Towards extending the applicability of density functional theory to weakly bound systems

While the attempts currently in progress in several groups for the rigorous inclusion of dispersion interactions in density functional theory (DFT) calculations mature and evolve into practical methodology, we contribute to the debate on the applicability of current functionals to the calculation of weak interaction with a systematic investigation of a few, typical, weakly bound systems. We have used both pure DFT and a hybrid approach in which the total interaction energy is partitioned into two parts: (a) the dispersion energy which, in a first approximation is the contribution due to intermonomer correlations and (b) all other interactions. The first component is accurately obtained at all distances of interest by means of a well-known damped multipolar expansion of the dispersion energy while for the second component different approximations will be evaluated. The need to avoid double counting a fraction of the correlation energy when using the hybrid approach and the choice of the appropriate functio...

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