A Density Functional Theory Based Protocol to Compute the Redox Potential of Transition Metal Complex with the Correction of Pseudo-Counterion: General Theory and Applications

We propose an accurate scheme to evaluate the redox-potential of a wide variety of transition metal complexes by adding a charge-dependent collection term for a counterion around the charged complexes, which is based on Generalized Born theory, to the solvation energy: The mean.. absolute error (MAE) toward:, experimental redox-potentials of charged complexes is considerably reduced from 0.81 V(maximum error 1.22 V) to 0.22 V (maximum error 0.50 V). We found a remarkable exchange-correlation functional dependence on the results rather than the basis set ones. The combination of Wachters+f (for metal) and 6-31++G(d,p) (for other. atoms) With the B3LYB functional gives the least MAE 0.15 V for the test complexes. This scheme is applicable to Other solvents, and heavier transition metal complexes such as M-1(CO)(5)(pycn) (M-1 = Cr, Mo, W), M-2(mnt)(2) (M-2 = Ni, Pd, Pt), and M-3(bpy)(3) (M-3 = Fe, Ru, Os) with the same quality.