TY - JOUR AU - Daul, Claude AU - Rauzy, Cédrick AU - Decurtins, Silvio AU - Franz, Patrick AU - Hauser, Andreas TI - DFT study of mixed-valent Mn(II/III) hexacyanide cluster PY - 2005 JF - International Journal of Quantum Chemistry JA - Intl. J. Quantum Chem. SN - 0020-7608 VL - 101 IS - 6 SP - 753 EP - 760 L1 - http://www3.interscience.wiley.com/cgi-bin/fulltext/109746160/PDFSTART L2 - http://www3.interscience.wiley.com/cgi-bin/fulltext/109746160/HTMLSTART L3 - http://www3.interscience.wiley.com/cgi-bin/abstract/109746160/ABSTRACT L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref00637.png M3 - 10.1002/qua.20333 UR - http://dx.doi.org/10.1002/qua.20333 KW - cluster KW - cyanide bridging ligand KW - DFT KW - manganese complexes KW - Prussian blue analogue N2 - The cubic Prussian blue analogue Mn3[Mn(CN)6]2 · 15 H2O, which has the advantage of being transparent and magnetic (TN = 35 K) at the same time, has been investigated by density functional theory (DFT) calculations. The three-dimensional structure is built of MnII ions linked to MnIII ions by μ-bridging cyanides, to form a crystal structure, which is related to the NaCl type. In a first step, the relative stabilities of the mononuclear complexes [Mn(CN)6]z- (z = 2 to 4) have been studied as a function of the oxidation state, spin configuration, and the linkage isomerism of the cyanide ligand. The results we have obtained by this investigation are in good agreement with our chemical expertise. In addition, the calculations have been extended to the dinuclear [Mn2(CN)11]z- (z = 5 and 6) clusters. Furthermore, we used DFT to model the magnetic properties as well as the 3T1 → 1T2 transition, which has been observed by single-crystal near-IR spectra of Mn3[Mn(CN)6]2 · 15 H2O. ID - 637 ER -