Shedding Light on the Basis Set Dependence of the Minnesota Functionals: Differences Between Plane Waves, Slater Functions, and Gaussians

Abstract

The Minnesota family of exchange-correlation (xc) functionals are among the most popular, accurate, and abundantly used functionals available to date. However, their use in plane-wave based first-principles MD has been limited by their sparse availability. Here, we present an implementation of the M05, M06, and M11 families of xc functionals within a plane wave/pseudopotential framework allowing for a comprehensive analysis of their basis set dependence. While it has been reported that in Gaussian bases some members of the Minnesota family only converge slowly to the basis set limit, (1) we show that converged energies can be conveniently obtained from plane waves if sufficiently dense integration meshes are used. Based on the HC7/11 database, we assess the influence of basis set type on the calculation of reaction enthalpies and show that complete basis set values obtained in plane waves may occasionally differ notably from their atom-centered counterparts. We provide an analysis of the origin of these differences and discuss implications on practical usage.