The interactions between thermodynamic anomalies. 2019

Domagoj Fijan, and Mark Wilson
Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.

The origin of and interactions between key thermodynamic anomalies are derived and analyzed, as are the interactions with the stability (or cavitation) limits. The conditions for interaction are derived from the underlying thermodynamic relations rather than using the more-commonly applied Taylor expansion method. As a result, we derive a general set of equations that govern the interactions between different lines of thermodynamic anomalies using standard manipulation of thermodynamic equations. The validity of the derivations is investigated by comparing them to numerical simulation data and previous Taylor expansion-based results. Simulations are performed using a modified Stillinger-Weber potential in which the balance of the two- and three-body interactions is varied and which serves to highlight the relationships between the various anomalies. The deeply supercooled regime is explored by employing replica exchange methods. The behavior of the anomalies is considered in terms of previously constructed thermodynamic "scenarios." Based on the newly uncovered interaction schemes, we propose a classification strategy for the thermodynamic anomalies (as first- or second-order) which could be extended to additional related anomalies.

UI MeSH Term Description Entries

Related Publications

Domagoj Fijan, and Mark Wilson
May 2007, Langmuir : the ACS journal of surfaces and colloids,
Domagoj Fijan, and Mark Wilson
October 2017, Langmuir : the ACS journal of surfaces and colloids,
Domagoj Fijan, and Mark Wilson
October 2002, Acta crystallographica. Section D, Biological crystallography,
Domagoj Fijan, and Mark Wilson
April 2014, The Journal of chemical physics,
Domagoj Fijan, and Mark Wilson
January 2021, Ultrasonics sonochemistry,
Domagoj Fijan, and Mark Wilson
June 2018, Nature communications,
Domagoj Fijan, and Mark Wilson
January 2010, Journal of molecular recognition : JMR,
Copied contents to your clipboard!