Computational studies of photophysical properties of porphin, tetraphenylporphyrin and tetrabenzoporphyrin

• Published in: Physical chemistry chemical physics : PCCP Vol. 14; no. 32; p. 11508
• Main Authors: Valiev, Rashid R, Cherepanov, Victor N, Artyukhov, Victor Ya, Sundholm, Dage
• Format: Journal Article
• Language: English
• Published: England 28-08-2012
• Subjects: Computer Simulation; Electrons; Fluorescence; Luminescent Measurements; Models, Molecular; Porphyrins - chemistry; Quantum Theory
• ISSN: 1463-9084
• DOI: 10.1039/c2cp40468k

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.