Tungsten and Molybdenum Heteropolyanions with Different Central Ions—Correlation between Theory and Experiment |
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Authors: | Piotr Niemiec Renata Tokarz-Sobieraj Magorzata Witko |
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Institution: | 1.Faculty of Mathematics and Natural Sciences, Department of Chemistry, University of Applied Sciences in Tarnow, Mickiewicza 8, 33-100 Tarnow, Poland;2.Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krakow, Poland; |
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Abstract: | Density functional theory calculations were carried out to investigate the electronic structures of Keggin-typed XMo12O40]n− and XW12O40]n− anions with different heteroatoms (X = Zn2+, B3+, Al3+, Ga3+, Si4+, Ge4+, P5+, As5+, and S6+). The influence of solvent on redox properties of heteropolyanions was discussed. For XW12O40]n− systems two linear correlation: first, between the experimental redox potential and energies of LUMO orbital; and second, between the experimental redox potential and total energy interaction (calculated between internal tetrahedron (XO4n−), and rest of Kegging anion skeleton, (W12O36)) were designated. Taking into account the similarity of XW12O40n− and XMo12O40n− systems (in geometry and electronic structure), the estimated redox potential of molybdenum heteropolyanions (with X being p block elements) in different solvent were proposed. |
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Keywords: | heteropolyacids DFT calculations correlations analysis redox potential energy decomposition analysis (EDA) |
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