Chalcogen bonds: Hierarchical ab initio benchmark and density functional theory performance study.

摘要: We have performed a hierarchical ab initio benchmark and DFT performance study of D2 Ch•••A- chalcogen bonds (Ch = S, Se; D, A F, Cl). The is based on series ZORA-relativistic quantum chemical methods [HF, MP2, CCSD, CCSD(T)], all-electron relativistically contracted variants Karlsruhe basis sets (ZORA-def2-SVP, ZORA-def2-TZVPP, ZORA-def2-QZVPP) with without diffuse functions. highest-level ZORA-CCSD(T)/ma-ZORA-def2-QZVPP counterpoise-corrected complexation energies (ΔECPC ) are converged within 1.1-3.4 kcal mol-1 1.5-3.1 respect to the method set, respectively. Next, we used as reference data for analyzing 13 different approaches in combination Slater-type QZ4P set. find that three-best performing functionals M06-2X, B3LYP, M06, mean absolute errors (MAE) 4.1, 4.2, 4.3 , MAE BLYP-D3(BJ) PBE amount 8.5 9.3