Minimum in the pressure dependence of the interfacial free energy between ice Ih and water

TL;DR

This study investigates the pressure dependence of interfacial free energy between ice Ih and water, revealing a shallow minimum around -2000 bar and establishing universal empirical expressions for homogeneous ice nucleation across a wide pressure range.

Contribution

The paper introduces the first detailed analysis of interfacial free energy behavior under negative pressures, identifying a minimum and deriving universal nucleation expressions.

Findings

Interfacial free energy shows a shallow minimum near -2000 bar.

Universal empirical expressions for nucleation are valid from -2600 to 500 bar.

Interfacial free energy change correlates with excess entropy and melting line slope.

Abstract

Despite the importance of ice nucleation, this process has been barely explored at negative pressures. Here, we study homogeneous ice nucleation in stretched water by means of Molecular Dynamics Seeding simulations using the TIP4P/Ice model. We observe that the critical nucleus size, interfacial free energy, free energy barrier, and nucleation rate barely change between isobars from -2600 to 500 bar when they are represented as a function of supercooling. This allows us to identify universal empirical expressions for homogeneous ice nucleation in the pressure range from -2600 to 500 bar. We show that this universal behavior arises from the pressure dependence of the interfacial free energy which we compute by means of the mold integration technique finding a shallow minimum around -2000 bar. Likewise, we show that the change in the interfacial free energy with pressure is proportional to the excess entropy and the slope of the melting line, exhibiting the latter a reentrant behavior also at the same negative pressure. Finally, we estimate the excess energy and the excess entropy of the ice Ih-water interface.