Abstract
Liquid water nanodroplets are important in earth's climate, and are valuable for studying supercooled water because they resist crystallisation well below the bulk freezing temperature. Bulk liquid water has well-known thermodynamic anomalies, such as a density maximum, and when supercooled is hypothesised to exhibit a liquid-liquid phase transition (LLPT) at elevated pressure. However, it is not known how these bulk anomalies might manifest themselves in nanodroplets. Here we show, using simulations of the TIP4P/2005 water model, that bulk anomalies occur in nanodroplets as small as 360 molecules. We also show that the Laplace pressure inside small droplets reaches 220 MPa at 180 K, conditions close to the LLPT of TIP4P/2005. While the density and pressure inside nanodroplets coincide with bulk values at moderate supercooling, we show that deviations emerge at lower temperature, as well as significant radial density gradients, which arise from and signal the approach to the LLPT.