Density functional theory studies of inorganic metallocene multidecker V(n)(P(6))(n+1) (n=1-4) sandwich clusters

Motivated by the synthesis of the first entirely inorganic metallocene sandwich ion eta(5)-Ti-(P(5))(2)](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.