Macro and nano scale modelling of water-water interactions at ambient and low temperature: relaxation and residence times

The decay dynamics of ambient and low temperature liquid water has been investigated through all-atom molecular dynamics simulations, residence times calculations and time correlation functions from 300 K down to 243 K. Those simulations replicate the experimental value of the self-diffusion constant as a function of temperature by tuning the damping factor of the Langevin equation of motion. A stretched exponential function exp[−(t/τ)β] has been found to properly describe the relaxation of residence times calculated at different temperatures for solvent molecules in a nanodrop of free water modelled as a sphere of nanometric dimensions. As the temperature goes down the decay time τ increases showing a divergence at Ts = 227 ± 3 K. The temperature independence of the dimensionless stretched exponent β = 0.59 ± 0.01 suggests the presence of, not a characteristic relaxation time (since β ≠ 1), but a distribution of decay times that also holds at low temperature. An explanation for such heterogeneity can be found at the nanoscopic level. Moreover it can be concluded that the distribution of times already reported for the dynamics of water surrounding proteins (β ≤ 0.5) can not be exclusively due to the presence of the biomolecule itself since isolated water also exhibits such behaviour. The above reported Ts and β values quantitatively reproduce experimental data.This work was funded by the Spanish MICINN (Ministerio de Ciencia e Innovación) and the FEDER (ERDF European Regional Development Fund) through Projects No. FIS2014-55867-P and FIS2011-25167. Financial support though Grant No. E19 (Gobierno de Aragón, Spain) to Research Group FENOL is also acknowledged.Peer Reviewe

Towards a microscopic description of the free-energy landscape of water

Free-energy landscape theory is often used to describe complex molecular systems. Here, a microscopic description of water structure and dynamics based on configuration-space-networks and molecular dynamics simulations of the TIP4P/2005 model is applied to investigate the free-energy landscape of water. The latter is built on top of a large set of water microstates describing the kinetic stability of local hydrogen-bond arrangements up to the second solvation shell. In temperature space, the landscape displays three regions with an overall different organization. At ambient conditions, the free-energy surface is characterized by structural inhomogeneities with multiple, structurally well defined, short-lived basins of attraction. Below around ambient temperature, the liquid rapidly becomes homogeneous. In this regime, the landscape is funneled-like, with fully-coordinated water arrangements at the bottom of the funnel. Finally, a third region develops below the temperature of maximal compressibility (Widom line) where the funnel becomes steeper with few interconversions between microstates other than the fully coordinated ones. Our results present a viable a way to manage the complexity of water structure and dynamics, connecting microscopic properties to its ensemble behavior