The fluorescence quantum yield for fluorescent organic molecules is an important molecular property, and tuning it up is desired for various applications. For the computational estimation of the fluorescence quantum yield, the theoretical prediction of the nonradiative decay rate constant has become an attractive subject of study. The rate constant of thermally activated nonradiative decay is related to the activation energy in the photoreaction; thus, the accuracy and reliability of the excited-state potential energies in the quantum chemical computation are critical. In this study, we employed a second-order multireference perturbation wave-function theory for studying the thermally activated decay via conical intersection (CI) of 1,1-dimethyldibenzo[b,f]silepin derivatives. The correlation between the computed activation energy to reach the CI geometry in the S-1 state and the experimentally determined fluorescence quantum yield implied that silepins nonradiatively decay via the CI triggered by the twisting of the central C-C bond. Geometry optimization of the transition state using multireference perturbation theory drastically reduced the estimated activation energy. Our computation gave reasonable predictions of the activation free energies of photoexcited 1,1-dimethyldibenzo[b,f]silepin. The energy profiles and geometry optimizations using proper quantum chemical methods played a critical role in reliable estimation of the rate constant and fluorescence quantum yield.