Structural, vibrational and thermodynamic properties of Ag(n)Cu(34-n) nanoparticles

We report results of a systematic study of structural, vibrational and thermodynamical properties of 34-atom bimetallic nanoparticles from the Ag(n)Cu(34-n) family using model interaction potentials as derived from the embedded atom method and invoking the harmonic approximation of lattice dynamics. Systematic trends in the bond length and dynamical properties can be explained largely from arguments based on local coordination and elemental environment. Thus an increase in the number of silver atoms in a given neighborhood introduces a monotonic increase in bond length, while an increase of the copper content does the reverse. Moreover, for the bond lengths of the lowest-coordinated (six and eight) copper atoms with their nearest neighbors (Cu atoms), we find that the nanoparticles divide into two groups with the average bond length either close to (∼2.58 Å) or smaller than (∼2.48 Å) that in bulk copper, accompanied by characteristic features in their vibrational density of states. For the entire set of nanoparticles, we find vibrational modes above the bulk bands of copper/silver. We trace a blue shift in the high-frequency end of the spectrum that occurs as the number of copper atoms increases in the nanoparticles, leading to shrinkage of the bond lengths from those in the bulk. The vibrational densities of states at the low-frequency end of the spectrum scale linearly with frequency as for single-element nanoparticles, with a more pronounced effect for these nanoalloys. The Debye temperature is found to be about one-third of that of the bulk for pure copper and silver nanoparticles, with a non-linear increase as copper atoms increase in the nanoalloy.