Fig. 5. (a) The ground- and excited-state PESs of 1tmeda, colored according to the electronic configurations of the ground state (red) and the 1(dd) (green), 3(C-to-Ni CT) (yellow), and T1 (cyan) excited states of the NiII(SC2−) reactant (R), the NiI(SC˙−) intermediate (I, black), and the Ni0 + SC0 product (P, blue). A plausible photo-induced RE pathway from the 1(dd) state and the dark RE pathway are drawn with red and black solid arrows, respectively. Alternative paths are noted with dashed arrows. (b) Electronic configuration and potential energy (in kcal mol−1) changes over the reactions presented in (a).
