English

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

Chemical Physics 2026-03-25 v1 Computational Physics Quantum Physics

Abstract

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.

Keywords

Cite

@article{arxiv.2603.23466,
  title  = {Reaching for the performance limit of hybrid density functional theory for molecular chemistry},
  author = {Jiashu Liang and Martin Head-Gordon},
  journal= {arXiv preprint arXiv:2603.23466},
  year   = {2026}
}