Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdO n-1/0 ( n = 1-4) Clusters.
Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdO n-1/0 ( n = 1-4) Clusters.
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DOI：
10.1021/acs.jpca.8b09058
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发表时间：
2018-10
期刊：
影响因子：
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通讯作者：
J. Chen;Huan Yang;Jing Wang;Shibo Cheng
中科院分区：
文献类型：
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作者：
J. Chen;Huan Yang;Jing Wang;Shibo Cheng
大量4f电子的存在显著增加了精确确定镧系氧化物团簇几何结构和电子结构的复杂性和难度。在此，通过结合光电子成像光谱和密度泛函理论（DFT）计算，GdO的电子结构进行了研究。电子亲和势（EA）为1.16 ± 0.09 eV，各向异性参数（β）的测量为GdO-中分离电子的轨道对称性提供了直接的实验证据。采用密度泛函理论（DFT）计算得到了GdO n-1/0（n = 2-4）团簇的最佳几何构型，并在这些氧化物团簇中发现了多种活性氧物种，包括自由基、过氧化物、超氧化物、三自由基和臭氧化物自由基.研究了GdO n-1/0（n = 2-4）团簇的模拟光电子能谱（PES），为进一步研究氧化钆团簇提供了实验依据.此外，还讨论了这些簇合物的价分子轨道（MO），以揭示镧系金属（Gd）与O原子之间的相互作用。
The existence of abundant 4f electrons significantly increases the complexity and difficulty in precisely determining the geometric and electronic structures of the lanthanide oxide clusters. Herein, by combining the photoelectron imaging spectroscopy and density functional theory (DFT) calculations, the electronic structure of GdO was investigated. An electron affinity (EA) of 1.16 ± 0.09 eV is obtained, and the measured anisotropy parameter (β) provides direct experimental evidence about the orbital symmetry of the detached electron in GdO-. DFT calculations have been employed to acquire the optimized geometries of the GdO n-1/0 ( n = 2-4) clusters, and multiple activated oxygen species, which are radical, peroxide, superoxide, triradical, and ozonide radical, are found in these oxide clusters. Simulated photoelectron spectra (PES) of the GdO n-1/0 ( n = 2-4) clusters are examined, which may stimulate further experimental investigations on the gadolinium oxide clusters. In addition, the valence molecular orbitals (MOs) of these clusters are also discussed to reveal the interaction between the lanthanide metal (Gd) and O atoms.