Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study

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Title: Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study
Authors: Byrne, Aaron
English, Niall J.
Schwingenschlögl, Udo
Coker, David F.
Permanent link: http://hdl.handle.net/10197/9744
Date: 14-Jan-2016
Online since: 2019-03-29T16:38:43Z
Abstract: Ab 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.
Funding Details: European Commission
European Commission Horizon 2020
European Commission - European Regional Development Fund
Type of material: Journal Article
Publisher: ACS
Journal: Journal of Physical Chemistry C
Volume: 120
Issue: 1
Start page: 21
End page: 30
Copyright (published version): 2015 ACS
Keywords: Dye-sensitized solar cellsPhoto-responsive dyesN719
DOI: 10.1021/acs.jpcc.5b08964
Language: en
Status of Item: Peer reviewed
Appears in Collections:Solar Energy Conversion (SEC) Cluster Research Collection
Physics Research Collection
CASL Research Collection
Chemical and Bioprocess Engineering Research Collection

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