Hou Liyuan, Yang Jucai, Liu Yuming
School of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot, 010051, People's Republic of China.
Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, Hohhot, 010051, People's Republic of China.
J Mol Model. 2017 Apr;23(4):117. doi: 10.1007/s00894-017-3271-6. Epub 2017 Mar 13.
The structures and properties of Ho-doped Si clusters, including their adiabatic electron affinities (AEAs), simulated photoelectron spectra (PESs), stabilities, magnetic moments, and charge-transfer characteristics, were systematically investigated using four density-functional methods. The results show that the double-hybrid functional (which includes an MP2 correlation component) can accurately predict the ground-state structure and properties of Ho-doped Si clusters. The ground-state structures of HoSi (n = 3-9) are sextuplet electronic states. The structures of these Ho-doped Si clusters (aside from HoSi) are substitutional. The ground-state structures of HoSi are quintuplet electronic states. Their predicted AEAs are in excellent agreement with the experimental ones. The mean absolute error in the theoretical AEAs of HoSi (n = 4-9) is only 0.04 eV. The simulated PESs for HoSi (n = 5-9) are in good agreement with the experimental PESs. Based on its simulated PES and theoretical AEA, we reassigned the experimental PES of HoSi and obtained an experimental AEA of 2.2 ± 0.1 eV. The dissociation energies of Ho from HoSi and HoSi (n = 3-9) were evaluated to test the relative stabilities of the clusters. HOMO-LUMO gap analysis indicated that doping the Si clusters with the rare-earth metal atom significantly increases their photochemical reactivity. Natural population analysis showed that the magnetic moments of HoSi (n = 3-9) and their anions derive mainly from the Ho atom. It was also found that the magnetic moments of Ho in the HoSi clusters are larger than the magnetic moment of an isolated Ho atom.
采用四种密度泛函方法系统研究了掺钬硅团簇的结构和性质，包括其绝热电子亲和能（AEA）、模拟光电子能谱（PES）、稳定性、磁矩和电荷转移特性。结果表明，双杂化泛函（包括MP2相关分量）能够准确预测掺钬硅团簇的基态结构和性质。HoSi （n = 3 - 9）的基态结构为六重态电子态。这些掺钬硅团簇（除HoSi外）的结构为取代型。HoSi的基态结构为五重态电子态。其预测的AEA与实验值吻合良好。HoSi （n = 4 - 9）理论AEA的平均绝对误差仅为0.04 eV。HoSi （n = 5 - 9）的模拟PES与实验PES吻合良好。基于其模拟PES和理论AEA，我们重新确定了HoSi的实验PES，并得到了2.2±0.1 eV的实验AEA。评估了Ho从HoSi 和HoSi （n = 3 - 9）的解离能，以测试团簇的相对稳定性。HOMO-LUMO能隙分析表明，用稀土金属原子掺杂硅团簇显著提高了它们的光化学反应活性。自然布居分析表明，HoSi （n = 3 - 9）及其阴离子的磁矩主要来自Ho原子。还发现HoSi 团簇中Ho的磁矩大于孤立Ho原子的磁矩。
