The dynamics of NO release upon photodissociation of nitroaromatic compounds is dependent on the nature of the interaction between the NO group and substituent in the position. A bimodal (slow and fast) translational energy distribution of the NO photofragment indicates the presence of two distinct NO elimination channels. The slow-to-fast branching ratio for the NO release is regulated by the hydrogen bonding ability of the substituent and follows the order [OH > NH > CH > OCH], indicating that the intramolecular hydrogen bonding plays a pivotal role in NO release dynamics. Further, the topology of the triplet state potential energy surface acts as a doorway to the dissociation pathway switching between the roaming and nonroaming mechanisms, with hydrogen bonding substituents (OH and NH) favoring the roaming mechanism.
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