Linear-response time-dependent density-functional theory with local range separation: Core and valence resonances of the neon atom
We investigate range-separated hybrids (RSHs) and locally range-separated hybrids (LRSHs) for linear-response time-dependent density-functional theory (TDDFT) Sternheimer calculations of the photoionization spectrum of the Ne atom. This system constitutes a stringent test for approximate exchange-correlation treatments because it exhibits both valence and core resonances with very different energy scales. Building on a previous study employing a simple one-parameter local range-separation function, we assess here a more flexible two-parameter range-separation function designed to improve the high-density limit. We compare photoionization spectra and resonance parameters obtained with RSHs and LRSHs. We find that the LRSH approach with the two-parameter range-separation function provides an overall satisfactory description of the photoionization spectrum, including energies for both valence and core resonances. The lifetimes of the 2s → np valence resonances are also reasonably reproduced since their decay does not involve double excitations. In contrast, the lifetimes of the 1s → np core resonances are overestimated by orders of magnitude because their Auger decay channels involve double excitations that are absent in adiabatic, single-determinant TDDFT. Obtaining more accurate resonance widths within the linear-response range-separated TDDFT would require using multideterminant schemes and/or adding a frequency-dependent response kernel.
Authors
- Julien Toulouse (ORCID: https://orcid.org/0000-0003-2855-1835)
- Jari van Gog
- Felipe Zapata
Institutions
- Universidad Complutense de Madrid (ES)
- Centre National de la Recherche Scientifique (FR)
- Sorbonne Université (FR)
- Laboratoire de Chimie Théorique (FR)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2026-09-01
- DOI
- https://doi.org/10.1063/5.0346283
- Primary Topic
- Spectroscopy and Quantum Chemical Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00