Structures and excitation energies of Zn-tetraarylporphyrin analogues: A theoretical study

Mannix P. Balanay, Dong Hee Kim

Research output: Contribution to journalArticlepeer-review

70 Citations (Scopus)

Abstract

The photophysical properties of β-substituted Zn-tetraarylporphyrin (ZnTAP) analogues used as dyes in dye-sensitized solar cells were studied using density functional theory (DFT). Singlet-excitation energy calculations of ZnTAP analogues were performed using time-dependent DFT with B3LYP, B3PW91, PBE0 exchange-correlation functionals at 6-31G(d) and 6-31+G(d) basis sets using B3LYP/6-31G(d) geometries. The PBE0 functional at 6-31+G(d) basis set provided a better correlation with the experimental data for both B- and Q-bands. The inclusion of solvation effect in the calculations provided a good agreement in terms of B:Qave ratio of the oscillator strengths for both analogues with the experimental values. Analogue 2 has a higher and a more balanced charge-carrier transport rates than analogue 1. In general, the addition of an electron-donating group in the meso-substituent (analogue 2) resulted in a narrower band gap, higher oscillator strength, a more red-shifted absorption spectra, and better charge-transfer characteristics than analogue 1.

Original languageEnglish
Pages (from-to)20-26
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Volume910
Issue number1-3
DOIs
Publication statusPublished - Sep 30 2009
Externally publishedYes

Keywords

  • DSSC
  • Electronic structure
  • Reorganization energy
  • TD-DFT
  • Zn-Porphyrin

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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