Computation of covalent and noncovalent structural parameters at low computational cost: Efficiency of the DH‐SVPD method

Abstract

DH‐SVPD is a tailored atomic basis set originally developed to enhance the domain of applicability of double‐hybrid density functionals to large molecular systems in weak interactions. In combination with any density functional belonging to this approximation, it provides an accurate estimate of noncovalent interaction energies at the cost of a double‐ζ basis set, without adding a posteriori an empirical dispersion correction. Here, we show that the accuracy/cost ratio observed previously for energy properties can be safely extended to the modeling of structural parameters of small‐ and medium‐sized organic molecules. In particular, we demonstrate that, in combination with the nonempirical PBE‐QIDH double hybrid, DH‐SVPD is competitive with very large quadruple‐ζ basis sets when modeling both covalent and noncovalent structural parameters.