opt-DDAP: Optimisable density-derived atomic point charges via automatic differentiation
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| Format: | Preprint |
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2026
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| _version_ | 1866917402083590144 |
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| author | H., Mohith Vijay, Sudarshan |
| author_facet | H., Mohith Vijay, Sudarshan |
| contents | Interatomic potentials which accurately describe long-range electrostatics require atom-centred charges. One such method to determine these atom-centred charges from density functional theory (DFT) calculations is the density-derived atomic point (DDAP) charge method. DDAP fits atom-centred Gaussians to the ground-state DFT charge density and preserves the multipole moments that govern long-range electrostatics. While these charges accurately predict long-range behaviour, in practice, they are limited by their reliance on fixed, heuristic parameters and a constrained solver that becomes numerically unstable for complex or covalent systems. In this work, we present opt-DDAP, which solves this limitation by reformulating the algorithm as a differentiable computational graph. This reformulation allows for the optimisation of Gaussian basis parameters and the reciprocal-space cutoff using automatic differentiation. To ensure numerical robustness through this automatic differentiation process, we replace the conventional Lagrange-multiplier approach with a pseudo-inverse solution followed by charge renormalisation, maintaining stability even in the presence of ill-conditioned matrices. We validate the framework on NaCl vacancy supercells and on MoS$_2$, demonstrating faithful reconstruction of both absolute and difference charge densities. The optimised charges are intended to serve as inputs to effective electrostatic models in machine-learning and empirical interatomic potentials that incorporate long-range interactions. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2604_10984 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | opt-DDAP: Optimisable density-derived atomic point charges via automatic differentiation H., Mohith Vijay, Sudarshan Materials Science Chemical Physics Interatomic potentials which accurately describe long-range electrostatics require atom-centred charges. One such method to determine these atom-centred charges from density functional theory (DFT) calculations is the density-derived atomic point (DDAP) charge method. DDAP fits atom-centred Gaussians to the ground-state DFT charge density and preserves the multipole moments that govern long-range electrostatics. While these charges accurately predict long-range behaviour, in practice, they are limited by their reliance on fixed, heuristic parameters and a constrained solver that becomes numerically unstable for complex or covalent systems. In this work, we present opt-DDAP, which solves this limitation by reformulating the algorithm as a differentiable computational graph. This reformulation allows for the optimisation of Gaussian basis parameters and the reciprocal-space cutoff using automatic differentiation. To ensure numerical robustness through this automatic differentiation process, we replace the conventional Lagrange-multiplier approach with a pseudo-inverse solution followed by charge renormalisation, maintaining stability even in the presence of ill-conditioned matrices. We validate the framework on NaCl vacancy supercells and on MoS$_2$, demonstrating faithful reconstruction of both absolute and difference charge densities. The optimised charges are intended to serve as inputs to effective electrostatic models in machine-learning and empirical interatomic potentials that incorporate long-range interactions. |
| title | opt-DDAP: Optimisable density-derived atomic point charges via automatic differentiation |
| topic | Materials Science Chemical Physics |
| url | https://arxiv.org/abs/2604.10984 |