Ultrafast intersystem crossings in Fe-Co Prussian blue analogues

van Veenendaal, Michel

doi:10.1038/s41598-017-06664-4

Title: 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)

Cite

Export

Save

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

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1393194

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

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 9 works

Citation information provided by
Web of Science

References (33)

Vibronic Theory of Ultrafast Intersystem Crossing Dynamics in a Single Spin-Crossover Molecule at Finite Temperature beyond the Born–Oppenheimer Approximation Klinduhov, Nikolay; Boukheddaden, Kamel The Journal of Physical Chemistry Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acs.jpclett.6b00014	journal	February 2016
X-ray Magnetic Circular Dichroism Investigation of the Electron Transfer Phenomena Responsible for Magnetic Switching in a Cyanide-Bridged [CoFe] Chain Baker, Michael L.; Kitagawa, Yasutaka; Nakamura, Tetsuya Inorganic Chemistry, Vol. 52, Issue 24 https://doi.org/10.1021/ic402580n	journal	December 2013
Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex Bressler, Ch.; Milne, C.; Pham, V. -T. Science, Vol. 323, Issue 5913 https://doi.org/10.1126/science.1165733	journal	January 2009
Spin-Crossover Materials. Properties and Applications. Edited by Malcolm A. Halcrow. Hauser, Andreas Angewandte Chemie International Edition, Vol. 52, Issue 40 https://doi.org/10.1002/anie.201306160	journal	August 2013
Ab Initio Multiple Spawning Method for Intersystem Crossing Dynamics: Spin-Forbidden Transitions between ³ B ₁ and ¹ A ₁ States of GeH ₂ Fedorov, Dmitry A.; Pruitt, Spencer R.; Keipert, Kristopher The Journal of Physical Chemistry A, Vol. 120, Issue 18 https://doi.org/10.1021/acs.jpca.6b01406	journal	April 2016
On Krylov Subspace Approximations to the Matrix Exponential Operator Hochbruck, Marlis; Lubich, Christian SIAM Journal on Numerical Analysis, Vol. 34, Issue 5 https://doi.org/10.1137/S0036142995280572	journal	October 1997
Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy Bonhommeau, Sébastien; Pontius, Niko; Cobo, Saioa Physical Chemistry Chemical Physics, Vol. 10, Issue 38 https://doi.org/10.1039/b806783j	journal	January 2008
Effects of Intra- and Intercenter Interactions in Spin Crossover: Application of the Density Matrix Method to the Nonequilibrium Low-Spin↔High-Spin Transitions Induced by Light Klokishner, S.; Linares, J. The Journal of Physical Chemistry C, Vol. 111, Issue 28 https://doi.org/10.1021/jp070126j	journal	July 2007
Tracking excited-state charge and spin dynamics in iron coordination complexes Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe Nature, Vol. 509, Issue 7500 https://doi.org/10.1038/nature13252	journal	May 2014
Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics Huse, Nils; Cho, Hana; Hong, Kiryong The Journal of Physical Chemistry Letters, Vol. 2, Issue 8 https://doi.org/10.1021/jz200168m	journal	March 2011
Photoinduced Magnetization of a Cobalt-Iron Cyanide Sato, O.; Iyoda, T.; Fujishima, A. Science, Vol. 272, Issue 5262 https://doi.org/10.1126/science.272.5262.704	journal	May 1996
Model of Ultrafast Intersystem Crossing in Photoexcited Transition-Metal Organic Compounds van Veenendaal, Michel; Chang, Jun; Fedro, A. J. Physical Review Letters, Vol. 104, Issue 6 https://doi.org/10.1103/physrevlett.104.067401	journal	February 2010
Ultrafast X-ray spectroscopy as a probe of nonequilibrium dynamics in ruthenium complexes Chang, Jun; Fedro, A. J.; van Veenendaal, Michel Chemical Physics, Vol. 407 https://doi.org/10.1016/j.chemphys.2012.08.024	journal	October 2012
Sequential Activation of Molecular Breathing and Bending during Spin-Crossover Photoswitching Revealed by Femtosecond Optical and X-Ray Absorption Spectroscopy Cammarata, Marco; Bertoni, Roman; Lorenc, Maciej Physical Review Letters, Vol. 113, Issue 22 https://doi.org/10.1103/PhysRevLett.113.227402	journal	November 2014
Thermally activated charge transfer in a Prussian blue derivative probed by resonant inelastic x-ray scattering Jarrige, I.; Cai, Y. Q.; Ishii, H. Applied Physics Letters, Vol. 93, Issue 5 https://doi.org/10.1063/1.2966355	journal	August 2008
Novel mechanism of photoinduced reversible phase transitions in molecule-based magnets Kawamoto, Tohru; Asai, Yoshihiro; Abe, Shuji arXiv https://doi.org/10.48550/arxiv.cond-mat/0006076	text	January 2000
Capturing a Photoexcited Molecular Structure Through Time-Domain X-ray Absorption Fine Structure Chen, L. X. Science, Vol. 292, Issue 5515 https://doi.org/10.1126/science.1057063	journal	April 2001
Ultrafast cascading theory of intersystem crossings in transition-metal complexes Chang, Jun; Fedro, A. J.; van Veenendaal, Michel Physical Review B, Vol. 82, Issue 7 https://doi.org/10.1103/PhysRevB.82.075124	journal	August 2010
Novel Mechanism of Photoinduced Reversible Phase Transitions in Molecule-Based Magnets Kawamoto, Tohru; Asai, Yoshihiro; Abe, Shuji Physical Review Letters, Vol. 86, Issue 2 https://doi.org/10.1103/PhysRevLett.86.348	journal	January 2001
Quantum coherence in photosynthesis for efficient solar-energy conversion Romero, Elisabet; Augulis, Ramunas; Novoderezhkin, Vladimir I. Nature Physics, Vol. 10, Issue 9 https://doi.org/10.1038/nphys3017	journal	July 2014
Exceptional Excited-State Lifetime of an Iron(II)– N -Heterocyclic Carbene Complex Explained Fredin, Lisa A.; Pápai, Mátyás; Rozsályi, Emese The Journal of Physical Chemistry Letters, Vol. 5, Issue 12 https://doi.org/10.1021/jz500829w	journal	May 2014
An improved model electronic Hamiltonian for potential energy surfaces and spin−orbit couplings of low-lying d−d states of [Fe(bpy) ₃ ] ²⁺ Iuchi, Satoru; Koga, Nobuaki The Journal of Chemical Physics, Vol. 140, Issue 2 https://doi.org/10.1063/1.4861229	journal	January 2014
Photoswitchable coordination compounds GÃ¼tlich, P. Coordination Chemistry Reviews, Vol. 219-221 https://doi.org/10.1016/s0010-8545(01)00381-2	journal	October 2001
Microscopic theory of cooperative spin crossover: Interaction of molecular modes with phonons Palii, Andrew; Ostrovsky, Serghei; Reu, Oleg The Journal of Chemical Physics, Vol. 143, Issue 8 https://doi.org/10.1063/1.4928642	journal	August 2015
Reversible mechanism for spin crossover in transition-metal cyanides Kabir, Mukul; Van Vliet, Krystyn J. Physical Review B, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevB.85.054431	journal	February 2012
Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+ Auböck, Gerald; Chergui, Majed Nature Chemistry, Vol. 7, Issue 8 https://doi.org/10.1038/nchem.2305	journal	July 2015
Ultrafast Deactivation Mechanism of the Excited Singlet in the Light-Induced Spin Crossover of [Fe(2,2′-bipyridine) ₃ ] ²⁺ Sousa, Carmen; de Graaf, Coen; Rudavskyi, Andrii Chemistry - A European Journal, Vol. 19, Issue 51 https://doi.org/10.1002/chem.201302992	journal	November 2013
Ultrafast Cascading Theory in Intersystem Crossings in Transition-Metal Complexes Chang, Jun; Fedro, A. J.; van Veenendaal, Michel arXiv https://doi.org/10.48550/arxiv.1004.4823	text	January 2010
Local Probe for Spin-Orbit Interaction van der Laan, G.; Thole, B. T. Physical Review Letters, Vol. 60, Issue 19 https://doi.org/10.1103/physrevlett.60.1977	journal	May 1988
Time-dependent approaches for the calculation of intersystem crossing rates Etinski, Mihajlo; Tatchen, Jörg; Marian, Christel M. The Journal of Chemical Physics, Vol. 134, Issue 15 https://doi.org/10.1063/1.3575582	journal	April 2011
Molecular spin crossover phenomenon: recent achievements and prospects Bousseksou, Azzedine; Molnár, Gábor; Salmon, Lionel Chemical Society Reviews, Vol. 40, Issue 6 https://doi.org/10.1039/c1cs15042a	journal	January 2011
TD-DFT study of the light-induced spin crossover of Fe( iii ) complexes Saureu, Sergi; de Graaf, Coen Physical Chemistry Chemical Physics, Vol. 18, Issue 2 https://doi.org/10.1039/c5cp06620d	journal	January 2016
Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated $[Co (terpy)_{2}]^{2 +}$ Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S. Physical Review Letters, Vol. 117, Issue 1 https://doi.org/10.1103/PhysRevLett.117.013002	journal	June 2016

Cited By (3)

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
Deactivation of Excited States in Transition-Metal Complexes: Insight from Computational Chemistry Sousa, Carmen; Alías, Marc; Domingo, Alex Chemistry - A European Journal, Vol. 25, Issue 5 https://doi.org/10.1002/chem.201801990	journal	November 2018

Similar Records

Time-dependent nonequilibrium soft x-ray response during a spin crossover

Journal Article · Thu Mar 08 00:00:00 EST 2018 · Physical Review B · OSTI ID:1393194

van Veenendaal, Michel

Ultrafast Spin Crossover in a Room-Temperature Ferrimagnet: Element-Specific Spin Dynamics in Photoexcited Cobalt Ferrite

Journal Article · Mon May 04 00:00:00 EDT 2020 · Journal of Physical Chemistry. C · OSTI ID:1393194

Londo, Stephen; Biswas, Somnath; Husek, Jakub; +7 more

First principles calculation of a large variation in dielectric tensor through the spin crossover in the CsFe[Cr(CN){sub 6}] Prussian blue analogue

Journal Article · Mon Apr 14 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:1393194

Related Subjects

36 MATERIALS SCIENCE

Title: Ultrafast intersystem crossings in Fe-Co Prussian blue analogues

Citation Formats

References (33)

Cited By (3)

Similar Records

Related Subjects