Chaves Anderson S, Piotrowski Maurício J, Da Silva Juarez L F
Gleb Wataghin Institute of Physics, University of Campinas, PO Box 6165, 13083 - 859, Campinas, SP, Brazil.
Phys Chem Chem Phys. 2017 Jun 14;19(23):15484-15502. doi: 10.1039/c7cp02240a.
Subnanometric transition-metal (TM) clusters have attracted great attention due to their unexpected physical and chemical properties, leastwise compared to their bulk counterparts. An in-depth understanding of the evolution of the properties as a function of the number of atoms for such systems is a basic prerequisite to leverage countless applications, from catalysis to magnetic storage, as well as to answer fundamental questions related to their intrinsic stability. Here, we reported a systematic density functional study to investigate the structural, electronic properties and stability of all TM (30 elements) unary clusters as a function of the number of atoms (n = 2-15). We provided the complete structural patterns for all TM periodic table groups, considering the growth evolution as well as the main trends of the structural and electronic properties. The combination of the occupation of the bonding/anti-bonding d-states and the s-d hybridization is found to be the main stabilization mechanism, helping in the understanding of the structural patterns. Most TM clusters have a magic number of atoms, for which there are peaks in s-d hybridization and null electric dipole moments. Thus, our extensive and comparative study addresses size effects along with the evolution of d-orbital occupation for the TM gas-phase cluster properties.
亚纳米级过渡金属（TM）团簇因其意想不到的物理和化学性质而备受关注，至少与它们的块状对应物相比是这样。深入了解此类系统的性质随原子数的演变，是利用从催化到磁存储等无数应用以及回答与其固有稳定性相关的基本问题的基本前提。在此，我们报告了一项系统的密度泛函研究，以研究所有TM（30种元素）一元团簇的结构、电子性质和稳定性随原子数（n = 2 - 15）的变化。我们给出了所有TM周期表族的完整结构模式，考虑了生长演化以及结构和电子性质的主要趋势。发现成键/反键d态的占据与s - d杂化的结合是主要的稳定机制，有助于理解结构模式。大多数TM团簇具有原子幻数，此时s - d杂化出现峰值且电偶极矩为零。因此，我们广泛的比较研究探讨了TM气相团簇性质的尺寸效应以及d轨道占据的演变。
