Nonlocal Orbital-Free Kinetic Energy Functional from the Jellium-with-Gap Model for Finite Systems

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Authors: Abhishek Bhattacharjee, Subrata Jana, Szymon Śmiga, Prasanjit Samal
Cited by: 1
References: 86

Abstract

The quasi-linear scaling of orbital-free density functional theory (OF-DFT) with system size makes it a computationally efficient alternative to conventional Kohn-Sham density functional theory for many condensed-matter applications. However, its applicability remains limited, particularly for finite systems such as molecular clusters, due to the lack of accurate kinetic energy density functionals. In this context, the development of nonlocal kinetic energy density functionals (NL-KEDFs) has significantly advanced the practical utility of OF-DFT. Here, following an alternative formulation based on the linear-response kernel derived from the jellium-with-gap model (JGM), we develop an NL-KEDF capable of accurately describing the diverse density regimes characteristic of finite systems, including molecular clusters. Benchmark calculations, together with an analysis of the corresponding Pauli potentials, demonstrate that the proposed functional achieves higher accuracy than state-of-the-art orbital-free approaches for finite systems. Furthermore, the optical properties computed using the present method show good agreement with reference results, highlighting its reliability. These results indicate that the proposed NL-KEDF provides a robust and efficient framework for extending OF-DFT to finite systems, with potential implications for nanomaterial design and a deeper understanding of nanoscale phenomena.

Fields of Study & Subjects

Thermoelastic and Magnetoelastic Phenomena Thermodynamic and Structural Properties of Metals and Alloys Advanced Physical and Chemical Molecular Interactions

Publication details

Journal / source
Journal of Chemical Theory and Computation
Publisher
American Chemical Society (ACS)
Volume
22
Issue
13
Pages
6510–6524
Publication date
12 June 2026
Language
EN