Photodissociation dynamics of 2-chloro-6-nitrotoluene and nitrocyclopentane in gas phase: Laser-induced fluorescence detection of OH

Photodissociation of 2-chloro-6-nitrotoluene (ClNT) at 193, 248 and 266 nm and nitrocyclopentane (NCP) at 193 nm leads to the formation of OH, as detected by laser-induced fluorescence (LIF). The nascent OH produced from the photolysis of ClNT at all the wavelengths is vibrationally cold, with the Boltzmann type rotational state distributions. However, the nascent OH product from NCP is in the ground and vibrationally excited states with the measured average relative population in nu '' = 1 to that in nu '' = 0 of 0.12 +/- 0.03, and these levels are characterized by rotational temperatures of 650 +/- 180 K and 1570 +/- 90 K, respectively. The translational energy partitioned in the OH fragment has been measured for photodissociation of both ClNT and NCP. On the basis of both the experimental results and the ground state molecular orbital (MO) calculations, a plausible mechanism for the OH formation has been proposed. (C) 2014 Elsevier B. V. All rights reserved.