Understanding photoinduced chemical reactions beyond the Born-Oppenheimer paradigm requires a comprehensive examination of vibronic interactions. Although femtosecond studies have unveiled the influence of vibrational modes strongly coupled to ultrafast intramolecular reactions in the excited state, they often lack direct observations of how vibrations modulate electronic properties due to the rapid disappearance of reactants. To address this gap, our research investigates the dynamics of photoexcited molecules that do not react. Specifically, we focus on the coherent librational motion of molecular transition dipole moments, discovering that the coherent libration primarily originates from symmetry-breaking components in vibronically excited vibrational modes. Symmetry breaking motion can significantly impact the excited-state dynamics of highly symmetric molecules, potentially leading to nonadiabatic transitions. In essence, the data analysis framework introduced in this study can be harnessed to uncover potential reactivity in photoexcited molecules, further enhancing our understanding of the mechanisms governing these reactions.