Unveiling the electronic structures and ligation effect of the superatom-polymeric zirconium oxide clusters: a computational study.
Unveiling the electronic structures and ligation effect of the superatom-polymeric zirconium oxide clusters: a computational study.
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DOI：
10.1039/c9cp01870k
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发表时间：
2019-07
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影响因子：
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通讯作者：
Jing Wang;Yang-yong Zhao;Jun Li;Haicai Huang;J. Chen;Shibo Cheng
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文献类型：
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作者：
Jing Wang;Yang-yong Zhao;Jun Li;Haicai Huang;J. Chen;Shibo Cheng
发现非贵金属ZrO簇作为贵金属催化剂Pd的类似物对于使用超原子概念设计具有微调性能的功能材料具有重要意义。然而，逐渐组装 ZrO 超原子单元对较大 ZrO 聚合物簇的电子结构和化学键合的影响尚不清楚。在此，通过使用密度泛函理论（DFT）计算，优化了（ZrO）n-/0（n = 2-5）团簇的最低能量结构和低位异构体，其中这些团簇中的每个O原子倾向于连接其相邻的两个Zr原子形成金属氧桥键。通过分析这些团簇的分子轨道（MO）和态密度（DOS），可以深入了解这些团簇的电子特性。更重要的是，我们对CO（电子受体）和PH3（电子供体）连接的Zr3O3团簇的研究表明，连接过程可以通过调节HOMO和LUMO状态来显着改变团簇的电子特性，这可能在光伏领域具有潜在的应用。引人注目的是，PH3 在 Zr3O3 上的连续附着显着降低了连接簇的绝热电离势 (AIP)，从而形成具有大 HOMO-LUMO 间隙的稳定超碱簇。此外，还考察了构建超碱Zr3O3(PH3)5基一维簇组装材料的潜力。
Discovering the non-noble ZrO cluster as an analog of the noble metal catalyst Pd is of significance toward designing functional materials with fine-tuned properties using the superatom concept. The effect of gradually assembling the ZrO superatomic unit on the electronic structures and chemical bonding of larger ZrO-polymeric clusters, however, is unclear. Herein, by using density functional theory (DFT) calculations, the lowest-energy structures and low-lying isomers of the (ZrO)n-/0 (n = 2-5) clusters were optimized, in which every O atom in these clusters tends to connect its adjacent two Zr atoms forming metal oxygen bridge bonds. Insights into the electronic characteristics of these clusters were obtained by analyzing their molecular orbitals (MOs) and density of states (DOS). More importantly, our studies on the CO (electron acceptor) and PH3 (electron donor) ligated Zr3O3 clusters unveil that the ligation process can substantially alter the electronic properties of the clusters by tuning the HOMO and LUMO states, which may have potential applications in photovoltaics. Strikingly, the successive attachment of PH3 on Zr3O3 dramatically lowers the adiabatic ionization potential (AIP) of the ligated clusters, resulting in the formation of stable superalkali clusters with large HOMO-LUMO gaps. Furthermore, the potential of constructing the superalkali Zr3O3(PH3)5 based 1-D cluster assembled material was also examined.