Schwedland Winni, Penna Tatiana C, Windeck Henning, Müller Fabian, Leach Stephen, Sauer Joachim, Advincula Xavier R, Berger Fabian, Ishida Nanako, Ohshimo Keijiro, Misaizu Fuminori, Li Ya-Ke, Chakraborty Arghya, Horn Francine, Asmis Knut R
Institut für Chemie, Humboldt-Universität zu Berlin Unter den Linden 6 10099 Berlin Germany
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig Linnéstraße 2 04103 Leipzig Germany
Chem Sci. 2025 May 19. doi: 10.1039/d5sc02681d.
The structure and reactivity of the mixed metal oxide clusters AlMO and AlMO (M = Fe, Co), formally obtained by transition metal ion substitution from AlO , are studied using infrared photodissociation (IRPD) spectroscopy, ion-mobility mass-spectrometry (IM-MS) and quantum chemistry. We use density functional theory (DFT) in combination with global structure optimization to identify low energy structures and to connect them to the IRPD and IM-MS data. Insights into anharmonic and temperature effects are obtained from machine learning-based molecular dynamics simulations. While all metal ions are equal in the cone-shaped structure of MO , the mixed metal oxide clusters attain different, more stable structures, in which the metal ions are either in different oxidation states (AlMO ) or have different coordination numbers (AlMO ). The present results illustrate that different DFT functionals may accurately describe local minimum structures, but reliable relative energies of isomers with differently coordinated transition metal ions require multi-reference wavefunction calculations.
通过从AlO 进行过渡金属离子取代而正式获得的混合金属氧化物簇AlMO 和AlMO （M = Fe，Co）的结构和反应活性，采用红外光解离（IRPD）光谱、离子迁移质谱（IM-MS）和量子化学进行了研究。我们使用密度泛函理论（DFT）结合全局结构优化来识别低能量结构，并将它们与IRPD和IM-MS数据相关联。基于机器学习的分子动力学模拟获得了对非谐和温度效应的深入了解。虽然在MO 的锥形结构中所有金属离子是等同的，但混合金属氧化物簇具有不同的、更稳定的结构，其中金属离子要么处于不同的氧化态（AlMO ），要么具有不同的配位数（AlMO ）。目前的结果表明，不同的DFT泛函可以准确描述局部极小结构，但具有不同配位过渡金属离子的异构体的可靠相对能量需要多参考波函数计算。
