Self-consistent implementation of meta-GGA functionals for the ONETEP linear-scaling electronic structure package

Abstract

Accurate and computationally efficient exchange-correlation functionals are critical to the successful application of linear-scaling density functional theory (DFT). Local and semi-local functionals of the density are naturally compatible with linear-scaling approaches, having a general form which assumes the locality of electronic interactions and which can be efficiently evaluated by numerical quadrature. Presently, the most sophisticated and flexible semi-local functionals are members of the meta-generalized-gradient approximation (meta-GGA) family, and depend upon the kinetic energy density, tau, in addition to the charge density and its gradient. In order to extend the theoretical and computational advantages of tau-dependent meta-GGA functionals to large-scale DFT calculations on thousands of atoms, we have implemented support for tau-dependent meta-GGA functionals in the ONETEP program. In this paper we lay out the theoretical innovations necessary to implement tau-dependent meta-GGA functionals within ONETEP's linear-scaling formalism. We present expressions for the gradient of the tau-dependent exchange-correlation energy, necessary for direct energy minimization. We also derive the forms of the tau-dependent exchange-correlation potential and kinetic energy density in terms of the strictly localized, self-consistently optimized orbitals used by ONETEP. To validate the numerical accuracy of our self-consistent meta-GGA implementation, we performed calculations using the B97M-V and PKZB meta-GGAs on a variety of small molecules. Using only a minimal basis set of self-consistently optimized local orbitals, we obtain energies in excellent agreement with large basis set calculations performed using other codes. Finally, to establish the linear-scaling computational cost and applicability of our approach to large-scale calculations, we present the outcome of self-consistent meta-GGA calculations on amyloid fibrils of increasing size, up to tens of thousands of atoms.

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Identifiers

ORCID for James C. Womack: orcid.org/0000-0001-5497-4482

ORCID for Chris Skylaris: orcid.org/0000-0003-0258-3433

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