The interactions between thermodynamic anomalies

Area of Science:

• Thermodynamics
• Physical Chemistry
• Statistical Mechanics

Background:

• Thermodynamic anomalies, such as the liquid-liquid phase transition, are crucial for understanding water's unique properties.
• Existing models often rely on Taylor expansions, which may not fully capture the complex interactions governing these anomalies.

Purpose of the Study:

• To derive and analyze the origin and interactions of key thermodynamic anomalies.
• To investigate the relationship between thermodynamic anomalies and stability (or cavitation) limits.
• To propose a new classification strategy for thermodynamic anomalies.

Main Methods:

• Derivation of interaction conditions from fundamental thermodynamic relations, avoiding Taylor expansions.
• Numerical simulations using a modified Stillinger-Weber potential to vary interatomic interaction balances.
• Exploration of the deeply supercooled regime using replica exchange methods.

Main Results:

• A general set of equations governing interactions between thermodynamic anomalies was derived.
• The derived equations were validated against numerical simulations and previous Taylor expansion results.
• New interaction schemes were uncovered, highlighting relationships between various anomalies.

Conclusions:

• The study provides a robust theoretical framework for understanding thermodynamic anomalies and their interactions.
• A novel classification strategy for thermodynamic anomalies (first- or second-order) is proposed.
• The findings can be extended to classify additional related anomalies in various systems.