Mechanism for ultrafast internal conversion of adenine

Abstract

The mechanism for the internal conversion of adenine was investigated by femtosecond pump–probe transient ionization time-of-flight mass spectrometry. In particular, we tried to determine which of the nπ* and πσ* states was responsible for the ultrafast decay of adenine by comparing the dynamics of adenine and its several derivatives with methyl or deuterium substitution. Adenine and all its derivatives studied here had more or less the same decay time of ∼1 ps at the excitation energy of 37 500 cm−1. These results provide compelling evidence that the nπ* state, rather than the πσ* state, plays the role of a doorway state for internal conversion via a conical intersection to the ground state.