Correlation Consistent Basis Sets and Core Polarization Potentials for Al-Ar with ccECP Pseudopotentials

New correlation consistent basis sets for the second-row atoms (Al-Ar) to be used with the neon-core correlation consistent effective core potentials (ccECPs) have been developed. The basis sets, denoted cc-pV(n+d)Z-ccECP (n = D, T, Q), include the tight-d functions that are known to be important for second-row elements. Sets augmented with additional diffuse functions are also reported. Effective core polarization potentials (CPPs) to account for the effect of core-valence correlation have been adjusted for the same elements, and two different forms of the CAP cutoff function have been analyzed. The accuracy of both the basis sets and the CPAs is assessed through benchmark calculations at the coupled-duster level of theory for atomic and molecular properties. Agreement with all-electron results is much improved relative to the basis sets that originally accompanied the ccECPs; moreover, the combination of cc-pV(n+d)Z-ccECP and CPPs is found to be a computationally efficient and accurate alternative to including core electrons in the correlation treatment.

Automated summary

New correlation consistent basis sets have been developed for second-row atoms to be used with neon-core correlation consistent effective core potentials (ccECPs). Sets with additional diffuse functions and adjusted effective core polarization potentials (CPPs) have been analyzed. The accuracy of the basis sets and CPPs is assessed through benchmark calculations, showing improved agreement with all-electron results.