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
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Abstract
We propose an accurate
scheme to evaluate the redox potential of
a wide variety of transition metal complexes by adding a charge-dependent
correction 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 B3LYP 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<sub>1</sub>(CO)<sub>5</sub>(pycn)
(M<sub>1</sub> = Cr, Mo, W), M<sub>2</sub>(mnt)<sub>2</sub> (M<sub>2</sub> = Ni, Pd, Pt), and M<sub>3</sub>(bpy)<sub>3</sub> (M<sub>3</sub> = Fe, Ru, Os) with the same quality
