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Calculated Structural and Electronic Interactions of a Titanium Dioxide Nanocrystal Sensitized with the Ruthenium Dye N3

Persson, Petter LU and Lundqvist, M. J. (2005) In The Journal of Physical Chemistry Part B 109(24). p.11918-11924
Abstract
Structural and electronic properties of a small anatase TiO2 nanocrystal sensitized by the ruthenium dye N3 (Ru(4,4‘-dicarboxy-2,2‘-bipyridine)2(NCS)2) have been investigated using density functional theory (DFT) with support from Hartree−Fock (HF) and time dependent DFT (TD-DFT) calculations. Significant structural adjustments of both the dye and the nanocrystal are predicted to be induced by the strain imposed by the simultaneous formation of multiple dye−surface bonds. Electronic properties of the combined dye−nanocrystal system have also been calculated, including information about interfacial orbital mixing and the lowest excited singlet states. Ultrafast photoinduced electron transfer processes across the dye−nanoparticle interface... (More)
Structural and electronic properties of a small anatase TiO2 nanocrystal sensitized by the ruthenium dye N3 (Ru(4,4‘-dicarboxy-2,2‘-bipyridine)2(NCS)2) have been investigated using density functional theory (DFT) with support from Hartree−Fock (HF) and time dependent DFT (TD-DFT) calculations. Significant structural adjustments of both the dye and the nanocrystal are predicted to be induced by the strain imposed by the simultaneous formation of multiple dye−surface bonds. Electronic properties of the combined dye−nanocrystal system have also been calculated, including information about interfacial orbital mixing and the lowest excited singlet states. Ultrafast photoinduced electron transfer processes across the dye−nanoparticle interface in dye-sensitized solar cells are finally discussed in view of estimated electronic coupling strengths. The calculations predict injection times on the order of 10 fs for MLCT excitations to the ligand π* levels that interact most strongly with the TiO2 conduction band, and an order of magnitude increase in the injection times for excitations to dye levels with poor spatial or energetic overlaps with the substrate conduction band. (Less)
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author
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
109
issue
24
pages
11918 - 11924
publisher
The American Chemical Society
external identifiers
  • scopus:22544458191
ISSN
1520-5207
DOI
10.1021/jp050513y
language
English
LU publication?
no
id
6a5cdb22-c0e2-4447-9749-b587964d09c8 (old id 1457760)
date added to LUP
2009-08-25 17:46:23
date last changed
2017-09-03 04:33:40
@article{6a5cdb22-c0e2-4447-9749-b587964d09c8,
  abstract     = {Structural and electronic properties of a small anatase TiO2 nanocrystal sensitized by the ruthenium dye N3 (Ru(4,4‘-dicarboxy-2,2‘-bipyridine)2(NCS)2) have been investigated using density functional theory (DFT) with support from Hartree−Fock (HF) and time dependent DFT (TD-DFT) calculations. Significant structural adjustments of both the dye and the nanocrystal are predicted to be induced by the strain imposed by the simultaneous formation of multiple dye−surface bonds. Electronic properties of the combined dye−nanocrystal system have also been calculated, including information about interfacial orbital mixing and the lowest excited singlet states. Ultrafast photoinduced electron transfer processes across the dye−nanoparticle interface in dye-sensitized solar cells are finally discussed in view of estimated electronic coupling strengths. The calculations predict injection times on the order of 10 fs for MLCT excitations to the ligand π* levels that interact most strongly with the TiO2 conduction band, and an order of magnitude increase in the injection times for excitations to dye levels with poor spatial or energetic overlaps with the substrate conduction band.},
  author       = {Persson, Petter and Lundqvist, M. J.},
  issn         = {1520-5207},
  language     = {eng},
  number       = {24},
  pages        = {11918--11924},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Calculated Structural and Electronic Interactions of a Titanium Dioxide Nanocrystal Sensitized with the Ruthenium Dye N3},
  url          = {http://dx.doi.org/10.1021/jp050513y},
  volume       = {109},
  year         = {2005},
}