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Partial charges are a central concept in general chemistry and chemical biology, yet dozens of different computational definitions exist. In prior work [Cho et al.,  ChemPhysChem   21 , 688‐696 (2020)], we showed that these can be reduced to at most three ‘principal components of ionicity’. The present study addressed the dependence of computed partial charges    q    on 1‐particle basis set and (for WFT methods)    n   ‐particle correlation treatment or (for DFT methods) exchange‐correlation functional, for several representative partial charge definitions such as QTAIM, Hirshfeld, Hirshfeld‐I, HLY (electrostatic), NPA, and GAPT. Our findings show that semi‐empirical double hybrids can closely approach the CCSD(T) ‘gold standard’ for this property. In fact, owing to an error compensation in MP2, CCSD partial charges are further away from CCSD(T) than is MP2. The nonlocal correlation is important, especially when there is a substantial amount of nonlocal exchange. Employing range separation proves to be “mostly" not advantageous, while global hybrids perform optimally for 20%–30% Hartree‐Fock exchange across all charge types. Basis set convergence analysis shows that an augmented triple‐zeta heavy‐aug‐cc‐pV(T+d)Z basis set or a partially augmented jun‐cc‐pV(T+d)Z basis set is sufficient for Hirshfeld, Hirshfeld‐I, HLY, and GAPT charges. In contrast, QTAIM and NPA display slower basis set convergence. It is noteworthy that for both NPA and QTAIM, HF exhibits markedly slower basis set convergence than the correlation components of MP2 and CCSD. Triples corrections in CCSD(T), denoted as CCSD(T)‐CCSD, exhibit even faster basis set convergence.

On the sensitivity of computed partial charges toward basis set and (exchange‐)correlation treatment