Photoactive transition-metal nitrosyl complexes are particularly interesting as potential drugs that deliver nitric oxide (NO) upon UV-light irradiation to be used, e.g., in photodynamic therapy. It is well-recognized that quantum-chemical calculations can guide the rational design and synthesis of molecules with specific functions. In this contribution, it is shown how electronic structure calculations and dynamical simulations can provide a unique insight into the photodissociation mechanism of NO. Exemplarily, [Ru(PaPy3)(NO)](2+) is investigated in detail, as a prototype of a particularly promising class of photoactive metal nitrosyl complexes. The ability of time-dependent density functional theory (TD-DFT) to obtain reliable excited-state energies compared with more sophisticated multiconfigurational spin-corrected calculations is evaluated. Moreover, a TD-DFT-based trajectory surface-hopping molecular dynamics study is employed to reveal the details of the radiationless decay of the molecule via internal conversion and intersystem crossing. Calculations show that the ground state of [Ru(PaPy3)(NO)](2+) includes a significant admixture of the Ru(III)(NO)(0) electronic configuration, in contrast to the previously postulated Ru(II)(NO)(+) structure of similar metal nitrosyls. Moreover, the lowest singlet and triplet excited states populate the antibonding metal d → πNO* orbitals, favoring NO dissociation. Molecular dynamics show that intersystem crossing is ultrafast (<10 fs) and dissociation is initiated in less than 50 fs. The competing relaxation to the lowest S1 singlet state takes place in less than 100 fs and thus competes with NO dissociation, which mostly takes place in the higher-lying excited triplet states. All of these processes are accompanied by bending of the NO ligand, which is not confined to any particular state.