title: Combined DFT and BS study on the exchange coupling of dinuclear sandwich-type POM: comparison of different functionals and reliability of structure modeling.
abstract: The exchange coupling of a group of three dinuclear sandwich-type polyoxomolybdates [MM'(AsMo7O27)2](12-) with MM' = CrCr, FeFe, FeCr are theoretically predicted from combined DFT and broken-symmetry (BS) approach. Eight different XC functionals are utilized to calculate the exchange-coupling constant J from both the full crystalline structures and model structures of smaller size. The comparison between theoretical values and accurate experimental results supports the applicability of DFT-BS method in this new type of sandwich-type dinuclear polyoxomolybdates. However, a careful choice of functionals is necessary to achieve the desired accuracy. The encouraging results obtained from calculations on model structures highlight the great potential of application of structure modeling in theoretical study of POM. Structural modeling may not only reduce the computational cost of large POM species but also be able to take into account the external field effect arising from solvent molecules in solution or counterions in crystal.
authors: Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, People’s Republic of China. rayinyin@gmail.com
authors: Bing
authors: B
authors: Yin
authors: GangLin
authors: G
authors: Xue
authors: JianLi
authors: J
authors: Li
authors: Lu
authors: L
authors: Bai
authors: YuanHe
authors: Y
authors: Huang
authors: ZhenYi
authors: Z
authors: Wen
authors: ZhenYi
authors: Z
authors: Jiang
mesh_terms: D001149:Arsenates / Q000737:chemistry*; D001151:Arsenic / Q000737:chemistry; D002857:Chromium / Q000737:chemistry; D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D003460:Crystallization; D007501:Iron / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents; D013816:Thermodynamics
chemical_list: D001149:Arsenates; D056831:Coordination Complexes; D012997:Solvents; D002857:Chromium; D008982:Molybdenum; D007501:Iron; D001151:Arsenic