Observation of reversible conformational interconversion accompanied by 3p internal conversions in Rydberg-excited N,N-dimethylethylamine.

Conformational dynamics has been well observed in the 3s Rydberg state of amines, whereas its observation in higher-energy, non-equilibrium 3p Rydberg states is very rare, especially for a reversible conformational transition that could compete with other non-adiabatic transitions. Herein, we report the observation of a reversible conformational interconversion phenomenon in the 3p Rydberg excited-state dynamics of N,N-dimethylethylamine (DMEA). Upon electronic excitation, a forward and backward interconversion between the initially prepared 3p_l and 3p_h conformers accompanied by 3p internal conversions occurs, resulting in a 3p_l/3p_h equilibrium ratio of 61 %/39 % within ∼1.