000184431 001__ 184431
000184431 005__ 20181203023016.0
000184431 0247_ $$2doi$$a10.1021/jp306186y
000184431 022__ $$a1932-7447
000184431 02470 $$2ISI$$a000308120000017
000184431 037__ $$aARTICLE
000184431 245__ $$aModeling Ruthenium-Dye-Sensitized TiO2 Surfaces Exposing the (001) or (101) Faces: A First-Principles Investigation
000184431 260__ $$bAmerican Chemical Society$$c2012$$aWashington
000184431 269__ $$a2012
000184431 300__ $$a8
000184431 336__ $$aJournal Articles
000184431 520__ $$aWe present a first-principles computational investigation on the adsorption mode and electronic structure of the highly efficient heteroleptic ruthenium dye C101, [NaRu(4,4'-bis(5-hexylthiophene-2-yl)-2,2'-bipyridine)(4-carboxylic acid-4'-carboxylate-2,2'-bipyridine) (NCS)(2)], on anatase TiO2 models exposing the (001) and (101) surfaces. The electronic structure of the TiO2 models shows a conduction band energy upshift for the (001)-surface ranging between similar to 50 and similar to 110 meV compared with the (101) surface, in agreement with previous interfacial impedance and recent spectro-electrochemical data. TDDFT excited-state calculations provided the same optical band gap, within 0.01 eV, for the (001)- and (101) models. Two dominant adsorption modes for C101 dye Adsorption on the (001) and (101) surfaces were found, which differ by the binding of the dye carboxylic groups to the TiO2 surfaces (bridged bidentate vs monodentate), leading to sizably different tilting of the anchoring bipyridine plane with respect to the TiO2 surface. The different adsorption mode leads to a smaller dye coverage on the (001) surface, as experimentally found, due to partial contact of the thiophene and alkyl bipyridine substituents with the TiO2 surface. For the energetically favored adsorption modes, we calculate a larger average spatial separation, by 1.3 angstrom, between the dye-based HOMO and the semiconductor surface in (001) and (101) TiO2 models. In terms of simple nonadiabatic electron-transfer considerations, our model predicts a retardation of the charge recombination kinetics, in agreement with the experimental observations.
000184431 700__ $$uIst CNR Sci & Tecnol Mol, Computat Lab Hybrid Organ Photovolta CLHYO, I-06123 Perugia, Italy$$aDe Angelis, Filippo
000184431 700__ $$uIst CNR Sci & Tecnol Mol, Computat Lab Hybrid Organ Photovolta CLHYO, I-06123 Perugia, Italy$$aVitillaro, Giuseppe
000184431 700__ $$0240197$$g114460$$uAcad Sci Czech Republic, J Heyrovsky Inst Phys Chem, Vvi, CZ-18223 Prague 8, Czech Republic$$aKavan, Ladislav
000184431 700__ $$0240422$$g105958$$aNazeeruddin, Mohammad K.
000184431 700__ $$aGraetzel, Michael$$g105292$$0240191
000184431 773__ $$j116$$tJournal Of Physical Chemistry C$$k34$$q18124-18131
000184431 909C0 $$xU10101$$0252060$$pLPI
000184431 909CO $$pSB$$particle$$ooai:infoscience.tind.io:184431
000184431 917Z8 $$x105528
000184431 937__ $$aEPFL-ARTICLE-184431
000184431 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000184431 980__ $$aARTICLE