Are Conical Intersections Responsible for the Ultrafast Processes of Adenine, Protonated Adenine, and the Corresponding Nucleosides?

Excited-state potential energy surfaces of adenine, protonated adenine, and their N9-methylated analogs are explored by means of a complete active space (CAS) and time-dependent density functional theory (TD-DFT) study to understand the dynamics associated with internal conversion. After photoexcitation of the ground-state molecules to the S(1) state, the nuclear motions that are responsible for taking the wavepacket out of the Franck-Condon region are either an H--N9/C--N9 stretch or a ring-puckering motion that leads to pyramidalization. These motions lead to accessible conical intersections with the ground-state surface. The results are used to successfully interpret previous measurements on the photodissociation of adenosine 5'-monophosphate nucleotide anions and cations, where the latter react in a highly nonstatistical manner.