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Issue 2, 2012
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Computational modelling of TiO2 surfaces sensitized by organic dyes with different anchoring groups: adsorption modes, electronic structure and implication for electron injection/recombination

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Abstract

We present a Density Functional Theory investigation aimed to model the possible adsorption modes to the TiO2 surface of two representative TPA-based dyes, termed L0 and rh-L0, having the two mostly employed anchoring groups, namely the cyanoacrylic and rhodanine-3-acetic acids respectively. The bidentate coordination with proton transfer to a nearby surface oxygen is found to be the energetically favored anchoring mode for both dyes. The calculations show that the different dye anchoring groups give rise to a very different electronic coupling between the dye and the manifold of unoccupied semiconductor states, thus implying different electron injection mechanisms. The strongly coupled L0 dye possibly shows an adiabatic electron injection mechanism, while a non-adiabatic electron injection can be foreseen for the weakly coupled rh-L0 dye. The different orientation with respect to the TiO2 surface for the two classes of dyes, implying different distances of the donor group from the oxide surface, together with the different electron injection mechanisms might account for the faster recombination reaction measured for the rhodanine-based dyes.

Graphical abstract: Computational modelling of TiO2 surfaces sensitized by organic dyes with different anchoring groups: adsorption modes, electronic structure and implication for electron injection/recombination

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Publication details

The article was received on 19 Aug 2011, accepted on 03 Nov 2011 and first published on 25 Nov 2011


Article type: Paper
DOI: 10.1039/C1CP22663K
Citation: Phys. Chem. Chem. Phys., 2012,14, 920-928
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    Computational modelling of TiO2 surfaces sensitized by organic dyes with different anchoring groups: adsorption modes, electronic structure and implication for electron injection/recombination

    M. Pastore and F. De Angelis, Phys. Chem. Chem. Phys., 2012, 14, 920
    DOI: 10.1039/C1CP22663K

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