The performances of 19 density functionals,including pure generalized gradient approximations(GGAs),hybrid GGAs,hybrid-meta GGAs,and range-separated and double hybrid functionals,in combination with 5 types of correlation consistent basis sets,have been gauged for the prediction of electronic energy barriers for the benchmark set(NiS4),which contains four elementary reactions of S-coordinated Ni complexes.The geometry structures of transition states and minima were optimized by B3LYP method and the corresponding electronic energies were obtained from single-point energy calculations by the 19 density functional with Grimme D3 dispersion corrections(if available).The electronic energy barriers determined by the 19 density functionals were compared to those generated from CCSD(T)/aug-cc-CV∞Z calculations.Of the functionals employed,ωB97X/cc-pVQZ yielded the best overall results with both mean absolute deviations(MADs)and root mean square deviations(RMSDs)from CCSD(T)/aug-cc-CV∞Z electronic energy barriers of 1.92 and 1.29 kcal mol-1,respectively.However,the double hybrid functionals B2GP-PLYP and mPW2-PLYP resulted in deviations from CCSD(T)results of nearly 12 kcal mol-1 averagely.