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

Institutions

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
Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

Linear-response time-dependent density-functional theory with local range separation: Core and valence resonances of the neon atom

Julien Toulouse, Jari van Gog, Felipe Zapata
The Journal of Chemical Physics
Spectroscopy and Quantum Chemical Studies
article

Linear-response time-dependent density-functional theory with local range separation: Core and valence resonances of the neon atom

Julien Toulouse, Jari van Gog, Felipe Zapata
article en

Abstract

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.

The Journal of Chemical PhysicsVol. 165(9)
Universidad Complutense de Madrid (ES), Centre National de la Recherche Scientifique (FR), Sorbonne Université (FR), Laboratoire de Chimie Théorique (FR)
Affordable and clean energy
Openalex Percentile: Top 18%
Spectroscopy and Quantum Chemical Studies
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.