Freiburg 2024 – wissenschaftliches Programm

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MO: Fachverband Molekülphysik

MO 18: Poster: Cluster

MO 18.2: Poster

Mittwoch, 13. März 2024, 17:00–19:00, Tent C

DFT and TD-DFT study of the gas-phase nickel tetracarbonyl complex — •A. Hreben^1,2, O. S. Ablyasova^2,3, M. Flach^2,3, M. Timm², M. da Silva Santos^2,3, V. Zamudio-Bayer², K. Hirsch², and J. T. Lau^2,3 — ¹Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany — ²HZB, Albert-Einstein-Straße 15, 12489 Berlin, Germany — ³Universität Freiburg, Hermann-Herder-Straße 3, 79104 Freiburg, Germany

Investigations of transition metal carbonyl complexes have a significant role in the rapid development of coordination chemistry. Metal carbonyls are widely used as catalysts in synthesis and industrial processes and also find applications in electrochemistry and laser chemistry as precursors. The first discovered homoleptic carbonyl complex was Ni(CO)₄, whose structure and binding properties are still under discussion. In this research, we focused on calculating the most stable structure of Ni(CO)₄⁺ using DFT methods. Four possible multiplicities of the given complex were analyzed using three different functionals (B3LYP, M06L, TPSSh) and two basis sets (def2-TZVP, 6-311+G(3df)). Based on the comparison of the obtained final total energies of optimized geometries, the method giving minimal energy was used for further TD-DFT calculations. The obtained simulated oxygen K-edge of the X-ray absorption spectra (XAS) are compared to experimental data. For that matter, gas-phase Ni(CO)₄⁺ complex measurements were performed via XAS in ion yield mode at the oxygen K-edge on mass-selected ions, cryogenically cooled in the Ion-Trap end station located in BESSY II.

Keywords: DFT; Ni(CO)4+ complex; XAS; Single point energy; K-edge