Optical excitations in stoichiometric uncapped ZnS nanostructures

Abstract

We calculate the optical absorption spectra of low-energy uncapped zinc sulfide nanostructures found by global optimisation (basin-hopping/simulated annealing) using time–dependent density functional theory (TD-DFT) and compare the results with experimental spectra. We predict that for all nanostructures studied the lowest excited state found by TD-DFT corresponds to an exciton with an exciton binding energy that is much larger than that of excitons in bulk zinc sulfide. We further show that for the more symmetrical nanostructures some of the excitons are dark and that the absorption on-sets, the energy of the lowest exciton, for the different nanostructures show no clear evidence of quantum confinement. We propose that this apparent lack of quantum confinement finds its origin in the fact that the lowest exciton is not evenly spread over the whole nanostructure but shows large contributions for specific groups of atoms. Finally, we show that the predicted optical absorption spectra fit with those reported experimentally.