TY - JOUR
T1 - Computational investigation of photo induced processes in alkyl nitrites and the product alkoxy radicals
AU - Rosenberg, Martin
AU - Sølling, Theis Ivan
N1 - Paper id:: doi:10.1016/j.physletb.2003.10.071
PY - 2010/1/7
Y1 - 2010/1/7
N2 - 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.
AB - 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.
U2 - 10.1016/j.cplett.2009.11.001
DO - 10.1016/j.cplett.2009.11.001
M3 - Letter
SN - 0009-2614
VL - 484
SP - 113
EP - 118
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 4-6
ER -