Comprehensive investigations on DNa⋯A (D = H/F) complexes show why 'sodium bonding' is not commonly observed

- D-Na⋯A bond can be formed with all acceptors that form H-, Cl-, and Li-bonds.
- NaD frequency shifts have no correlation with interaction energies of the complexes.
- Linear and anti-parallel minima exist for NaF dimer, but neither for HF dimer.
- Anti-parallel structure is the global minimum for NaF dimer, not the linear one.
- Na/Li-bond radii are closer to their ionic radii and do not show polar flattening.