Ultrafast intersystem crossings in Fe-Co Prussian blue analogues

van Veenendaal, Michel

doi:10.1038/s41598-017-06664-4

Ultrafast intersystem crossings in Fe-Co Prussian blue analogues

Journal Article · Thu Jul 27 00:00:00 EDT 2017 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-017-06664-4· OSTI ID:1393194

van Veenendaal, Michel ^[1]

Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Ultrafast spincrossover is studied in Fe-Co Prussian blue analogues using a dissipative quantum-mechanical model of a cobalt ion coupled to a breathing mode. All electronic interactions are treated on an equal footing. It is theoretically demonstrated that the divalent cobalt ion reaches 90% of the S = 3/2 value within 20 fs after photoexciting a low-spin Co³⁺ ion by an iron-to-cobalt charge transfer. The doublet-to-quartet spin crossover is significantly faster than the oscillation period of the breathing mode. The system relaxes to the lowest manifold of divalent cobalt (⁴T₁) in 150-200 fs. In conclusion, strong oscillations in spin-orbit coupling and the involvement of higher-lying quartets are found.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: Northern Illinois University, Institute for Nanoscience, Engineering and Technology; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Materials Sciences and Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1393194

Journal Information:: Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 7; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Photoinduced valence tautomerism of a cobalt-dioxolene complex revealed with femtosecond M-edge XANES Ash, Ryan; Zhang, Kaili; Vura-Weis, Josh The Journal of Chemical Physics, Vol. 151, Issue 10 https://doi.org/10.1063/1.5115227	journal	September 2019
Dissipation and dynamics in ultrafast intersystem crossings van Veenendaal, Michel The Journal of Chemical Physics, Vol. 152, Issue 2 https://doi.org/10.1063/1.5125005	journal	January 2020

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