Optimized Pseudopotentials and Basis Sets for Semiempirical Density Functional Theory for Electrocatalysis Applications.

A complete set of Goedecker, Teter, and Hutter (GTH) norm-conserving pseudopotentials (PPs) have been optimized, in conjunction with molecular optimized (MOLOPT) basis sets, for both the B97M-rV and ωB97X-V density functionals for members of the main-group elements and 3d and noble metals. The resulting small-core PPs and corresponding DZVP, TZVP, and TZV2P basis sets yield notable improvements compared to the original PBE defaults when validated against all electron calculations for redox reaction energies and geometries, binding energies, and vibrational Stark effects for metal monocarbonyls in vacuum. Further validation of the optimized PP/MOLOPT basis set combinations was performed using ab initio molecular dynamics simulations and shows greatly improved agreement with experimental trends for metal surface relaxations and the adsorption behavior of CO on solid metal surfaces.