Transforming Ni9Te6 from Electron Donor to Acceptor via Ligand Exchange

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• 作者：Vikas Chauhan ; Arthur C. Reber ; Shiv N. Khanna
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：August 25, 2016
• 年：2016
• 卷：120
• 期：33
• 页码：6644-6649
• 全文大小：432K
• 年卷期：0
• ISSN：1520-5215

文摘

The ability to donate or accept charge is a fundamental property of a chemical species. This property is typically rooted in the valence electron count and may be determined from the ionization potential and electron affinity. First-principles theoretical studies have been carried out to show that a cluster may be transformed from a donor to an acceptor by changing only the ligand. Our studies on a chalcogenide Ni₉Te₆ cluster show that the ionization potential and electron affinity undergo substantial changes as the attachment of phosphine PH₃ decreases the ionization potential to be less than that of sodium, whereas the attachment of PCl₃ or CO increases the adiabatic electron affinity to be greater than iodine. The ligands change the electronic properties by creating a coulomb well that can shift the electronic spectrum. Studies on Co₉Te₆(CO)₈ clusters show agreement with experiment and demonstrate that the ideas developed here are applicable to a wider group of clusters.