Byrne, AaronAaronByrneEnglish, Niall J.Niall J.EnglishSchwingenschlögl, UdoUdoSchwingenschlöglCoker, David F.David F.Coker2019-03-292019-03-292015 ACS2016-01-14Journal of Physical Chemistry C1932-7447http://hdl.handle.net/10197/9744Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL), solvating a N719 sensitizing dye adsorbed onto an anatase titania (101) surface. The effect of explicit dispersion on the properties of this dye-sensitized solar cell (DSC) interface has also been studied. Upon inclusion of dispersion interactions in simulations of the solvated system, the average separation between the cations and anions decreases by 0.6 Å; the mean distance between the cations and the surface decreases by about 0.5 Å; and the layering of the RTIL is significantly altered in the first layer surrounding the dye, with the cation being on average 1.5 Å further from the center of the dye. Inclusion of dispersion effects when a solvent is not explicitly included (to dampen longer-range interactions) can result in unphysical "kinking" of the adsorbed dye's configuration. The inclusion of solvent shifts the HOMO and LUMO levels of the titania surface by +3 eV. At this interface, the interplay between the effects of dispersion and solvation combines in ways that are often subtle, such as enhancement or inhibition of specific vibrational modes.enThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © 2015 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b08964Dye-sensitized solar cellsPhoto-responsive dyesN719Journal Article1201213010.1021/acs.jpcc.5b089642019-03-28643998: MSCA-RISE-2014https://creativecommons.org/licenses/by-nc-nd/3.0/ie/