Self-interaction correction in water–ion clusters

We study the importance of self-interaction errors in density functional approximations for various water–ion clusters. We have employed the Fermi–Löwdin orbital self-interaction correction (FLOSIC) method in conjunction with the local spin-density approximation, Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA), and strongly constrained and appropriately normed (SCAN) meta-GGA to describe binding energies of hydrogen-bonded water–ion clusters, i.e., water–hydronium, water–hydroxide, water–halide, and non-hydrogen-bonded water–alkali clusters. In the hydrogen-bonded water–ion clusters, the building blocks are linked by hydrogen atoms, although the links are much stronger and longer-ranged than the normal hydrogen bonds between water molecules because the monopole on the ion interacts with both permanent and induced dipoles on the water molecules. We find that self-interaction errors overbind the hydrogen-bonded water–ion clusters and that FLOSIC reduces the error and brings the binding energies into closer agreement with higher-level calculations. The non-hydrogen-bonded water–alkali clusters are not significantly affected by self-interaction errors. Self-interaction corrected PBE predicts the lowest mean unsigned error in binding energies (≤50 meV/H2O) for hydrogen-bonded water–ion clusters. Self-interaction errors are also largely dependent on the cluster size, and FLOSIC does not accurately capture the subtle variation in all clusters, indicating the need for further refinement.