Optimally Tuned Multiconfigurational Short-Range DFT for Linear Response Properties
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| Format: | Preprint |
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2026
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| _version_ | 1866918369715814400 |
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| author | Hapka, Michał Pernal, Katarzyna Pastorczak, Ewa |
| author_facet | Hapka, Michał Pernal, Katarzyna Pastorczak, Ewa |
| contents | 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 $μ= 0.4\,\mathrm{bohr}^{-1}$ parameter. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2603_04106 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Optimally Tuned Multiconfigurational Short-Range DFT for Linear Response Properties Hapka, Michał Pernal, Katarzyna Pastorczak, Ewa Chemical Physics 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 $μ= 0.4\,\mathrm{bohr}^{-1}$ parameter. |
| title | Optimally Tuned Multiconfigurational Short-Range DFT for Linear Response Properties |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2603.04106 |