Laplacian-level meta-generalized gradient approximation for solid and liquid metals

2022/03/17 by Aaron D. Kaplan, John P. Perdew, Kaplan, Aaron D. +1 · 4 citations
Chemistry · Earth and Planetary Sciences · Materials Science · Physics and Astronomy · #Alkali metal #Atomic physics #Chemical Physics (physics.chem-ph) #Chemistry #Crystallography #FOS: Physical sciences #Ground state #Kinetic energy #Laplace operator #Lattice (music) #Lattice constant #Machine Learning in Materials Science #Materials Science (cond-mat.mtrl-sci) #Materials science #Other Condensed Matter (cond-mat.other) #Physics #Quantum mechanics #Surface and Thin Film Phenomena #Tetrahedron #cond-mat.mtrl-sci #cond-mat.other #nanoparticles nucleation surface interactions #physics.chem-ph

paper · pdf · doi:10.48550/arxiv.2203.09403

published in arXiv (Cornell University) (Cornell University) · Significant revisions in response to referee comments. Under review at Physical Review Materials

openalex publication_date 2022/03/17 · arxiv created 2022/08/01 · arxiv updated 2022/08/02 · openalex created_date 2023/02/13 · openalex updated_date 2026/08/08

Abstract

We derive and motivate a Laplacian-level, orbital-free meta-generalized-gradient approximation (LL-MGGA) for the exchange-correlation energy, targeting accurate ground-state properties of sp and sd metallic condensed matter, in which the density functional for the exchange-correlation energy is only weakly nonlocal due to perfect long-range screening. Our model for the orbital-free kinetic energy density restores the fourth-order gradient expansion for exchange to the r²SCAN meta-GGA [Furness et al., J. Phys. Chem. Lett. 11, 8208 (2020)], yielding a LL-MGGA we call OFR2. OFR2 matches the accuracy of SCAN for prediction of common lattice constants and improves the equilibrium properties of alkali metals, transition metals, and intermetallics that were degraded relative to the PBE GGA values by both SCAN and r²SCAN. We compare OFR2 to the r²SCAN-L LL-MGGA [D. Mejia-Rodriguez and S.B. Trickey, Phys. Rev. B 102, 121109 (2020)] and show that OFR2 tends to outperform r²SCAN-L for the equilibrium properties of solids, but r²SCAN-L much better describes the atomization energies of molecules than OFR2 does. For best accuracy in molecules and non-metallic condensed matter, we continue to recommend SCAN and r²SCAN. Numerical performance is discussed in detail, and our work provides an outlook to machine learning.

Cited by

• Effect of the Gradient of the Spin-Polarization in Density Functional Approximations
• Electron Localization in Non-Compact Covalent Bonds Captured by the r2SCAN+V Approach
• Mott vs Kondo: Influence of Various Density Functional Based Methods on the Ce Isostructural Phase Transition Mechanism
• Finite-temperature bulk moduli from an EOS-based Grüneisen function
• Optical properties of a diamond NV color center from capped embedded multiconfigurational correlated wavefunction theory

Related

• Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry
• Assessing the Performance of Recent Density Functionals for Bulk Solids
• Testing the r²SCAN density functional for the thermodynamic stability of solids with and without a van der Waals correction
• First steps towards achieving both ultranonlocality and a reliable description of electronic binding in a meta-generalized gradient approximation
• Implementation of the SCAN Exchange-Correlation Functional with Numerical Atomic Orbitals