The electronic structure of the hydrated proton: A comparative X-ray absorption study of aqueous HCl and NaCl solutions

The oxygen K edge X-ray absorption spectra of aqueous HCl and NaCl solutions reveal distinct perturbations of the local water molecules by the respective solutes. While the addition of NaCl leads to large spectral changes, the effect of HCl on the observed X-ray absorption spectrum is surprisingly small. Density functional theory calculations suggest that this difference primarily reflects a strong blue shift of the hydrated proton (in either the Eigen (H(9)O(4)(+)) or Zundel (H(2)O(5)(+)) forms) spectrum relative to that of H(2)O, indicating the tighter binding of electrons in H(3)O(+). This spectral shift counteracts the spectral changes that arise from direct electrostatic perturbation of water molecules in the first solvation shell of Cl(-). Consequently, the observed spectral changes effected by HCl addition are minimal compared to those engendered by NaCl. Additionally, these results indicate that the effect of monovalent cations on the nature of the unoccupied orbitals of water molecules in the first solvation shell is negligible, in contrast to the large effects of monovalent anions.