Extending Nonlocal Kinetic Energy Density Functionals to Isolated Systems via a Density-Functional-Dependent Kernel
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arXiv
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| Format: | Preprint |
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2025
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| _version_ | 1866918388690845696 |
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| author | Sun, Liang Chen, Mohan |
| author_facet | Sun, Liang Chen, Mohan |
| contents | The Wang-Teter-like nonlocal kinetic energy density functional (KEDF) in the framework of orbital-free density functional theory, while successful in some bulk systems, exhibits a critical Blanc-Cances instability [J. Chem. Phys. 122, 214106 (2005)] when applied to isolated systems, where the total energy becomes unbounded from below. We trace this instability to the use of an ill-defined average charge density, which causes the functional to simultaneously violate the scaling law and the positivity of the Pauli energy. By rigorously constructing a density-functional-dependent kernel, we resolve these pathologies while preserving the formal exactness of the original framework. By systematically benchmarking single-atom systems of 56 elements, we find the resulting KEDF retains computational efficiency while achieving an order-of-magnitude accuracy enhancement over the WT KEDF. In addition, the new KEDF preserves WT's superior accuracy in bulk metals, outperforming the semilocal functionals in both regimes. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2507_08442 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Extending Nonlocal Kinetic Energy Density Functionals to Isolated Systems via a Density-Functional-Dependent Kernel Sun, Liang Chen, Mohan Materials Science Chemical Physics Computational Physics The Wang-Teter-like nonlocal kinetic energy density functional (KEDF) in the framework of orbital-free density functional theory, while successful in some bulk systems, exhibits a critical Blanc-Cances instability [J. Chem. Phys. 122, 214106 (2005)] when applied to isolated systems, where the total energy becomes unbounded from below. We trace this instability to the use of an ill-defined average charge density, which causes the functional to simultaneously violate the scaling law and the positivity of the Pauli energy. By rigorously constructing a density-functional-dependent kernel, we resolve these pathologies while preserving the formal exactness of the original framework. By systematically benchmarking single-atom systems of 56 elements, we find the resulting KEDF retains computational efficiency while achieving an order-of-magnitude accuracy enhancement over the WT KEDF. In addition, the new KEDF preserves WT's superior accuracy in bulk metals, outperforming the semilocal functionals in both regimes. |
| title | Extending Nonlocal Kinetic Energy Density Functionals to Isolated Systems via a Density-Functional-Dependent Kernel |
| topic | Materials Science Chemical Physics Computational Physics |
| url | https://arxiv.org/abs/2507.08442 |