DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Mannix P. Balanay, Dong Hee Kim

Research output: Contribution to journalArticlepeer-review

117 Citations (Scopus)


Density functional theory (DFT) and time-dependent DFT calculations have been employed to model Zn meso-tetraphenylporphyrin (ZnTPP) complexes having different β-substituents, in order to design an efficient sensitizer for dye-sensitized solar cells. To calculate the excited states of the porphyrin analogues, at least the TD-B3LYP/6-31G* level of theory is needed to replicate the experimental absorption spectra. Solvation results were found to be invariant with respect to the type of model used (PCM vs. C-PCM). Most of the electronic transitions based on Gouterman's four-orbital model of ZnTPP-A and ZnTPP-B are π → π* transitions, so that cell efficiency can be enhanced by increasing the π-conjugation and electron-withdrawing capability of the β-substituent. This proposition was tested by inserting thiophene into the β-substituent of ZnTPP-A to form a new analogue, ZnTPP-C. Compared with ZnTPP-A and ZnTPP-B, ZnTPP-C has a smaller band gap, which brings LUMO closer to the conduction band of TiO2, and a red-shifted absorption spectrum with higher extinction coefficients, especially in the Q-band position.

Original languageEnglish
Pages (from-to)5121-5127
Number of pages7
JournalPhysical Chemistry Chemical Physics
Issue number33
Publication statusPublished - 2008
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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