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The interactions between thermodynamic anomalies.

Domagoj Fijan1, Mark Wilson1

  • 1Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.

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This summary is machine-generated.

This study derives new equations for thermodynamic anomalies and their interactions with stability limits, offering a novel classification strategy based on these findings.

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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.