Until now, applications of CT-TSH have been limited to model systems of one or two dimensions including only two electronic states . In this study, we aim to demonstrate its efficiency and reliability for the first time on a molecular system. We investigate, in full dimensionality, the photoisomerization of the trans-azobenzene (TAB) molecule combining the semiempirical FOMO-CI electronic structure method with the CT-TSH algorithm. We choose to use the semiempirical Floating Occupation Molecular Orbitals-Configuration Interaction (FOMO-CI) method because it offers high computational efficiency and reasonable accuracy (when properly parametrized), making it ideal for easily computing multiple trajectories for medium to large molecular systems over time scales of up to few picoseconds .