Incorporation of surface correction and anharmonic correction to vacancy formation energy for nickel and copper: bridging the gap between Density Functional Theory and experiment

TL;DR

This study improves the accuracy of vacancy formation energy predictions for nickel and copper by incorporating surface and anharmonic corrections into DFT calculations, aligning them more closely with experimental results.

Contribution

The paper introduces a combined correction approach, including surface and anharmonic effects, to enhance DFT estimates of vacancy formation energies for transition metals.

Findings

Surface correction significantly reduces DFT underestimation.

Anharmonic correction further improves agreement with experiments.

Combined corrections bridge the gap between theory and experimental data.

Abstract

Density functional theory (DFT) has been used to estimate vacancy formation enthalpy (H_fv) for a few transition metals like nickel (Ni) and copper (Cu). It is shown that, for these metals, H_fv is underestimated considerably by DFT. The aim of the present work is to bridge the gap between the estimates made by DFT calculations and experiments. The sources of this discrepancy are identified as to be related to the opening up of the surface like region surrounding the vacancy, and the temperature induced anharmonic contribution. The surface related correction to H_fv has been estimated by a jellium based model originally proposed by Mattsson et al. [Phys. Rev. B 73 (2006) 195123] and subsequently modified by Nandi et al. [J. Phys.:Cond. Matt. 22 (2010) 345501]. In this paper, we have estimated the temperature induced anharmonic contribution to H_fv using density functional perturbation theory. Finally, it is shown that incorporation of both the surface correction and anharmonic correction to H_fv, results in a better agreement with the experimental data.