First-principles computation of the vibrational entropy of ordered and disorderedPd3V

Abstract

Experimental as well as theoretical work indicates that the relative stability of the ordered and the disordered states of a compound may be significantly affected by their difference in vibrational entropy. The origin of this difference is usually attributed to the fact that disordering reduces the number of stiff bonds between different atomic species in favor of soft bonds between identical atomic species. The results of previous theoretical investigations, however, suggest that this simple mechanism is significantly modified as a result of local atomic relaxations. To gain further insight regarding the importance of relaxations, we employ first-principles calculations to investigate the magnitude of the vibrational entropy difference between the ordered and the disordered state of ${\mathrm{Pd}}_3\mathrm{V}.$ Our investigation reveals that bond stiffness changes due to relaxation entirely mask the large configurational dependence of vibrational entropy provided by bond stiffness differences. Our analysis also suggests a simple technique to estimate vibrational entropy based on the relationship between bond length and bond stiffness.