MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China.
Phys Chem Chem Phys. 2012 Jan 21;14(3):1121-30. doi: 10.1039/c1cp22928a. Epub 2011 Dec 7.
The structures, relative stabilities, vertical detachment energies and magnetic coupling properties of a series of manganese-based dinuclear superhalogens and their isoelectronic analogues are explored via a combined density functional theory and broken symmetry study. Both the capabilities of various exchange-correlation functionals and basis set effects are investigated. The large magnitudes of the calculated exchange coupling constants indicate clearly the apparent molecular magnetism of these new types of superhalogen. Encouragingly, the high possibility of the coexistence of both high stability and strong magnetic coupling in these new polynuclear superhalogens is also confirmed. Besides these, the larger magnitudes of the calculated coupling constants of iron-based clusters here, compared with the homodinuclear Mn(2)Cl(5) cluster, demonstrate the possibility of the existence of strong magnetic coupling in potential iron-based homo- and heterodinuclear superhalogens. The analysis of spin density distribution is also performed in order to understand the coupling mechanisms.
通过密度泛函理论和非对称研究，探索了一系列锰基双核超卤化物及其等电子类似物的结构、相对稳定性、垂直离解能和磁耦合性质。研究了各种交换相关泛函和基组效应的能力。计算得到的交换耦合常数的大数值清楚地表明了这些新型超卤化物的明显分子磁性。令人鼓舞的是，这些新型多核超卤化物中同时存在高稳定性和强磁耦合的可能性也得到了证实。此外，与同核Mn(2)Cl(5)簇相比，这里计算得到的铁基簇的耦合常数的较大数值表明，潜在的铁基同核和异核超卤化物中可能存在强磁耦合。还进行了自旋密度分布分析，以理解耦合机制。
