Acioli Paulo H
Department of Physics and Astronomy Northeastern Illinois University Chicago, Illinois 60625 USA.
ChemistryOpen. 2020 May 4;9(5):545-549. doi: 10.1002/open.202000079. eCollection 2020 May.
We have recently developed a computational methodology to separate the effects of size, composition, symmetry and fluxionality in explaining the experimental photoelectron spectra of mixed-metal clusters. This methodology was successfully applied first in explaining the observed differences between the spectra of Al and AlNi and more recently to explain the measured spectra of AlMo, n=3-5,7 clusters. The combination of our approach and new synthesis techniques can be used to prepare cluster-based materials with tunable properties. In this work we use the methodology to predict the spectrum of AlMo. This system was chosen because its neutral counterpart is a perfect octahedron and it is distorted to a D symmetry and was not observed in the recent experiments. This high symmetry cluster bridges the less symmetric AlMo and AlMostructures.The measured spectra of AlMo has well defined peaks, while that of AlModoes not. This can be explained by the fluxionality of AlMo, as at least 6 different structures lie within the range that can be reached by thermal effects. We predict that AlMo has well defined peaks, but some broadening is expected as there are two low-lying isomers, one of D and the second of D symmetry that are only 0.052 eV apart.
我们最近开发了一种计算方法，用于在解释混合金属团簇的实验光电子能谱时，分离尺寸、组成、对称性和分子流动性的影响。该方法首先成功应用于解释铝和铝镍团簇光谱之间观察到的差异，最近又用于解释铝钼（n = 3 - 5, 7）团簇的测量光谱。我们的方法与新的合成技术相结合，可用于制备具有可调性质的基于团簇的材料。在这项工作中，我们使用该方法预测铝钼团簇的光谱。选择这个体系是因为它的中性对应物是一个完美的八面体，它会扭曲成D对称性，并且在最近的实验中未被观测到。这个高对称团簇连接了对称性较低的铝钼和铝钼结构。铝钼的测量光谱有明确的峰，而铝钼的光谱则没有。这可以用铝钼的分子流动性来解释，因为至少有6种不同的结构处于热效应可达到的范围内。我们预测铝钼有明确的峰，但预计会有一些展宽，因为有两个低能异构体，一个是D对称性，另一个是D对称性，它们之间的能量差仅为0.052电子伏特。
