Comparison of complex formation mechanisms in hydrogen abstraction reaction between the nitro compound and ammonia

Present work aimes to compare two possible pathways of a pre-reaction complex in the reaction of transfer of a hydrogen atom from ammonia to a nitro compound forming. Nitrobenzene, nitromethane and HNO₂ were used as nitro compounds. The proposed paths are: nitro compound intersystem crossing with a subsequent search for a substrate or the formation of a complex with its subsequent excitation. The calculations were performed using TDPBE0/TDA/aug-cc-pVDZ method in NWChem-6.8 program. In verification purposes, some additional calculations were performed using RASCI/aug-cc-pVDZ method in PSI4 program. The location of the levels and the geomety of the complexes shows that the triplet complex (exciplex) is more stable than the singlet complex. The weak coupling between molecules in the singlet complex indicates that the probability of its excitation is very small. Moreover, there are experimental data, where the quantum yields of such reactions reaches 0.3. The presented calculations confirm the mechanism of the nitro compound intersystem crossing with a subsequent search for a substrate.