The effects of dispersion damping and three-body interactions for accurate layered-material exfoliation energies

TL;DR

This paper evaluates the impact of dispersion damping functions and three-body interactions on the accuracy of exfoliation energy predictions in layered materials using density-functional theory, achieving improved results on benchmark data.

Contribution

It presents the first assessment of the Z-damping function in XDM and demonstrates that including three-body interactions enhances exfoliation energy accuracy.

Findings

XDM(Z) performs well on LM26 benchmark.

Including three-body interactions improves exfoliation energy predictions.

Achieves best performance on LM26 with semi-local functionals.

Abstract

Accurate predictions of exfoliation energies and lattice constants of layered materials hinge on a correct description of London dispersion physics. Modern a posteriori dispersion corrections in density-functional theory (DFT), such as the exchange-hole dipole moment (XDM) model, capture the proper asymptotic behaviour at long range while making use of damping functions to prevent unphysical divergence at short range. In the united-atom limit, the dispersion energy is damped to a finite, non-zero value by both the canonical Becke--Johnson (BJ) damping function and the new Z-damping function. XDM(BJ) has previously demonstrated exceptional accuracy for modelling layered materials, such as in the LM26 benchmark, which includes graphite, hexagonal boron nitride, lead(II) oxide, and transition-metal dichalcogenides. This work presents the first assessment of XDM(Z) on the same benchmark. We also show that inclusion of three-body interactions via the Axilrod--Teller--Muto (ATM) term further improves the computed exfoliation energies for both XDM(BJ) and XDM(Z), yielding the best performance achieved on LM26 using semi-local functionals to date, relative to reference data from the random-phase approximation.