Kotrle Kamil, Atanasov Mihail, Neese Frank, Herchel Radovan
Department of Inorganic Chemistry, Faculty of Science, Palacký University Olomouc, Olomouc CZ-77146, Czech Republic.
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr D-45470, Germany.
Inorg Chem. 2023 Oct 23;62(42):17499-17509. doi: 10.1021/acs.inorgchem.3c02916. Epub 2023 Oct 9.
A detailed computational study of hypothetical sandwich dysprosium double-decker complexes, bridged by various numbers of aliphatic linkers, was performed to evaluate the effect of the structural modifications on their ground-state magnetic sublevels and assess their potential as candidates for single-molecule magnets (SMMs). The molecular structures of seven complexes were optimized using the TPSSh functional, and the electronic structure and magnetic properties were investigated using the complete active space self-consistent field method (CASSCF). Estimates of the magnetic moment blocking barrier () and blocking temperatures () are reported. In addition, a new method based on computed derivatives of effective demagnetization barriers with respect to vibrational normal modes was introduced and applied to evaluate the impact of spin-phonon coupling on the SMM properties. On the basis of the computed parameters, we have identified promising candidates with properties superior to those of the existing single-molecule magnets.
对由不同数量脂肪族连接体桥联的假设夹心钬双层配合物进行了详细的计算研究，以评估结构修饰对其基态磁子能级的影响，并评估它们作为单分子磁体（SMM）候选物的潜力。使用TPSSh泛函优化了七种配合物的分子结构，并使用完全活性空间自洽场方法（CASSCF）研究了电子结构和磁性。报告了磁矩阻挡势垒（）和阻挡温度（）的估计值。此外，引入了一种基于有效退磁势垒相对于振动简正模式的计算导数的新方法，并将其应用于评估自旋 - 声子耦合对SMM性质 的影响。基于计算出的参数，我们确定了具有优于现有单分子磁体性质的有前景的候选物。
