Dissociation dynamics of 3- and 4-nitrotoluene radical cations: Coherently driven C$-$NO$_2$ bond homolysis

Abstract: Monosubstituted nitrotoluenes serve as important model compounds for nitroaromatic energetic molecules such as trinitrotoluene. This work investigates the ultrafast nuclear dynamics of 3- and 4-nitrotoluene radical cations using femtosecond pump-probe measurements and the results of density functional theory calculations. Strong-field adiabatic ionization of 3- and 4-nitrotoluene using 1500 nm, 18 fs pulses produces radical cations in the ground electronic state with distinct coherent vibrational excitations. In both nitrotoluene isomers, a one-photon excitation with the probe pulse results in \ce{NO2} loss to form \ce{C7H7+}, which exhibits out-of-phase oscillations in yield with the parent molecular ion. The oscillations in 4-nitrotoluene with a period of 470 fs are attributed to the torsional motion of the \ce{NO2} group based on theoretical results showing that the dominant relaxation pathway in 4-nitrotoluene radical cation involves the rotation of the \ce{NO2} group away from the planar geometry. The distinctly faster oscillation period of 216 fs in 3-nitrotoluene is attributed to an in-plane bending motion of the \ce{NO2} and \ce{CH3} moieties based on analysis of the normal modes. These results demonstrate that coherent nuclear motions determine the probability of \ce{C-NO2} homolysis in the nitrotoluene radical cations upon optical excitation within several hundred femtoseconds of the initial ionization event.