College of Engineering, Huaqiao University, Quanzhou, 362021, China.
Phys Chem Chem Phys. 2012 Apr 21;14(15):5272-83. doi: 10.1039/c2cp40112f. Epub 2012 Mar 8.
The structural evolution and bonding of a series of early transition-metal oxide clusters, V(n)O(q) (n = 3-9, q = 0,-1), have been investigated with the aid of previous photoelectron spectroscopy (PES) and theoretical calculations. For each vanadium monoxide cluster, many low-lying isomers are generated using the Saunders "Kick" global minimum stochastic search method. Theoretical electron detachment energies (both vertical and adiabatic) were compared with the experimental measurements to verify the ground states of the vanadium monoxide clusters obtained from the DFT calculations. The results demonstrate that the combination of photoelectron spectroscopy experiments and DFT calculation is not only powerful for obtaining the electronic and atomic structures of size-selected clusters, but also valuable in resolving structurally and energetically close isomers. The second difference energies and adsorption energies as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. The adsorption energies of one O atom on the anionic (6.64 → 8.16 eV) and neutral (6.41 → 8.13 eV) host vanadium clusters are shown to be surprisingly high, suggesting strong capabilities to activate O by structural defects in vanadium oxides.
利用先前的光电子能谱（PES）和理论计算，研究了一系列早期过渡金属氧化物团簇 V(n)O(q)（n = 3-9，q = 0，-1）的结构演变和键合。对于每个氧化钒团簇，使用 Saunders“Kick”全局最小随机搜索方法生成了许多低能异构体。将理论电子离解能（垂直和绝热）与实验测量值进行比较，以验证从 DFT 计算中获得的氧化钒团簇的基态。结果表明，光电子能谱实验与 DFT 计算的结合不仅可用于获得尺寸选择的团簇的电子和原子结构，而且在解决结构和能量上接近的异构体方面也很有价值。第二差分能量和吸附能随团簇尺寸的变化表现出明显的奇偶交替现象。一个 O 原子在阴离子（6.64→8.16 eV）和中性（6.41→8.13 eV）主体钒团簇上的吸附能出乎意料地高，表明在氧化钒中通过结构缺陷激活 O 的能力很强。
