Details

Autor(en) / Beteiligte

• Wang, Han
• Su, Gregory M
• Barnett, Brandon R
• Drisdell, Walter S
• Long, Jeffrey R
• Prendergast, David

Titel

Understanding 2p core-level excitons of late transition metals by analysis of mixed-valence copper in a metal-organic framework

Ist Teil von

• Physical chemistry chemical physics : PCCP, 2024-04, Vol.26 (15), p.1198-11987

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2024

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The L 2,3 -edge X-ray absorption spectra of late transition metals such as Cu, Ag, and Au exhibit absorption onsets lower in energy for higher oxidation states, which is at odds with the measured spectra of earlier transition metals. Time-dependent density functional theory calculations for Cu 2+ /Cu + reveal a larger 2p core-exciton binding energy for Cu 2+ , overshadowing shifts in single-particle excitation energies with respect to Cu + . We explore this phenomenon in a Cu + metal-organic framework with ∼12% Cu 2+ defects and find that corrections with self-consistent excited-state total energy differences provide accurate XAS peak alignment. We simulated XAS with LR-TDDFT for Cu 2+ /Cu + in MOF Cu I -MFU-4 l and revealed a larger 2p core-exciton binding energy for Cu 2+ , finding that corrections with self-consistent excited-state total energy differences provide accurate XAS peak alignment.