Orbital-free functional with sub-milliHartree errors for slabs

2023/03/22 by Pavel Okun, Okun, Pavel, Antonio C. Cancio +3
Earth and Planetary Sciences · Physics and Astronomy · #Advanced Chemical Physics Studies #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #Quantum Physics (quant-ph) #Spectroscopy and Quantum Chemical Studies #nanoparticles nucleation surface interactions

paper · pdf · doi:10.48550/arxiv.2304.11115

openalex publication_date 2023/03/22 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

Using principles of asymptotic analysis, we derive the exact leading corrections to the Thomas-Fermi kinetic energy approximation for Kohn-Sham electrons for slabs. This asymptotic expansion approximation includes crucial quantum oscillations missed by standard semilocal density functionals. Because these account for the derivative discontinuity, chemical accuracy is achieved at fourth-order. The implications for both orbital-free electronic structure and exchange-correlation approximations are discussed.

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