Dispersion corrections in graphenic systems: a simple and effective model of binding

TL;DR

The paper develops a simple, parametrized dispersion correction model for graphenic systems that accurately matches high-level ab initio results and improves predictions of binding energies and exfoliation properties.

Contribution

A new additive dispersion correction model for DFT that effectively captures non-pairwise dispersion interactions in graphite and related materials.

Findings

Accurately predicts graphite interlayer binding and exfoliation energies.

Provides a reliable correction for DFT calculations in graphenic systems.

Material properties of LiC6 remain unchanged with the correction.

Abstract

We combine high-level theoretical and \emph{ab initio} understanding of graphite to develop a simple, parametrised force-field model of interlayer binding in graphite, including the difficult non-pairwise-additive coupled-fluctuation dispersion interactions. The model is given as a simple additive correction to standard density functional theory (DFT) calculations, of form $\Delta U(D)=f(D)[U^{vdW}(D)-U^{DFT}(D)]$ where $D$ is the interlayer distance. The functions are parametrised by matching contact properties, and long-range dispersion to known values, and the model is found to accurately match high-level \emph{ab initio} results for graphite across a wide range of $D$ values. We employ the correction on the difficult bigraphene binding and graphite exfoliation problems, as well as lithium intercalated graphite LiC$_6$. We predict the binding energy of bigraphene to be 0.27 J/m^2, and the exfoliation energy of graphite to be 0.31 J/m^2, respectively slightly less and slightly more than the bulk layer binding energy 0.295 J/m^2/layer. Material properties of LiC$_6$ are found to be essentially unchanged compared to the local density approximation. This is appropriate in view of the relative unimportance of dispersion interactions for LiC$_6$ layer binding.