DFT Methods Benchmarking against Systems with Transition Metal Species

3 DFT Methods Benchmarking against Systems with Transition Metal Species 

DFT Methods Benchmarking against 3d Transition Metal Systems 

Wilson and coworkers assessed the performance of 13 hybrid-GGA, hybrid-meta-GGA, and double-hybrid DFT functionals on the cc-CA-TM/11 dataset [83]. The hybrid B97-1 [42, 84] functional and the double-hybrid functional mPW2-PLYP [85] were found to give the best performance over experimental results with mean absolute deviations of 7.2 and 7.3 kcal mol . The dataset (cc-CA-TM/11) is rather diverse and consists of AyH of 193 3d transition metal molecules (Sc(C5H5)3 and (Cr03)3, halides, oxides, and heavy chalcogenides, hydrides, nitrides, small clusters, metal carbonyls, and other coordination complexes) [86]. 

Wilson and coworkers studied calculated reaction energetics and barriers for catalytic C-O bond cleavage in dimethyl ether meditated by Fe+, Co+, Ni+, Cu+, Ru , Rh , Pd+, and Ag cations using the CCSD(T)/CBS procedure [94]. BLYP [91, 95], B3LYP, M06, M06-L, B97-1, B97-D, TPSS [96], and PBEO DFT functionals were benchmarked (the aug-cc-pVTZ basis set was adopted). PBEO, B3LYP, and B97-1 showed the least RMSD (root-mean-square deviation) of 3.4, 7.5, and 10.9 kcal mol for 3d transition metals. In the case of 4d metals, PBEO was also found to be the best followed by M06 and B97-1 functionals (RMSD = 6.9,7.1, and 8.3, respectively). Notably, M06-L and B97-D were found to be the only functionals that correctly predicted the ground-state multiplicities for all the species. 

Chan and Yim computed cohesive energies of Au2 g clusters with a composite CCSD(T) F12b-based protocol and found TPSS-D3, TPSSh-D3, B1B95-D3 [105], and conventional PBE-D3 to offer best accuracy compared to ab initio reference data [106] (the mean absolute deviations were 3.2,3.3, 3.3,4.6 kcal mol , respectively). 

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