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

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

2009-07-13

arxiv.org/abs/0907.2166v1

Physics

Condensed Matter

Mesoscale and Nanoscale Physics

Scientific paper

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.

Affiliated with

Also associated with

No associations

Rating

A multideterminant assessment of mean field methods for the description of electron transfer in the weak coupling regime does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with A multideterminant assessment of mean field methods for the description of electron transfer in the weak coupling regime, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and A multideterminant assessment of mean field methods for the description of electron transfer in the weak coupling regime will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFWR-SCP-O-100912