Theoretical investigation of fluorescence properties of EDTA and DTPA substituted tetraphenylporphyrin molecules

The matrix elements of spin–orbit coupling operator (HSO) and non-adiabatic coupling operator (Ω) for the H2ATPP–EDTA and H2ATPP–DTPA molecules were calculated using INDO method. Rate constants of internal conversion and of intersystem crossing were calculated using the values of matrix elements of HSO and Ω operators and excitation energies both calculated with the ADC(2) and TDDFT methods and obtained from experimental data. Results of calculations show that the probability of radiationless deactivation in internal conversion channel is greater than the probability of radiationless transition in intersystem crossing channel for considered molecules. Obtained theoretical values of fluorescence quantum yield have good agreement with their experimental values.

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► The rate constants of photophysical processes were obtained for considered objects.
► The rate constant of internal conversion is greater than the other rate ones.
► The matrix elements of spin–orbit coupling operator were obtained using INDO.
► The matrix elements of non-adiabatic coupling operator were obtained using INDO.