High-energy excitations in silicon nanoparticles.

We have investigated high energy excitations in approximately 1-2 nm Si nanoparticles (NPs) by ab initio time-dependent density functional calculations, focusing on the influence on excitation spectra, of surface reconstruction, surface passivation by alkyl groups, and the interaction between NPs. We have found that surface reconstruction may change excitation spectra dramatically at both low and high energies above the gap; absorption may be enhanced nonlinearly by the presence of alkyl groups, compared to that of unreconstructed, hydrogenated Si NPs, and by the interaction between NPs. Our findings can help interpret the recent experiments on multielectron generation in colloidal semiconductor NPs as well as help optimize photovoltaic applications of NPs.