Can range-separated functionals be optimally tuned to predict spectra and excited state dynamics in photoactive iron complexes?

Autor: Zobel JP; Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 19 1090 Vienna Austria jan.patrick.zobel@univie.ac.at., Kruse A; Institute of Physics, University of Rostock, Albert-Einstein-Straße 23-24 18059 Rostock Germany olga.bokareva@uni-rostock.de.; Department of Life, Light and Matter, University of Rostock 18051 Rostock Germany., Baig O; Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 19 1090 Vienna Austria jan.patrick.zobel@univie.ac.at., Lochbrunner S; Institute of Physics, University of Rostock, Albert-Einstein-Straße 23-24 18059 Rostock Germany olga.bokareva@uni-rostock.de.; Department of Life, Light and Matter, University of Rostock 18051 Rostock Germany., Bokarev SI; Institute of Physics, University of Rostock, Albert-Einstein-Straße 23-24 18059 Rostock Germany olga.bokareva@uni-rostock.de.; Chemistry Department, Technical University of Munich, Lichtenbergstr. 4 Garching 85748 Germany., Kühn O; Institute of Physics, University of Rostock, Albert-Einstein-Straße 23-24 18059 Rostock Germany olga.bokareva@uni-rostock.de., González L; Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 19 1090 Vienna Austria jan.patrick.zobel@univie.ac.at., Bokareva OS; Institute of Physics, University of Rostock, Albert-Einstein-Straße 23-24 18059 Rostock Germany olga.bokareva@uni-rostock.de.; Institute of Physics, University of Kassel Heinrich-Plett-Straße 40 34132 Kassel Germany.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2023 Jan 12; Vol. 14 (6), pp. 1491-1502. Date of Electronic Publication: 2023 Jan 12 (Print Publication: 2023).
DOI: 10.1039/d2sc05839a
Abstrakt: Density functional theory is an efficient computational tool to investigate photophysical and photochemical processes in transition metal complexes, giving invaluable assistance in interpreting spectroscopic and catalytic experiments. Optimally tuned range-separated functionals are particularly promising, as they were created to address some of the fundamental deficiencies present in approximate exchange-correlation functionals. In this paper, we scrutinize the selection of optimally tuned parameters and its influence on the excited state dynamics, using the example of the iron complex [Fe(cpmp) 2 ] 2+ with push-pull ligands. Various tuning strategies are contemplated based on pure self-consistent DFT protocols, as well as on the comparison with experimental spectra and multireference CASPT2 results. The two most promising sets of optimal parameters are then employed to carry out nonadiabatic surface-hopping dynamics simulations. Intriguingly, we find that the two sets lead to very different relaxation pathways and timescales. While the set of optimal parameters from one of the self-consistent DFT protocols predicts the formation of long-lived metal-to-ligand charge transfer triplet states, the set in better agreement with CASPT2 calculations leads to deactivation in the manifold of metal-centered states, in better agreement with the experimental reference data. These results showcase the complexity of iron-complex excited state landscapes and the difficulty of obtaining an unambiguous parametrization of long-range corrected functionals without experimental input.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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