DSD-PBEP86-NL and DOD-PBEP86-NL functionals for noncovalent interactions: Basis set effects and tentative applications to large noncovalent systems

Abstract

Basis set effects on the DSD-PBEP86-NL and DOD-PBEP86-NL functionals for noncovalent interactions have been extensively studied in this work. The cc-pVXZ (X = D, T, Q, 5, 6) and augmented aug-cc-pVXZ (X = D, T, Q) basis sets are systematically tested without counterpoise (CP) corrections against the well-known S66 database. Additionally, the basis sets of def2-TZVPP and def2-TZVPPD are also examined. Based on our computations, the performances of the aug-cc-pVQZ, cc-pV5Z, and cc-pV6Z basis sets are very approximate to those obtained with the def2-QZVP basis set for both the DSD-PBEP86-NL and DOD-PBEP86-NL functionals. Note that the short-range attenuation parameters for these two functionals were directly optimized using the def2-QZVP basis set without CP corrections against the S66 database. Generally speaking, the cc-pVXZ (X = D, T, Q), aug-cc-pVXZ (X = D, T, Q), def2-TZVPP, and def2-TZVPPD basis sets favor half CP correction for these two functionals. Nevertheless, the aug-cc-pVQZ basis set already performs well without any CP correction, especially for the DOD-PBEP86-NL functional. With respect to accuracy and computational cost, the cc-pVTZ and def2-TZVPP basis sets with half CP corrections are recommended for these two functionals to evaluate interaction energies of large noncovalent complexes.