Computational investigation of photo induced processes in alkyl nitrites and the product alkoxy radicals

The mechanistic aspects of the photo induced reactions of gaseous amyl nitrite have been investigated using ab initio calculations. We show that the C5H11O–NO bond dissociation mechanism is different on the S1 and S2 surfaces, respectively. The subsequent conformational changes in the ground state 1-pentoxy radical involves several barriers. Interestingly, we show that the intramolecular 1,5-H transfer in the 1-pentoxy radical proceeds in the opposite direction on the S1 state compared to the S0 reaction. Moreover, the results show that the excited state reaction of the alkoxy radical may be a proton transfer that proceeds on a repulsive surface.