Atomic Structure of Glassy GeTe4 as a Playground to Assess the Performances of Density Functional Schemes Accounting for Dispersion Forces.

Abstract

The atomic structure of glassy GeTe4 is obtained in the framework of first-principles molecular dynamics (FPMD) by considering five different approaches for the description of the electronic structure within density functional theory (DFT). Among these schemes, one is not corrected by accounting for the dispersion forces and it is based on the BLYP exchange-correlation (XC) functional, while all of the others consider the dispersion forces according to different theoretical strategies. In particular, by maintaining the BLYP expression for the XC functional, two of them (BLYP-D2 and BLYP-D3) exploit the Grimme expressions for the dispersion forces, while the fourth scheme is based on the maximally localized Wannier functions (MLWFs). Finally, we also considered the rVV10 functional constructed to include seamlessly the dispersion part. Our results point out the better performances of BLYP-D3 and MLWF in terms of comparison with experimental data for the total pair correlation functions, with BLYP-D2 and rVV10 being closer to the uncorrected BLYP data. The implications of such findings are discussed by considering the overall limited impact of dispersion forces on the atomic structure of glassy GeTe4.