Beryllium(II): The Strongest Structure-Forming Ion in Water? A QMCF MD Simulation Study

Abstract

A quantum mechanical charge field (QMCF) molecular dynamics (MD) simulation including the first and second hydration shells in the QM region has been carried out to describe the structural and dynamical properties of Be(2+) in aqueous solution. In this methodology, the full first and second hydration shells are treated by ab initio quantum mechanics supplemented by a fluctuating electrostatic embedding technique. From the simulation, structural properties were extracted and were found to be in good agreement with previously published experimental and theoretical results. The radial distribution function (RDF) showed the maximum probability of the Be-O bond length at 1.62 A. The first tetrahedrally arranged hydration shell is highly inert with respect to ligand-exchange processes. Application of local-density-corrected three-body correlation analysis showed minor structural influence of the ion beyond the second hydration layer, contrary to the findings of a previous QM/MM MD simulation. The dynamics of the hydrate were studied in terms of ligand mean residence times (MRTs) and the power spectrum of the Be(2+)-O stretching frequency. A comparison of the "classical" QM/MM framework with the QMCF method clearly demonstrated the advantages of the latter, as ambiguities arising from the coupling of the subregions occurring in QM/MM MD simulations did not appear when the QMCF ansatz was applied.