Optimally Tuned Multiconfigurational Short-Range DFT for Linear Response Properties
Michał Hapka, Katarzyna Pernal, Ewa Pastorczak · The Journal of Physical Chemistry A · 2026
Multiconfigurational short-range density functional theory (MC-srDFT) rigorously combines ground-state wave function 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 = 0.4 bohr –1 parameter.