Configuration-Interaction Full-Multiplet Calculation to Analyze the Electronic Structure of a Cyano-Bridged Coordination Polymer Electrode

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• 作者：Yu虆suke Nanba ; Daisuke Asakura ; Masashi Okubo ; Yoshifumi Mizuno ; Tetsuichi Kudo ; Haoshen Zhou ; Kenta Amemiya ; Jinghua Guo ; Kozo Okada
• 刊名：The Journal of Physical Chemistry C
• 出版年：2012
• 出版时间：November 29, 2012
• 年：2012
• 卷：116
• 期：47
• 页码：24896-24901
• 全文大小：309K
• 年卷期：v.116,no.47(November 29, 2012)
• ISSN：1932-7455

文摘

To understand the electronic-structure changes of electrode materials during the charge/discharge processes is one of the most important fundamental aspects to improve the battery performance. Soft X-ray absorption spectroscopy (XAS) was used to study a bimetallic NiFe Prussian blue analogue electrode. XA spectra were obtained during the charge/discharge and were analyzed by the configuration-interaction full-multiplet (CIFM) calculation, in which the strong charge transfer due to the 蟽/蟺-donation and back-donation of cyanide was taken into account. The CIFM calculation revealed that the metal-to-ligand charge transfer (MLCT) played an important role in the electronic state of Ni鈥揘 bond. The Fe³⁺鈥揅 bond in the charged state is dominated by both the MLCT and ligand-to-metal charge transfer (LMCT), whereas only the MLCT strongly affects the Fe²⁺鈥揅 bond in the discharged state.