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Optimally Tuned Multiconfigurational Short-Range DFT for Linear Response Properties

Chemical Physics 2026-03-05 v1

Abstract

Multiconfigurational short-range density functional theory (MC-srDFT) rigorously combines ground state wavefunction theory with DFT. Unlike single-reference range-separated hybrid functionals, MC-srDFT has lacked theoretically grounded protocols for choosing the system-specific range-separation parameter. To address this problem, we introduce an optimal-tuning scheme based on enforcing the correct exponential decay of the electron density. We show that the range-separation parameter can be determined from the ionization potential given by the smallest-magnitude eigenvalue of the Extended Koopmans' Theorem matrix constructed for the model Hamiltonian. We validate this approach for static and dynamic dipole polarizabilities of ground-state molecular systems using MC-srDFT within both full linear response and its extended random phase approximation (ERPA) variant. Optimal tuning substantially improves polarizabilities relative to the commonly used universal μ=0.4bohr1\mu = 0.4\,\mathrm{bohr}^{-1} parameter.

Keywords

Cite

@article{arxiv.2603.04106,
  title  = {Optimally Tuned Multiconfigurational Short-Range DFT for Linear Response Properties},
  author = {Michał Hapka and Katarzyna Pernal and Ewa Pastorczak},
  journal= {arXiv preprint arXiv:2603.04106},
  year   = {2026}
}
R2 v1 2026-07-01T11:03:06.798Z