Confinement effects on the vibrational properties of III-V and II-VI nanoclusters

We present a first-principles study of the confinement effects on the vibrational properties of thousand atoms (radii up to 16.2 Å) colloidal III-V and II-VI nanoclusters. We describe how the molecular-type vibrations, such as surface-optical, surface-acoustic, and coherent acoustic modes, coexist and interact with bulk-type vibrations, such as longitudinal and transverse acoustic and optical modes. We link vibrational properties to structural changes induced by the surface and highlight the qualitative difference between III-Vs and II-VIs. We describe the size dependence of the vibrations and find good agreement for Raman shifts and for the frequency of coherent acoustic modes with experiments.