Molecular dynamics to rationalize EXAFS experiments: A dynamical model explaining hydration behaviour across the lanthanoid(III) series

In this paper we show how polarizable molecular dynamics can be successfully used to understand lanthanoid(III) (Ln) hydration. In particular, our modelling is in very good agreement with EXAFS data and thus the microscopic picture emerging directly from dynamics can be useful to understand experiments. We show three examples across the series: at the beginning (Nd 3+), middle (Gd3+) and end (Yb3+). Using these examples, we show that we are able to reproduce not only Ln-oxygen distances but also the changeover in coordination number across the series. The peculiarity of the changeover of lanthanoid coordination number in the middle of the series emerges from high exchange frequency, such that a molecular dynamics approach becomes a fundamental tool to understand this phenomenon. © 2009 IOP Publishing Ltd.