Setting aside aug-cc-pVDZ and def2-SVPD, the accuracy of the DLPNO approximation in the (aug-)cc-pVXZ and Karlsruhe basis set families is very good, even for the most aggressive loose-CCSD(T) threshold of T CutPNO = 10 -6 . To consider whether this accuracy benefits from error cancellation, Figs. S13-S18 present the DLPNO errors for the individual single-point energy calculations E AB , E A , and E B [Eq. ( )], across all of the S66 dimers. For the loosest thresholds, we observe individual errors up to 5 kcal/mol in some cases, even while the DLPNO errors in ∆E are ∼ 100× smaller. This is an error cancellation of sorts, though not an accidental or fortuitous one. Rather, it is akin to the error introduced by making the RI approximation, which introduces a small but size-extensive error per atom, yet one that is roughly constant across the potential energy surface. As such, energy differences remain faithful to the canonical calculation with almost negligible error. This is what we observe for the DLPNO errors, at least in these small dimers.