The linear photochemical response of materials depends on two critical parameters: the size of the optical band gap determines the onset of optical excitation, whereas the absolute energetic positions of the band edges define the reductive or oxidative character of photo-generated electrons and holes. Tuning these characteristics is necessary for many potential applications and can be achieved through changes in the bulk composition or particle size, adjustment of the surface chemistry or the application of electrostatic fields. In this contribution the influence of surface chemistry and fields is investigated systematically with the help of standard DFT calculations for a typical case, namely composites prepared from ZnS quantum dots and functionalized carbon nanotubes. After comparing results with existing qualitative and quantitative experimental data, it is shown conclusively, that the details of the surface chemistry (especially defects) in combination with electrostatic fields have the largest influence. In conclusion, the development of novel or improved photoresponsive materials therefore will have to integrate a careful analysis of the interplay between surface chemistry, surface charges and interaction with the material environment or substrate.
Keywords: DFT; band edge; nanocomposite; optical band gap; quantum dot.