Hydrated metal ions are important in a variety of biological and environmental systems, yet a comprehensive picture of the dynamic local environment associated with these ions remains elusive. We report ab initio molecular dynamics of water around Al3+, Cr3+, and Fe3+. Our results indicate starkly different behavior with facile water dissociation occurring near Cr3+ and Fe3+ but not Al3+. Dissociation occurs while proton transfer through a network of hydrogen bonds as originally proposed by Grotthuss in 1806. We note the existence of the hydrated proton as both a H5O2+ complex proposed by Zundel and a H9O4+ complex proposed by Eigen.
Pub Type: Journals
Car-Parrinello molecular dynamics, Eigen mechanism, Grotthuss, metal ions, transition path sampling, water dissociation, Zundel