Influences of size, shape, and wall thickness on melting entropy and enthalpy of metallic nanostructures

Abstract

From the perspective of a bond-order-length-strength correlation, we put forward an analytical solution to describe the size, shape, and wall thickness dependency of melting temperature, entropy, and enthalpy for metallic nanostructures. Theoretical reproduction of measurements clarified that (i) when the crystal size reduces, the atomic coordination number lowers, the atomic cohesive energy decreases, and the surface-to-volume ratio increases; (ii) at the same equivalent radius, with the decrease in the number of sides for polyhedral nanoparticles and polygonal nanowires or nanotubes, the melting temperature, entropy, and enthalpy depress; and (iii) the melting temperature, entropy, and enthalpy of nanotubes are always lower than those of nanowires with the same cross-sectional radius. The present formulation is accurate and convenient, which not only shows deeper insight into the physical origins of a melting thermodynamic property response to perturbations but also provides guidance for the design and optimization of electronic nanodevices.