Separable Force Matching of PBE0 Hybrid-Functional Reference Forces for Path-Integral Simulations of Liquid Water
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arXiv
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| Autori principali: | , , , |
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| Natura: | Preprint |
| Pubblicazione: |
2026
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| _version_ | 1866911714334736384 |
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| author | Kessler, Jan Spura, Thomas Karhan, Kristof Kühne, Thomas D. |
| author_facet | Kessler, Jan Spura, Thomas Karhan, Kristof Kühne, Thomas D. |
| contents | Force-matched water models provide a practical route from first-principles reference data to long classical and path-integral molecular simulations. Previous flexible four-site potentials in the spirit of q-TIP4P/F showed that fitting analytic models to density-functional-theory forces can reproduce key structural features of liquid water while retaining the efficiency required for quantum-nuclear sampling. Here we introduce two refinements aimed at making this strategy more accurate and more reproducible for molecular simulation. First, the production fit is based on PBE0 hybrid-functional reference forces and therefore includes the Hartree--Fock exact-exchange contribution in the electronic-structure target. Second, the parametrization is formulated as a separable nonlinear least-squares problem in which all linear force-field amplitudes are eliminated analytically for every trial set of nonlinear shape parameters. The resulting force-matching protocol lowers the dimension of the nonlinear search, reduces compensation between heterogeneous parameters, and enables a controlled comparison of Lennard-Jones and Buckingham oxygen--oxygen repulsion terms. Applied to CP2K reference forces for liquid water, the projected optimization reproduces target force distributions and yields radial distribution functions close to first-principles and neutron-scattering benchmarks. The Buckingham representation gives a more flexible short-range repulsive wall than a purely Lennard-Jones form, and the final flexible model remains stable in path-integral simulations. The method provides a transparent workflow for deriving simulation-ready water potentials from accurate hybrid density-functional reference forces. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2605_25081 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Separable Force Matching of PBE0 Hybrid-Functional Reference Forces for Path-Integral Simulations of Liquid Water Kessler, Jan Spura, Thomas Karhan, Kristof Kühne, Thomas D. Chemical Physics Disordered Systems and Neural Networks Soft Condensed Matter Computational Physics Force-matched water models provide a practical route from first-principles reference data to long classical and path-integral molecular simulations. Previous flexible four-site potentials in the spirit of q-TIP4P/F showed that fitting analytic models to density-functional-theory forces can reproduce key structural features of liquid water while retaining the efficiency required for quantum-nuclear sampling. Here we introduce two refinements aimed at making this strategy more accurate and more reproducible for molecular simulation. First, the production fit is based on PBE0 hybrid-functional reference forces and therefore includes the Hartree--Fock exact-exchange contribution in the electronic-structure target. Second, the parametrization is formulated as a separable nonlinear least-squares problem in which all linear force-field amplitudes are eliminated analytically for every trial set of nonlinear shape parameters. The resulting force-matching protocol lowers the dimension of the nonlinear search, reduces compensation between heterogeneous parameters, and enables a controlled comparison of Lennard-Jones and Buckingham oxygen--oxygen repulsion terms. Applied to CP2K reference forces for liquid water, the projected optimization reproduces target force distributions and yields radial distribution functions close to first-principles and neutron-scattering benchmarks. The Buckingham representation gives a more flexible short-range repulsive wall than a purely Lennard-Jones form, and the final flexible model remains stable in path-integral simulations. The method provides a transparent workflow for deriving simulation-ready water potentials from accurate hybrid density-functional reference forces. |
| title | Separable Force Matching of PBE0 Hybrid-Functional Reference Forces for Path-Integral Simulations of Liquid Water |
| topic | Chemical Physics Disordered Systems and Neural Networks Soft Condensed Matter Computational Physics |
| url | https://arxiv.org/abs/2605.25081 |