Electronic levels and electrical response of periodic molecular structures from plane-wave orbital-dependent calculations

TL;DR

This paper develops exact point-charge auxiliary functions for reciprocal-space corrections in plane-wave orbital-dependent DFT calculations, improving the accuracy of electronic levels and electrical response predictions for periodic molecular structures.

Contribution

It introduces a new derivation of point-charge auxiliary functions for arbitrary translational symmetry, including 1D cases, and assesses their performance in OD-DFT calculations.

Findings

Enhanced accuracy in electronic level predictions.

Improved electrical response calculations for conjugated polymers.

Demonstrated efficiency of reciprocal-space corrections.

Abstract

Plane-wave electronic-structure predictions based upon orbital-dependent density-functional theory (OD-DFT) approximations, such as hybrid density-functional methods and self-interaction density-functional corrections, are severely affected by computational inaccuracies in evaluating electron interactions in the plane-wave representation. These errors arise from divergence singularities in the plane-wave summation of electrostatic and exchange interaction contributions. Auxiliary-function corrections are reciprocal-space countercharge corrections that cancel plane-wave singularities through the addition of an auxiliary function to the point-charge electrostatic kernel that enters into the expression of interaction terms. At variance with real-space countercharge corrections that are employed in the context of density-functional theory (DFT), reciprocal-space corrections are computationally inexpensive, making them suited to more demanding OD-DFT calculations. Nevertheless, there exists much freedom in the choice of auxiliary functions and various definitions result in different levels of performance in eliminating plane-wave inaccuracies. In this work, we derive exact point-charge auxiliary functions for the description of molecular structures of arbitrary translational symmetry, including the yet unaddressed one-dimensional case. In addition, we provide a critical assessment of different reciprocal-space countercharge corrections and demonstrate the improved accuracy of point-charge auxiliary functions in predicting the electronic levels and electrical response of conjugated polymers from plane-wave OD-DFT calculations.