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A simplified form of the Bixon–Jortner–Plotnikov (BJP) method is derived for calculation of internal conversion (IC) rate in a symmetrical molecule. The rate is a sum of contributions from individual transitions between vibronic states. For each transition, vibrational modes are divided into two groups, the promoting (one or two modes per electronic transition) and the surrounding ones. In the case of the non-totally symmetric transition in a symmetric molecule, the overwhelming majority of transitions do not contribute to the overall rate. Moreover, the promoting and surrounding modes belong to different symmetry representations and can be separated. It is proposed to deal with the promoting modes directly, while approximating the effect of the surrounding modes by a Pekarian function. The method was tested on polyacenes and it was shown that the calculated IC rates are in agreement with the experimental ones. The simplified method can be applied for calculating the rates of non-totally symmetric transition in a symmetric molecule, if its point symmetry group does not change after transition.

A simplified Bixon–Jortner–Plotnikov method for fast calculation of radiationless transfer rates in symmetric molecules