Identification of Ion Pairs in Aqueous NaCl and KCl Solutions in Combination with Raman Spectroscopy, Molecular Dynamics, and Quantum Chemical Calculations

This work summarizes a theoretical analysis of the perturbation on Raman spectra in aqueous NaCl and KCl solutions with the aim to detect ion pairs. The experimental Raman spectra, both polarized and depolarized, are perturbed by these ions to a comparable extent or somewhat less by KCl than NaCl. This result appears to be contrary to the molecular dynamics (MD) simulation showing that the isolated and separated ions of KCl should have a larger perturbation than NaCl, as the solvation shell of K+ is larger than that of Na+. The apparent discrepancy signifies the ion pair formation which is more substantial for KCl than NaCl. The MD simulations and quantum chemical calculations revealed that KCl forms ion pairs more than NaCl and that the ion pair formation reduces the perturbation on the Raman spectra more for KCl. The present analysis shows that the perturbed Raman spectra provide a useful sign to evaluate the ion pair formation in aqueous solutions.