Photoabsorbance of supported metal clusters: ab initio density matrix and model studies of large Ag clusters on Si surfaces

Abstract

Metal clusters with 10 to 100 atoms supported by a solid surface show electronic structure typical of molecules and require ab initio treatments starting from their atomic structure, and they also can display collective electronic phenomena similar to plasmons in metal solids. We have employed ab initio electronic structure results from two different density functionals (PBE and the hybrid HSE06) and a reduced density matrix treatment of the dissipative photodynamics to calculate light absorbance by the large Ag clusters Ag_N, N = 33, 37(open shell) and N = 32, 34 (closed shell), adsorbed at the Si(111) surface of a slab, and forming nanostructured surfaces. Results on light absorption are quite different for the two functionals, and are presented here for light absorbances using orbitals and energies from the hybrid functional giving correct energy band gaps. Absorption of Ag clusters on Si increases light absorbance versus photon energy by large percentages, with peak increases found in regions of photon energies corresponding to localized plasmons. The present metal clusters are large enough to allow for modelling with continuum dielectric treatments of their medium. A mesoscopic Drude–Lorentz model is presented in a version suitable for the present structures, and provides an interpretation of our results. The calculated range of plasmon energies overlaps with the range of solar photon energies, making the present structures and properties relevant to applications to solar photoabsorption and photocatalysis.