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
Abstract
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.
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