Spontaneously Forming Dendritic Voids in Liquid Water Can Host Small Polymers

Area of Science:

• Physical Chemistry
• Materials Science
• Chemical Physics

Background:

• Certain liquids exhibit transient porosity, featuring large, dendritic-shaped voids.
• Understanding the thermodynamics and structural characteristics of these voids is crucial for comprehending liquid behavior.

Purpose of the Study:

• To investigate the presence and nature of transient porosity in liquid water and methane.
• To compare the thermodynamics of this porosity with classical nucleation theory.
• To explore the relationship between void morphology and polymer solvation.

Main Methods:

• Utilized a suite of data analysis tools to examine liquid structures.
• Performed free energy calculations to assess polymer solvation costs.
• Analyzed the thermodynamic contributions (entropic and enthalpic) to void formation and polymer hosting.

Main Results:

• Confirmed transient porosity in both liquid water and methane.
• Demonstrated that the thermodynamics of this porosity differs from classical cavitation.
• Observed that dendritic void shapes resemble small polymer structures.
• Found the solvation cost of hydrophobic polymers in water aligns with the energy required to create these dendritic voids.

Conclusions:

• Transient porosity in liquids like water and methane is a distinct thermodynamic phenomenon.
• The formation of dendritic voids is thermodynamically linked to the solvation of small hydrophobic polymers.
• The behavior of these voids can be explained by the thermodynamics of bulk liquid fluctuations.