Research in the Manganas group focuses on the development and application of advanced experimental and theoretical spectroscopic methodologies for the study of heterogeneous catalytic reactions.
Identifying catalytically active structures or intermediates in homogeneous and heterogeneous catalysis is a formidable challenge.It is well known that even for industrially leading catalytic processes there is a limited understanding regarding the catalytic activity of the working catalysts as well as the catalytic intermediates involved in the catalysis mechanisms. Such ‘missing’ information is however essential for the design of new functional materials. With all these in mind we have developed a joint project between several groups and departments in the MPI KoFo and MPI-CEC institutes aiming a spectroscopic and a reactivity understanding of the materials science processes.
With the aim to uniquely correlate spectroscopic properties to electronic structure and geometric properties of target materials, we are working closely with the experimental X-ray spectroscopy groups of the neighbor MPI-CEC institute and employ in house developed wavefunction based methods in an effort to evaluate unique spectroscopic signatures of transition metal complexes and materials in both equilibrium and under operando conditions. This requires to use methods that do not belong in the standard arsenal of quantum chemistry. Over the last years we have developed and employed the restricted open shell configuration interaction singles methods (ROCIS and PNO-ROCIS) and their parameterized versions, (ROCIS/DFT and PNO-ROCIS/DFT) to compute a large variety of XAS and valence to core resonance X-ray emission spectra (VtC-RXES) of classes of chemical systems ranging between molecules to ‘real-life’ molecular and solid systems. Recently even more accurate computational protocols based on the complete active space configuration interaction in conjunction with N-electron valence second order perturbation theory (CASCI/NEVPT2) as well as multireference configuration interaction (MRCI) and multireference equation of motion coupled cluster (MREOM-CC) methods have been employed to compute challenging metal L-edge XAS spectra of medium sized molecules with high predictive accuracy.
Representative Publications:
Roemelt, M.; Maganas, D.; DeBeer, S.; Neese, F., A Combined Dft and Restricted Open-Shell Configuration Interaction Method Including Spin-Orbit Coupling: Application to Transition Metal L-Edge X-Ray Absorption Spectroscopy. The Journal of chemical physics 2013, 138, 204101.
Maganas, D.; DeBeer, S.; Neese, F., A Restricted Open Configuration Interaction with Singles Method to Calculate Valence-to-Core Resonant X-Ray Emission Spectra: A Case Study. Inorganic chemistry 2017, 56, 11819-11836.
Maganas, D.; DeBeer, S.; Neese, F., Pair Natural Orbital Restricted Open-Shell Configuration Interaction (PNO-ROCIS) Approach for Calculating X-Ray Absorption Spectra of Large Chemical Systems. The Journal of Physical Chemistry A 2018, 122, 1215-1227.
Chantzis, A.; Kowalska, J. K.; Maganas, D.; DeBeer, S.; Neese, F., Ab Initio Wave Function-Based Determination of Element Specific Shifts for the Efficient Calculation of X-Ray Absorption Spectra of Main Group Elements and First Row Transition Metals. Journal of chemical theory and computation 2018, 14, 3686-3702.
Maganas, D.; Kowalska, J. K.; Nooijen, M.; DeBeer, S.; Neese, F., Comparison of Multireference Ab Initio Wavefunction Methodologies for X-Ray Absorption Edges: A Case Study on [Fe(II/III)Cl4]2–/1– Molecules. The Journal of chemical physics 2019, 150, 104106.
An important activity in the group is to develop valid spectroscopic protocols that are able to treat relevant problems that are met in the fields of homogeneous and heterogeneous catalysis. The ultimate goal here is to develop a spectroscopic information content that is transferable between the homogeneous and heterogeneous catalysis worlds.
Representative Publications:
Maganas, D.; Trunschke, A.; Schlögl, R.; Neese, F., A Unified View on Heterogeneous and Homogeneous Catalysts through a Combination of Spectroscopy and Quantum Chemistry. Faraday discussions 2016, 188, 181-197.
Kubas, A.; Noak, J.; Trunschke, A.; Schlögl, R.; Neese, F.; Maganas, D., A Combined Experimental and Theoretical Spectroscopic Protocol for Determination of the Structure of Heterogeneous Catalysts: Developing the Information Content of the Resonance Raman Spectra of M1 MoVOx. Chemical science 2017, 8, 6338-6353.
As in addition to spectroscopy, reactivity plays an essential role in understanding the structure and the properties of catalytic active centers, the group shows activity in defining protocols that can deliver accurate energetics in problems similar to those met in solid state catalysis. In a characteristic example it has been recently shown that using the domain-based pair natural orbital local correlation concept (DLPNO-CCSD(T)), allows for ab initio calculations providing reference adsorption energetics at solid surfaces with an accuracy approaching 1 kcal/mol and at affordable computational cost. In a more recent example we have demonstrated that for both organic and inorganic semiconductors the back-transformed Pair Natural Orbital Similarity Transformed Equation of Motion Coupled-Cluster (bt-PNO-STEOM-CCSD) method provides the best agreement with the available experimental values resulting in errors that are on average lower than 0.2 eV.
Representative publications:
Kubas, A.; Berger, D.; Oberhofer, H.; Maganas, D.; Reuter, K.; Neese, F., Surface Adsorption Energetics Studied with “Gold Standard” Wave-Function-Based Ab Initio Methods: Small-Molecule Binding to TiO2 (110). The journal of physical chemistry letters 2016, 7, 4207-4212.
Dittmer, A.; Izsák, R. b.; Neese, F.; Maganas, D., Accurate Band Gap Predictions of Semiconductors in the Framework of the Similarity Transformed Equation of Motion Coupled Cluster Theory. Inorganic chemistry 2019.
Dr. Cahier, Benjamin
+49(0)208/306-2168
cahier((atsign))kofo.mpg.de
Dr. Chantzis, Agisilaos
PostDoc 01.01.2018 - 31.01.2018
da Costa Gouveia Leyser, Tiago
+49 (0)208 306 - 3588
leyser((atsign))kofo.mpg.de
Dittmer, Anneke
+49 (0)208 306 - 2159
dittmer((atsign))kofo.mpg.de
Dr. Manganas, Dimitrios
+49 (0)208 306 - 3589
dimitrios.manganas((atsign))kofo.mpg.de
Shafei, Rami
+49 (0)208 306 - 3585
shafei((atsign))kofo.mpg.de