First-principles investigation of finite-temperature behavior in small sodium clusters

Abstract

A systematic and detailed investigation of the finite-temperature behavior of small sodium clusters, Na_n, in the size range of n=8-50 are carried out. The simulations are performed using density-functional molecular dynamics with ultrasoft pseudopotentials. A number of thermodynamic indicators such as specific heat, caloric curve, root-mean-square bond-length fluctuation, deviation energy, etc., are calculated for each of the clusters. Size dependence of these indicators reveals several interesting features. The smallest clusters with n = 8 and 10 do not show any signature of melting transition. With the increase in size, broad peak in the specific heat is developed, which alternately for larger clusters evolves into a sharper one, indicating a solidlike to liquidlike transition. The melting temperatures show an irregular pattern similar to the experimentally observed one for larger clusters [ Schmidt et al., Nature (London) 393, 238 (1998) ]. The present calculations also reveal a remarkable size-sensitive effect in the size range of n=40-55. While Na₄₀ and Na₅₅ show well-developed peaks in the specific-heat curve, Na₅₀ cluster exhibits a rather broad peak, indicating a poorly defined melting transition. Such a feature has been experimentally observed for gallium and aluminum clusters [ Breaux et al., J. Am. Chem. Soc. 126, 8628 (2004) ; Breaux et al., Phys. Rev. Lett. 94, 173401 (2005) ].