Recent experiments reported that spin state transitions were realized by applying bias voltages. However, these bias-induced transitions are not fully understood, especially the mechanism. It is well established in experiments that the metal-to-ligand charge transfer (MLCT) excitation activated by light radiation can lead to the transition from low spin (LS) to high spin (HS), and the transition from HS to LS can be achieved by light due to the metal-centered (MC) excitation. Moreover, electronic excitations are accessible by inelastic cotunneling in molecular junctions under bias voltages. Based on these two facts, we propose that the MLCT excitation is responsible for the bias-induced transition from LS to HS, and the bias-induced transition from HS to LS is attributed to the MC excitation. The rationality of our proposed mechanism is demonstrated by comparing first-principles results and experimental observations. Threshold voltages of MLCT and MC excitations predicted in theory are consistent with bias voltages used to reach the transition from LS to HS and that from HS to LS in the experiment [Miyamachi et al., Nat. Commun. 3, 938 (2012)]. Activation of MLCT or MC excitation depends on the bias polarity, which can explain the bias-polarity dependence of the transition in the experiment. Our study is important for further design of molecular spintronic devices working on the bias-controlled transition.

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