### 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 language | English |
---|---|

Pages (from-to) | 11508-11517 |

Number of pages | 10 |

Journal | Physical Chemistry Chemical Physics |

Volume | 14 |

Issue number | 32 |

DOIs | |

Publication status | Published - 28 Aug 2012 |

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### ASJC Scopus subject areas

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

### Cite this

*Physical Chemistry Chemical Physics*,

*14*(32), 11508-11517. https://doi.org/10.1039/c2cp40468k

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

Research output: Contribution to journal › Article

*Physical Chemistry Chemical Physics*, vol. 14, no. 32, pp. 11508-11517. https://doi.org/10.1039/c2cp40468k

}

TY - JOUR

T1 - Computational studies of photophysical properties of porphin, tetraphenylporphyrin and tetrabenzoporphyrin

AU - Valiev, Rashid R.

AU - Cherepanov, Victor N.

AU - Artyukhov, Victor Ya

AU - Sundholm, Dage

PY - 2012/8/28

Y1 - 2012/8/28

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84864209248&partnerID=8YFLogxK

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U2 - 10.1039/c2cp40468k

DO - 10.1039/c2cp40468k

M3 - Article

C2 - 22805735

AN - SCOPUS:84864209248

VL - 14

SP - 11508

EP - 11517

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 32

ER -