Solid-State Structure and Calculated Electronic Structure, Formation Energy, Chemical Bonding, and Optical Properties of Zn4O(FMA)3 and Its Heavier Congener Cd4O(FMA)<

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• 作者：Li-Ming Yang ; Ponniah Ravindran ; Mats Tilset
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 15, 2013
• 年：2013
• 卷：52
• 期：8
• 页码：4217-4228
• 全文大小：720K
• 年卷期：v.52,no.8(April 15, 2013)
• ISSN：1520-510X

文摘

The equilibrium solid-state structure of the experimentally synthesized but incompletely characterized Zn₄O(FMA)₃ is revised with the help of density functional theory computational methods. The electronic structure, formation energy, chemical bonding, and optical properties of Zn₄O(FMA)₃ and its heavier congener Cd₄O(FMA)₃ have been systematically investigated. The calculated bulk moduli for Zn₄O(FMA)₃ and Cd₄O(FMA)₃ are similarly small (and slightly smaller than the previously reported values for MOF-5), indicative of relatively soft materials. Their estimated band-gap values are ca. 3.2 eV (somewhat lower than that of MOF-5, 3.4鈥?.5 eV), indicating semiconducting character. The optical properties including dielectric function 蔚(蠅), refractive index n(蠅), absorption coefficient 伪(蠅), optical conductivity 蟽(蠅), reflectivity R(蠅), and electron energy-loss spectrum L(蠅) of M₄O(FMA)₃ (M = Zn, Cd) were systematically studied. Analysis of chemical bonding reveals that the M鈥揙 bonds are largely ionic, with an increase in ionicity from Zn to Cd. The total energy calculations establish that compounds M₄O(FMA)₃ have large negative formation energies, ca. 鈭?0 and 鈭?0 kJ路molp>鈥?p> for Zn and Cd, respectively. Whereas Zn₄O(FMA)₃ has already been synthesized, the results suggest that the heavier congener Cd₄O(FMA)₃ might be experimentally accessible.