the local density approximation.

References in corpus (13)

• Density functional method for nonequilibrium electron transport
• First-Principles Based Matrix-Green's Function Approach to Molecular Electronic Devices: General Formalism
• Self-interaction errors in density functional calculations of electronic transport
• Describing static correlation in bond dissociation by Kohn-Sham density functional theory
• Effects of self-interaction corrections on the transport properties of phenyl-based molecular junctions
• Molecular transport calculations with Wannier functions
• Probing electronic excitations in molecular conduction
• The Role of the Exchange-Correlation Potential in ab initio Electron Transport Calculations
• Coulomb blockade in electron transport through a C${}_{60}$ molecule from first principles
• Energy gaps and interaction blockade in confined quantum systems
• Theory of high bias Coulomb Blockade in ultrashort molecules
• Towards a theoretical description of molecular junctions in the Coulomb blockade regime based on density functional theory
• Screening effects in a density functional theory based description of molecular junctions in the Coulomb blockade regime

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