Finite temperature behavior of impurity doped Lithium cluster {\em viz} Li$_6$Sn

Abstract

We have carried out extensive isokinetic {\it ab initio} molecular dynamic simulations to investigate the finite temperature properties of the impurity doped cluster Li$_6$Sn along with the host cluster Li$_7$. The data obtained from about 20 temperatures and total simulation time of at least 3 ns is used to extract thermodynamical quantities like canonical specific heat. We observe a substantial charge transfer from all Li atoms to Sn which inturn weakens the Li-Li bonds in Li$_6$Sn compared to the bonds in Li$_7$. This weakening of bonds changes the finite temperature behavior of Li$_6$Sn significantly. Firstly, Li$_6$Sn becomes liquid-like around 250 K, a much lower temperature than that of Li$_7$ ($\approx$~425 K). Secondly, an additional quasirotational motion of lithium atoms appears at lower temperatures giving rise to a shoulder around 50 K in the specific heat curve of Li$_6$Sn. The peak in the specific heat of Li$_7$ is very broad and the specific heat does not show any premelting features.Comment: 16 pages, 10 figures Submitted to J. Chem. Phy