TY - JOUR
T1 - Time-dependent density functional theory investigations on the excited states of Ru(II)-dye-sensitized TiO2 nanoparticles
T2 - The role of sensitizer protonation
AU - De Angelis, Filippo
AU - Fantacci, Simona
AU - Selloni, Annabella
AU - Nazeeruddin, Mohammad K.
AU - Grätzel, Michael
PY - 2007/11/21
Y1 - 2007/11/21
N2 - We performed fully first principles quantum mechanical calculations of the ground- and excited-state properties of the [cis-(NCS)2-Ru(II)-bis(2,2′-bipyridine-4,4′-dicarboxylate)] dye, N719, adsorbed onto a model TiO2 nanoparticle. Our study confirms an indirect electron injection mechanism for Ru(II) dyes on TiO2 and indicates a remarkable effect of dye protonation on the electronic properties of N719-sensitized TiO2 nanoparticles. We find that two different electron injection mechanisms (adiabatic and nonadiabatic) may be present in DSSCs employing dyes carrying a different number of protons. Despite such differences, the absorption spectra corresponding to strongly and weakly coupled dye/TiO2 excited states are remarkably similar, so that a discrimination of the two electron injection regimes does not appear to be feasible based on inspection of the absorption spectra.
AB - We performed fully first principles quantum mechanical calculations of the ground- and excited-state properties of the [cis-(NCS)2-Ru(II)-bis(2,2′-bipyridine-4,4′-dicarboxylate)] dye, N719, adsorbed onto a model TiO2 nanoparticle. Our study confirms an indirect electron injection mechanism for Ru(II) dyes on TiO2 and indicates a remarkable effect of dye protonation on the electronic properties of N719-sensitized TiO2 nanoparticles. We find that two different electron injection mechanisms (adiabatic and nonadiabatic) may be present in DSSCs employing dyes carrying a different number of protons. Despite such differences, the absorption spectra corresponding to strongly and weakly coupled dye/TiO2 excited states are remarkably similar, so that a discrimination of the two electron injection regimes does not appear to be feasible based on inspection of the absorption spectra.
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U2 - 10.1021/ja076293e
DO - 10.1021/ja076293e
M3 - Article
C2 - 17960934
AN - SCOPUS:36448983981
SN - 0002-7863
VL - 129
SP - 14156
EP - 14157
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 46
ER -