Regularized and Opposite spin-scaled functionals from Møller-Plesset adiabatic connection -- higher accuracy at lower cost

Abstract

Non-covalent interactions (NCIs) play a crucial role in biology, chemistry, material science, and everything in between. To improve pure quantum-chemical simulations of NCIs, we propose a methodology for constructing approximate correlation energies by combining an interpolation along the Møller adiabatic connection (MP AC) with a regularization and spin-scaling strategy applied to MP2 correlation energies. This combination yields $c_{\mathrm{os}}{\kappa }_{\mathrm{os}}$-SPL2, which exhibits superior accuracy for NCIs compared to any of the individual strategies. With the $N^4$ formal scaling, $c_{\mathrm{os}}{\kappa }_{\mathrm{os}}$-SPL2, is competitive or often outperforms more expensive dispersion-corrected double hybrids for NCIs.The accuracy of $c_{\mathrm{os}}{\kappa }_{\mathrm{os}}$-SPL2 particularly shines for anionic halogen bonded complexes, where it surpasses standard dispersion-corrected DFT by a factor of 3 to 5.

12 pages + 5 SI, 8 figures + 6 SI