An Assessment of Long-Range Corrected Density Functional Approximations in the Calculation of the Reduction Potentials of Ni(S2C2H2)2, Ni(Se2C2H2)2, Ni(S2C2H2)(N2C2H4), and Ni(Se2C2H2)(N2C2H4) Complexes
Herein an assessment of several Long Range Corrected (LRC) Density Functional Theory (DFT) methods for the calculation of reduction potentials of the ([Ni(X2C2H2)2]n/[Ni(X2C2H2)2]n-1), and ([Ni(X2C2H2)(N2C2H4)]n/[Ni(X2C2H2)(N2C2H4)]n-1) and (where X= S or Se and n = 0, or -1) redox couples was done. From the results the values of ω that provide best agreement with CCSD(T) for the tested LRC DFT methods are 0.05 bohr-1, 0.15 bohr-1, 0.05 bohr-1, and 0.20 bohr-1 for ω-B97XD, LC-BLYP, CAM-B3LYP, and ω-B97, respectively. With these values the unsigned average in error was 0.12 V with a standard deviation of 0.13 V for ω-B97XD. For LC-BLYP, CAM-B3LYP, and ω-B97 the unsigned averages in relative errors were 0.12 V, 0.11 V, and 0.13 V, respectively, with respective standard deviations of 0.11 V, 0.12 V and 0.13 V.