Water dynamics in divalent and monovalent concentrated salt solutions.

Water hydrogen bond dynamics in concentrated salt solutions are studied using polarization-selective IR pump-probe spectroscopy and 2D IR vibrational echo spectroscopy performed on the OD hydroxyl stretching mode of dilute HOD in H(2)O/salt solutions. The OD stretch is studied to eliminate vibrational excitation transfer, which interferes with the dynamical measurements. Though previous research suggested that only the anion affected dynamics in solution, here it is shown that the cation plays a role as well. From FT-IR spectra of the OD stretch, it is seen that replacing either ion of the salt pair causes a shift in absorption frequency relative to that of the OD stretch absorption in bulk pure water. This shift becomes pronounced with larger, more polarizable anions or smaller, high charge-density cations. The vibrational lifetime of the OD hydroxyl stretch in these solutions is a local property and is primarily dependent on the nature of the anion and whether the OD is hydrogen bonded to the anion or to the oxygen of another water molecule. However, the cation still has a small effect. Time dependent anisotropy measurements show that reorientation dynamics in these concentrated solutions is a highly concerted process. While the lifetime, a local probe, displays an ion-associated and a bulk-like component in concentrated solutions, the orientational relaxation does not have two subensemble dynamics, as demonstrated by the lack of a wavelength dependence. The orientational relaxation of the single ensemble is dependent on the identity of both the cation and anion. The 2D IR vibrational echo experiments measure spectral diffusion that is caused by structural evolution of the system. The vibrational echo measurements yield the frequency-frequency correlation function (FFCF). The results also show that the structural dynamics are dependent on the cation as well as the anion.