Reaching for the performance limit of hybrid density functional theory for molecular chemistry

Fuente: arXiv
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Main Authors: Liang, Jiashu, Head-Gordon, Martin
Format: Preprint
Published: 2026
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author Liang, Jiashu
Head-Gordon, Martin
author_facet Liang, Jiashu
Head-Gordon, Martin
contents Density functional theory (DFT) offers an exceptional balance between accuracy and efficiency, but practical density functional approximations face an unavoidable trade-off among simplicity, accuracy, and transferability. A systematic protocol is therefore needed to develop functionals that are reliably most accurate within a chosen application domain. Here we present such a protocol by combining constraint enforcement, flexible functional forms, and modern optimization. Applying this strategy to the range-separated hybrid (RSH) meta-GGA framework, we obtain the carefully optimized and appropriately constrained hybrid (COACH) functional. Across broad molecular benchmarks, COACH improves both accuracy and transferability relative to leading RSH meta-GGAs, including \omegaB97M-V, while retaining the computational practicality of its rung. Finally, our analysis of the remaining trade-offs and saturation behavior suggests that further systematic progress will likely require the incorporation of genuinely nonlocal information.
format Preprint
id arxiv_https___arxiv_org_abs_2603_23466
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Reaching for the performance limit of hybrid density functional theory for molecular chemistry
Liang, Jiashu
Head-Gordon, Martin
Chemical Physics
Computational Physics
Quantum Physics
Density functional theory (DFT) offers an exceptional balance between accuracy and efficiency, but practical density functional approximations face an unavoidable trade-off among simplicity, accuracy, and transferability. A systematic protocol is therefore needed to develop functionals that are reliably most accurate within a chosen application domain. Here we present such a protocol by combining constraint enforcement, flexible functional forms, and modern optimization. Applying this strategy to the range-separated hybrid (RSH) meta-GGA framework, we obtain the carefully optimized and appropriately constrained hybrid (COACH) functional. Across broad molecular benchmarks, COACH improves both accuracy and transferability relative to leading RSH meta-GGAs, including \omegaB97M-V, while retaining the computational practicality of its rung. Finally, our analysis of the remaining trade-offs and saturation behavior suggests that further systematic progress will likely require the incorporation of genuinely nonlocal information.
title Reaching for the performance limit of hybrid density functional theory for molecular chemistry
topic Chemical Physics
Computational Physics
Quantum Physics
url https://arxiv.org/abs/2603.23466