A TD-DFT study of the effects of structural variations on the photochemistry of polyene dyes

We report a TD-DFT study of three polyene dyes namely: NKX-2553, NKX-2554 and NKX-2569 in isolation as well as upon their adsorption on TiO2 nanoparticles. By choosing closely related dyes we wish to focus on the effects of structural variations on the absorption and charge-transfer properties of these systems. These three dyes show a non-intuitive trend in their respective
efficiencies and therefore, were chosen to shed light on the structural components that contribute to this behaviour. Although,
NKX-2554 has an additional donor group, it is less efficient compared to the simpler NKX-2553 dye that contains only one donor group. When NKX-2554 structure is slightly modified by lengthening the linker-group, one obtains the most efficient dye among this set, namely, NKX-2569. In this work, we show that the changes in the donor moiety has very little or no effect on the efficiency of these dyes as can be seen in the case of NKX-2553 and NKX-2554. On the other hand, the improved performance of NKX-2569-titania complex can be understood to be a result of the longer linker group. A better understanding of these properties within different dye-titania complexes is important for the continual improvement of DSSCs. In this regards, this study will serve to provide guidelines to improve efficiencies of novel organic dyes.