Comprehensive Basis-Set Testing of Extended Symmetry-Adapted Perturbation Theory and Assessment of Mixed-Basis Combinations to Reduce Cost

Abstract

Hybrid or "extended" symmetry-adapted perturbation theory (XSAPT) replaces traditional SAPT's treatment of dispersion with better-performing alternatives, while at the same time extending two-body (dimer) SAPT to a many-body treatment of polarization using a self-consistent charge-embedding procedure. The present work presents a systematic study of how XSAPT interaction energies and energy components converge with respect to the choice of Gaussian basis set. Although errors can be reduced in a systematic way using correlation-consistent basis sets, similar performance at lower cost is obtained using Karlsruhe basis sets, and we introduce new versions with limited augmentation (diffuse functions) that are even more efficient. Pople-style basis sets, which are even more efficient, often afford good results if a large number of polarization functions are included. The dispersion models used in XSAPT afford much faster basis-set convergence as compared to the perturbative description of dispersion in conventional SAPT, meaning that "compromise" basis sets (such as jun-cc-pVDZ) are no longer required and benchmark-quality results can be obtained using basis sets of triple-zeta quality. The use of diffuse functions proves to be essential, especially for the description of hydrogen bonds. The "delta(Hartree-Fock)" correction that accounts for high-order induction can be performed in double-zeta basis sets without significant loss of accuracy, leading to a mixed-basis approach that offers 4x speedup over the existing (cubic-scaling) XSAPT approach.