Wang Jinlan, Zhang Xiuyun, von Ragué Schleyer Paul, Chen Zhongfang
Department of Physics, Southeast University, Nanjing, PR China.
J Chem Phys. 2008 Mar 14;128(10):104706. doi: 10.1063/1.2883971.
Motivated by the synthesis of the first entirely inorganic metallocene sandwich ion eta(5)-Ti-(P(5))(2) [E. Urnezius et al. Science 295, 832 (2002)], we have designed a new inorganic metallocene sandwich [eta(6)-V-(P(6))(2)] and multidecker sandwich clusters up to V(4)(P(6))(5) by employing an all electron gradient-corrected density functional theory. The binding energies of the V(n)(P(6))(n+1) complexes increase rapidly from half sandwich to the smallest full sandwich and become gradually afterwards. The highest occupied and lowest unoccupied molecular orbital gap and the vertical ionization energy decrease with increasing cluster size. The V(n)(P(6))(n+1) clusters are nonferromagnetic and prefer the lowest available spin states. The smallest sandwich cluster, V(P(6))(2), has the high stability and might serve as a building block for one-dimensional inorganic polymers with high stabilities.
受首个完全无机金属茂夹心离子η(5)-Ti-(P(5))(2)合成的启发[E. 乌尔内齐乌斯等人，《科学》295, 832 (2002)]，我们通过采用全电子梯度校正密度泛函理论设计了一种新的无机金属茂夹心[η(6)-V-(P(6))(2)]以及多达V(4)(P(6))(5)的多夹心簇。V(n)(P(6))(n + 1)配合物的结合能从半夹心迅速增加到最小的全夹心，随后逐渐增大。最高占据分子轨道和最低未占据分子轨道的能隙以及垂直电离能随簇尺寸的增加而减小。V(n)(P(6))(n + 1)簇是非铁磁性的，且倾向于最低可用自旋态。最小的夹心簇V(P(6))(2)具有高稳定性，可能作为具有高稳定性的一维无机聚合物的构建单元。
