Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics.

In this study, the photofragmentation dynamics of tetranitromethane (TNM) is explored by a spin-unrestricted time-dependent excited-state molecular dynamics (u-TDESMD) algorithm based on Rabi oscillations and principles similar to trajectory surface hopping, with a midintensity field approximation. The leading order process is represented by the molecule undergoing cyclic excitations and de-excitations. During excitation cycles, the nuclear kinetic energy is accumulated to overcome the dissociation barriers in the reactant and a sequence of intermediates. The dissociation pathway includes the ejection of NO2 groups followed by the formation of NO and CO. The simulated mass spectra at the ab initio level, based on the bond length in possible fragments, are extracted from simulation trajectories. The recently developed methodology has the potential to model and monitor photoreactions with open-shell intermediates and radicals.