In this work, we have studied the photodissociation of the protonated derivatives of N-nitrosodimethylamine [(CH3)2N-NO] with the CASPT2 method. It is found that only one of the four possible protonated species of the dialkylnitrosamine compound absorbs in the visible region at 453 nm, that is, N-nitrosoammonium ion [(CH3)2NH-NO]+. This species is also the only one whose first singlet excited state is dissociative to directly yield the aminium radical cation [(CH3)2NHN·]+ and nitric oxide. In addition, we have studied the intramolecular proton migration reaction {[(CH3)2N-NOH]+ → [(CH3)2NH-NO]+} both in the ground and excited state (ESIPT/GSIPT); our results indicate that this process is not accessible neither in the ground nor in the first excited state. Furthermore, as a first approximation, MP2/HF calculations on the nitrosamine-acid complex indicate that in acidic solutions of aprotic solvents, only [(CH3)2NH-NO]+ is formed.
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