Equilibrium between 5-and 6-Fold Coordination in the First Hydration Shell of Cu(II)

Chillemi, G (Cineca); Pace, E; D’Abramo, M; Benfatto, M.

The hydration structure dynamics of Cu(II) ion is characterized by a combination of classical molecular dynamics simulation and X-ray absorption near-edge, spectroscopy. Previous experimental data have been analyzed on the basis of 5- or 6-fold first hydration structure, with a quite well established equatorial structure. This 4-fold equatorial geometry has been our starting point to develop a simple but effective in silico model, which provides ab initio theoretical X-ray absorption spectra in very good agreement with the experimental data. Our results point out two equally populated 6- and 5-fold hydration structures with remarkable different water residence times of 5 and 98 ps, respectively, and a low free energy barrier between first and second hydration shell.

JOURNAL OF PHYSICAL CHEMISTRY A
Volume: 120
Issue: 22
Pages: 3958-3965
DOI: 10.1021/acs.jpca.6b03569
Published: JUN 9 2016