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 (assistant professor, 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.


Grant publications

In peer-reviewed journals

  1. M. Radoń, G. Drabik "Spin States and Other Ligand--Field States of Aqua Complexes Revisited with Multireference Methods", J. Chem. Theory Comput., 2018, 14, 4010–4027
  2. 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
  3. 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
  4. 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
  5. 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

In books

  1. 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)

Job offers

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


dr. hab. Mariusz Radoń, prof. UJ

Jagiellonian University in Kraków
Faculty of Chemistry
Gronostajowa 2
30-387 Krakow, Poland
ORCID | Publons