Computational studies of photophysical properties of porphin, tetraphenylporphyrin and tetrabenzoporphyrin

Rashid R. Valiev, Victor N. Cherepanov, Victor Ya Artyukhov, Dage Sundholm

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The molecular photonics of porphyrins are studied using a combination of first-principle and semi-empirical calculations. The applicability of the approach is demonstrated by calculations on free-base porphyrin, tetraphenylporphyrin, and tetrabenzoporphyrin. The method uses excitation energies and oscillator strengths calculated at the linear-response time-dependent density functional theory (TDDFT) or the corresponding values calculated at the linear-response approximate second-order coupled-cluster (CC2) levels. The lowest singlet excitation energies obtained in the TDDFT and CC2 calculations are 0.0-0.28 eV and 0.18-0.47 eV larger than the experimental values, respectively. The excitation energies for the first triplet state calculated at the TDDFT level are in excellent agreement with experiment, whereas the corresponding CC2 values have larger deviations from experiment of 0.420.66 eV. The matrix elements of the spin-orbit and non-adiabatic coupling operators have been calculated at the semi-empirical intermediate neglect of differential overlap (INDO) level using a spectroscopic parameterization. The calculations yield rate constants for internal conversion and intersystem crossing processes as well as quantum yields for fluorescence and phosphorescence. The main mechanism for the quenching of fluorescence in tetraphenylporphyrin and tetrabenzoporphyrin is the internal conversion, whereas for free-base porphyrin both the internal conversion and the intersystem crossing processes reduce the fluorescence intensity. The phosphorescence is quenched by a fast internal conversion from the triplet to the ground state.

Original languageEnglish
Pages (from-to)11508-11517
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number32
DOIs
Publication statusPublished - 28 Aug 2012

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internal conversion
Excitation energy
Porphyrins
porphyrins
Density functional theory
Phosphorescence
Fluorescence
phosphorescence
density functional theory
fluorescence
excitation
Quantum yield
Parameterization
parameterization
oscillator strengths
Photonics
Ground state
atomic energy levels
energy
Quenching

ASJC Scopus subject areas

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

Cite this

Computational studies of photophysical properties of porphin, tetraphenylporphyrin and tetrabenzoporphyrin. / Valiev, Rashid R.; Cherepanov, Victor N.; Artyukhov, Victor Ya; Sundholm, Dage.

In: Physical Chemistry Chemical Physics, Vol. 14, No. 32, 28.08.2012, p. 11508-11517.

Research output: Contribution to journalArticle

Valiev, Rashid R. ; Cherepanov, Victor N. ; Artyukhov, Victor Ya ; Sundholm, Dage. / Computational studies of photophysical properties of porphin, tetraphenylporphyrin and tetrabenzoporphyrin. In: Physical Chemistry Chemical Physics. 2012 ; Vol. 14, No. 32. pp. 11508-11517.
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