Vibrational Study of Iodide-Based Room-Temperature Ionic-Liquid Effects on Candidate N719-Chromophore/Titania Interfaces for Dye-Sensitised Solar-Cell Applications from Ab-Initio Based Molecular-Dynamics Simulation

The accurate ab-initio modelling of prototypical and well-representative photo-active interfaces for candidate dye-sensitised solar cells is a challenging problem. To this end, using ab-initio molecular-dynamics (AIMD) simulation based on Density Functional Theory (DFT), the effects of explicit solvation by iodide-based, I−[bmim]+ room-temperature ionic liquids (RTILs) have been assessed on modelling a N719-chromophore sensitising dye adsorbed onto an anatase-titania (101) surface. In particular, the vibrational spectra for this model photo-active interface were calculated by means of Fourier transformed mass-weighted velocity autocorrelation functions. These were compared with experiment and against each other to gain an understanding of how using iodine-based RTILs as the electrolytic hole acceptor alters the dynamical properties of the widely-used N719 dye. The effect of Perdew-Burke-Ernzerhof (PBE) and Becke-Lee-Yang-Parr (BLYP) functionals on the vibrational spectra were assessed. PBE generally performed best in producing spectra which matched the typically expected experimental frequency modes