Radiationless deactivation pathways versus H-atom elimination from the N-H bond photodissociation in PhNH₂-(Py)_n...

Minimum energy structures of the ground and lowest excited states of aniline (PhNH₂) solvated by pyridine (Py) show that the clusters formed are stabilized by hydrogen bonds in which only one or both hydrogen atoms of the NH₂ group take part. Two different N-H bonds photodissociation in PhNH₂-(Py)_n (n = 1,2) complexes, free and hydrogen bonded have been studied by analyzing excited state potential energy surfaces. In the first one, only N-H bonds engaged in hydrogen bonding in these complexes are considered. RICC2 calculations of potential energy (PE) profiles indicate that all photochemical reaction paths along N-H stretching occur mainly via the proton-coupled electron transfer (PCET) mechanism. The repulsive charge transfer ¹ππ*(CT) state dominates the PE profiles, leading to low-lying ¹ππ*(CT)/S₀ conical intersections and thus provide channels for ultrafast radiationless deactivation of the electronic excitation or stabilization to biradical complexes. The second photoreaction consists of a direct dissociation along the free N-H bond of the NH₂ group. It has been shown that this process is played by excited singlet states of ¹πσ* character having repulsive potential energy profiles with respect to the stretching of N-H bond, which dissociates over an exit barrier about 0.5 eV giving rise to the formation of a ¹πσ*/S₀ conical intersection. This may cause an internal conversion to the ground state or may lead to H-atom elimination. This photophysical process is the same in both planar and T-shaped conformers of the PhNH₂-Py monomer complex. Our findings reveal that there is no single dominating path in the photodissociation of N-H bonds in PhNH₂-(Py)_n complexes, but rather a variety of paths involving H-atom elimination and several quenching mechanisms.