Spontaneously Forming Dendritic Voids in Liquid Water Can Host Small Polymers

Some liquids are characterized by the presence of large voids with dendritic shapes and for this reason are dubbed transiently porous. By using a battery of data analysis tools, we demonstrate that liquid water and methane are both characterized by transient porosity. We show that the thermodynamics of porosity is distinct from that associated with cavitation a la classical nucleation theory. The shapes of dendritic voids in both liquids with very different chemistries resemble those of small polymers. We further show, using free energy calculations, that the cost of solvating small hydrophobic polymers in water is consistent with the work associated with creating dendritic voids. The entropic and enthalpic contributions associated with hosting these polymers can thus be rationalized by the thermodynamics of fluctuations in bulk water.