Authors
Jiacheng Niu, Qiuyang Zhao, Michael J Adams, Hao Lu, Yin Chen, Xinjian Wang, Hui Jin, Liejin Guo
Published in
The journal of physical chemistry letters. Volume 17. Issue 32. Pages 9128-9135. Aug 13, 2026.
Abstract
Supercritical water (SCW) is a promising green solvent, yet optimizing its performance requires a fundamental understanding of the thermodynamic behavior and solvation mechanisms. Here, molecular dynamics simulations are used to investigate the thermodynamic responses, cohesive-strength evolution, and cavity-formation behavior of SCW along isobars, with the NIST benchmark data serving as a reference for the classical Widom line (WL) behavior. The origin of the high-pressure WL divergence is analyzed from the perspective of statistical fluctuations and intermolecular interactions. Furthermore, cohesive energy density and the state-dependent mean-radius cavity-formation free energy, together with their corresponding thermal response coefficients, are introduced to establish a thermodynamic connection with the classical WL. Building on this connection, the high-pressure "Widom region" is delineated, and the thermodynamically driven evolution sequence along the isobaric heating path is revealed. This work provides a thermodynamic framework for understanding the evolution of the Widom region and its relevance to the solvation behavior of SCW.
PMID:
42593339
Bibliographic data and abstract were imported from PubMed on 13 Aug 2026.
Read full publication at:
Please sign in
to see all details.
Advertisement
Stats
- Recommendations n/a n/a positive of 0 vote(s)
- Views 4
- Comments 0