Competing πσ* States in the Photodissociation of Adenine

Despite the extensive investigations thus far, there is still debate regarding the role of the repulsive πσ* state in the photochemistry of adenine. We present evidence that suggests that H-atom elimination via both the azole group (N 9 ) and the often overlooked amino group (N 6 ) occurs following excitation at 200 nm. In contrast, excitation at 266 nm supports the view that the role of the πσ* states is minimal.