MuAPBEK: An Improved Analytical Kinetic Energy Density Functional for Quantum Chemistry

TL;DR

This paper introduces MuAPBEK, an improved kinetic energy density functional for orbital-free DFT, achieving higher accuracy and computational efficiency, enabling large-scale quantum simulations beyond traditional Kohn-Sham methods.

Contribution

The paper develops MuAPBEK, a novel functional with physically-motivated corrections, significantly enhancing OFDFT accuracy and speed for large systems.

Findings

MuAPBEK reduces energy errors compared to standard functionals.

MuAPBEK provides accurate densities with low error margins.

One density optimization step is much faster than KSDFT cycles.

Abstract

Orbital-free density functional theory (OFDFT) offers a true realization of the Hohenberg-Kohn theorems, enabling full quantum-mechanical studies of electronic systems based solely on electron densities. However, OFDFT remains limited by the difficulty of formulating accurate kinetic-energy density functionals. In this paper, we substantially enhance the accuracy of OFDFT energies and densities by tuning, during density initialization, the parameter $\mu$ of the APBEK functional, which arises in the second-order gradient expansion of the kinetic energy for semiclassical neutral atoms. We augment this parameterized APBEK functional with two physically-motivated, non-empirical corrections derived from Kato's cusp condition and the virial theorem. The resulting functional, which we call MuAPBEK, is benchmarked against Kohn-Sham density functional theory (KSDFT) on atoms, organic molecules from the QM9 dataset, and the anti-malarial drug artemisinin. MuAPBEK achieves much lower energy errors than standard APBEK and Thomas-Fermi-von-Weizsacker functionals, even when the latter two are evaluated on converged KSDFT densities. Its mean absolute energy errors on atoms and molecules are 161 and 122 kcal/mol, respectively, indicating that MuAPBEK's errors do not scale with system size. MuAPBEK also yields accurate densities, with a mean integrated absolute density error of 1.8 electrons for molecules. Importantly, one step of our density optimization scheme is at least ten times faster than a single KSDFT self-consistent field cycle and exhibits a lower-order computational time complexity of $O(N^{1.96})$ with respect to system size, $N$. Our results indicate that highly-accurate OFDFT for large-scale quantum simulations beyond the practical limits of KSDFT is within reach.