The combination of trajectory surface hopping on potentials parametrized in the linear vibronic coupling model is an efficient approach to perform photodynamics simulations. For transition metal complexes, despite their typically large number of vibrational degrees of freedom and many close-lying electronic states, it becomes affordable to screen the nonadiabatic dynamics of many individual ones in order to test and establish design principles to improve their photophysical and photochemical properties. In this work, we demonstrate this by screening the photophysics of open-shell vanadium(III) complexes derived from VCl 3 (ddpd). This complex, after excitation from the triplet ground state and following intersystem crossing to the singlet manifold, shows singlet-to-triplet phosphorescence in the nearinfrared region. Based on an analysis of the relaxation mechanism of VCl 3 (ddpd), we developed the hypothesis that by increasing the ligand-field strength in the complex could shift the electronic states to modify the mechanism in such a way as to lead to a higher phosphorescence yield. This was to be achieved by channeling more population from the triplet to the singlet states as well as reducing the amount of singlet-to-triplet reverse intersystem crossing that reduces the population available for phosphorescence.