Department of Physics, Southeast University, Nanjing 211189, People's Republic of China.
J Phys Chem A. 2010 Feb 18;114(6):2319-23. doi: 10.1021/jp907834v.
Ab initio spin-polarized density functional calculations have been performed on mixed-sandwich clusters V(n)Bz(m)Cp(k) (n = 1-3, m + k = n + 1, Bz = benzene, Cp = cyclopentadienyl) to study their size-dependent and composition-dependent structural, electronic, and magnetic properties. All of the mixed-sandwich clusters are thermodynamically stable with larger binding energies than those of V(n)Bz(n+1). Furthermore, the binding energies of V(n)Bz(m)Cp(k) show clear dependence on the number of Cp rings as well as on the relative positions of Cp (or Bz) rings inside of the molecules. More interestingly, the replacement of a Bz with a Cp ring in V(n)Bz(n+1) brings one net spin into the cluster, which is attributed to the transfer of one minority ddelta electron from the V atom to its adjacent Cp ligand. In addition, the ferromagnetism stability of V(n)Bz(n+1) is significantly enhanced upon Cp replacement.
运用从头算自旋极化密度泛函理论，对 V(n)Bz(m)Cp(k)（n=1-3，m+k=n+1，Bz=苯，Cp=环戊二烯基）混合夹心簇进行了计算，以研究其尺寸和组成依赖性的结构、电子和磁性质。所有的混合夹心簇都是热力学稳定的，其结合能大于 V(n)Bz(n+1)。此外，V(n)Bz(m)Cp(k)的结合能明显取决于 Cp 环的数量以及分子内 Cp（或 Bz）环的相对位置。更有趣的是，用 Cp 环取代 V(n)Bz(n+1)中的一个 Bz 环会向簇中引入一个净自旋，这归因于一个 minority ddelta 电子从 V 原子转移到其相邻的 Cp 配体。此外，Cp 取代后 V(n)Bz(n+1)的铁磁性稳定性显著增强。
