Reducing Systematic Uncertainty in Computed Redox Potentials for Aqueous Transition-Metal-Substituted Polyoxotungstates

[Image: see text] Polyoxometalates have attracted significant interest owing to their structural diversity, redox stability, and functionality at the nanoscale. In this work, density functional theory calculations have been employed to systematically study the accuracy of various exchange–correlation functionals in reproducing experimental redox potentials, U(0)(Red) in [PW(11)M(H(2)O)O(39)](q−) M = Mn(III/II), Fe(III/II), Co(III/II), and Ru(III/II). U(0)(Red) calculations for [PW(11)M(H(2)O)O(39)](q−) were calculated using a conductor-like screening model to neutralize the charge in the cluster. We explicitly located K(+) counterions which induced positive shifting of potentials by > 500 mV. This approximation improved the reproduction of redox potentials for K(x)[XW(11)M(H(2)O)O(39)](q−x) M = Mn(III/II)/Co(III/II). However, uncertainties in U(0)(Red) for K(x)[PW(11)M(H(2)O)O(39)](q−x) M = Fe(III/II)/Ru(III/II) were observed because of the over-stabilization of the ion-pairs. Hybrid functionals exceeding 25% Hartree–Fock exchange are not recommended because of large uncertainties in ΔU(0)(Red) attributed to exaggerated proximity of the ion-pairs. Our results emphasize that understanding the nature of the electrode and electrolyte environment is essential to obtain a reasonable agreement between theoretical and experimental results.