Towards accurate prediction of spin-state energetics for transition metal complexes in quantum-chemical calculations

Research grant (SONATA) 2017/26/D/ST4/00774 funded by National Science Centre, Poland

Principal investigator (PI): Dr. hab. Mariusz Radoń, prof. UJ (Jagiellonian University in Krakow, Faculty of Chemistry)

Scientific goals

We aim to provide a new insight into the problem of spin-state energetics of transition metal (TM) complexes and models of TM sites in catalytic systems (enzymes, zeolites, MOFs) by means of advanced quantum chemical calculations and careful comparison of their results with suitable experimental data. Specifically, we would like to obtain a detailed understanding of factors affecting the accuracy of quantum-chemical electronic-structure methods, including DFT and wave-function methods (CCSD(T), CASPT2, NEVPT2, MRCI), for open-shell transition metal systems. We also would like to learn to what extent (and how) various intermolecular interactions in the solution or in the crystal phase can perturb the spin-state energetics probed by experimental methods as compared with isolated molecules normally investigated by theory. We already know that these environmental effects can be in some cases crucial when comparing the theory predictions with the experiment. The main goal of the project is to construct a benchmark set of experimentall-derived quantitative data of spin-state energetics, including back-corrections for the environmental effects, in order to evaluate the accuracy of theoretical methods. This is expected to fill important "knowledge gaps" regarding the accuracy of quantum-chemical methods for spin-state energetics of TM complexes and to provide more precise estimates of "error bars" of different methods. Moreover, we would like to study spin-energetics of some experimentally challenging systems, such as selected metalloporphyrins, in order to support interpretation of experimental data and hence address some scientifically appealing questions.

Timeline

2024-04-04: published paper #6: "Approaching the Complete Basis Set Limit for Spin-State Energetics of Mononuclear First-Row Transition Metal Complexes" as article in JCTC
2023-12-06: the project formally ends, more papers still to come
2023-10-24: published paper #5: "Benchmarks for transition metal spin-state energetics: Why and how to employ experimental reference data?" as Perspective in PCCP; it was also selected by Editors as 2023 PCCP Hot Article and appears in themed collection Benchmark Experiments for Numerical Quantum Chemistry.
2023-08-30: PI gives an invited talk during QBIC-VI conference in Warsaw, Poland
2023-02-09: co-investigator Gabriela Drabik presents an online poster at Virtual Winter School on Computational Chemistry 2023.
2022-11-21: PI gives an on-line invited seminar in the Department of Chemistry at the University of South Dakota, Vermillion, SD (USA); invited by Dr. Bess Vlaisavljevich.
2022-07-04: PI gives as an invited communication at WATOC2020: 12th Triennial Congress of the World Association of Theoretical and Computational Chemists, Vancouver, Canada
2022-06-20: PI gives an invited lecture at QSCP 2022 - 25th International Workshop on Quantum Systems in Chemistry, Physics and Biology, Torun, Poland. Co-investigator Gabriela Drabik presents a poster at the same conference.
2022-02-24: co-investigator Gabriela Drabik presents an online poster at Virtual Winter School on Computational Chemistry 2022
2021-09-14: co-investigator Gabriela Drabik presents a talk about approaching the complete basis set limit for transition metal spin-state energetics at Polish national conference "63. Zjazd Naukowy Polskiego Towarzystwa Chemicznego"; PI presents a virtual poster on dealing with environmental and vibrational effects for spin states.
2021-09-03: published paper #4: "Experimental and Computational Insight into the Mechanism of NO Binding to Ferric Microperoxidase. The Likely Role of Tautomerization to Account for the pH Dependence" in Inorg. Chem. This paper results from our extensive colaboration with the experimental group, where we contributed high-level calculations (including spin-state energetics of ferric–porphyrin models at the coupled cluster level) and interpretations of critical importance to elucidate the reaction mechanism. Our work is highlighted on the supplementary journal cover of vol. 60, issue 21 "Renaissance in NO Chemistry".
2021-05-04: PI is nominated for Polish prize "Naukowiec Przyszłości 2021" ("The Scientist of the Future 2021") awarded by Centrum Inteligentnego Rozwoju; here is a copy of the nomination letter.
2021-02-24: PI participates (as invited expert) in 1st QBtopIC panel discussion on spin states, online event organized by Quantum Bio-Inorganic Chemistry Society. Discussion report is available here.
2021-02-15: co-investigator Gabriela Drabik presents online poster (SFP) at Virtual Winter School on Computational Chemistry: "Ferric microperoxidase: spin-state energetics and ligand exchange"
2021-01-06: our paper "Spin–state energetics of metallocenes..." has been selected by PCCP Editors as one of the 2021 HOT PCCP Articles. This paper is also part of themed collection Quantum Theory: The Challenge of Transition Metal Complexes
2020-11-13: published paper #3: "Heptacoordinated W(IV) Cyanido Supramolecular Complex Trapped by Photolysis of a [W(CN)₆(bpy)]^2-/Zn²⁺ System" in Crys. Growth Des.
2020-11-09: published paper #2: "Spin–state energetics of metallocenes: How do best wave function and density functional theory results compare with the experimental data?" in Phys. Chem. Chem. Phys.. This is a very detailed benchmark study of wave function theory and DFT methods against experimental data (including carefully revised experimental optical spectrum of ferrocene).
2020-02-07: the PI gives an invited talk during the Winter Symposium 2020 jointly organized by MPI CEC (inorganic spectroscopy group) and MPI KoFo (molecular theory and spectroscopy group); invited by Professor Frank Neese
2019-12-09: co-investigator Gabriela Drabik presents a poster at 35th Winter School in Theoretical Chemistry 2019, Helsinki, Finland
2019-11-07: master degree in chemistry awarded to Gabriela Drabik (co-investigator) for thesis related to this project (on the electronic structure and spin states of metallocenes). Congratulations!
2019-09-12: habilitation awarded to the PI by the Council of Faculty of Chemistry, Jagiellonian University in Krakow
2019-09-03: the PI gives a contributed talk at the international conference Current Trends in Theoretical Chemistry VIII in Krakow, Poland
2019-06-26: the PI gives invited seminar in the Center for Theoretical Chemistry at Ruhr-Universität Bochum, Germany; invited by Dr. Michael Römelt
2019-06-12: our paper ""Benchmarking quantum chemistry methods..." was selected by PCCP Editors as 2019 HOT PCCP Article
2019-02-11: published paper #1: "Benchmarking quantum chemistry methods for spin-state energetics of iron complexes against quantitative experimental data", Phys. Chem. Chem. Phys., 2019, 21, 4854–4870
2018-12-21: published book chapter "Toward accurate spin-state energetics of transition metal complexes" in Advances in Inorganic Chemistry, Academic Press, 2019, vol. 73, pp. 221–26 (edited by Rudi van Eldik and Ralph Puchta)
2018-09-19: the PI gives invited talk and chairs the session during the 61st Annual Scientific Meeting of the Polish Chemical Society, Krakow, Poland
2018-09-03: the PI gives an invited talk at Quantum Bio-Inorganic Chemistry Conference IV in Bath, UK
2018-05-07: the project formally starts
2018-02-21: grant award decision (with 1st position on the ranking list of this SONATA call!)

Publications

These are publications related to this project. See list of all publications.

In books

M. Radoń "Toward accurate spin-state energetics of transition metal complexes", Advances in Inorganic Chemistry, Academic Press, 2019, vol. 73, pp. 221–26 (edited by Rudi van Eldik and Ralph Puchta)

In peer-reviewed journals

M. Radoń "Benchmarking quantum chemistry methods for spin-state energetics of iron complexes against quantitative experimental data", Phys. Chem. Chem. Phys., 2019, 21, 4854–4870
G. Drabik, J. Szklarzewicz, M. Radoń "Spin–state energetics of metallocenes: How do best wave function and density functional theory results compare with the experimental data?" Phys. Chem. Chem. Phys., 2021, 23, 151–172
M. Hodorowicz, J. Szklarzewicz, M. Radoń, A. Jurowska "Heptacoordinated W(IV) Cyanido Supramolecular Complex Trapped by Photolysis of a [W(CN)6(bpy)]2-/Zn2+ System" Crys. Growth Des., 2020, 20, 7742–7749
M. Oszajca, G. Drabik, M. Radoń, A. Franke, R. van Eldik, G. Stochel "Experimental and Computational Insight into the Mechanism of NO Binding to Ferric Microperoxidase. The Likely Role of Tautomerization to Account for the pH Dependence: Inorg. Chem., 2021, 60, 15948–15967
M. Radoń "Benchmarks for transition metal spin-state energetics: Why and how to employ experimental reference data?" Phys. Chem. Chem. Phys., 2023, 25, 30800–30820
G. Drabik, M. Radoń "Approaching the Complete Basis Set Limit for Spin-State Energetics of Mononuclear First-Row Transition Metal Complexes" J. Chem. Theory. Comput., 2024, DOI: 10.1021/acs.jctc.4c00092 (open access).

Preprints

M. Radoń "Predicting Spin States of Iron Porphyrins with DFT Methods Including Crystal Packing Effects and Thermodynamic Corrections", ChemRxiv preprint.

Job offers

We offered two positions with sholarship in this project: student and PhD student. Both co-investigator positions have been successfully occupied. No position is currently offered.

Contact

dr. hab. Mariusz Radoń, prof. UJ

Jagiellonian University in Kraków
Faculty of Chemistry
Gronostajowa 2
30-387 Krakow, Poland
e-mail: mariusz.radon@uj.edu.pl
ORCID

Main website of Coordination Chemistry Group, Faculty of Chemistry JU.