Does the second critical-point of water really exist in nature?

TL;DR

This paper critically examines the existence of the second critical point of water in nature, arguing that previous simulation-based claims violate thermodynamic principles and clarifying the true nature of liquid-liquid phase transitions.

Contribution

The paper demonstrates that the hypothesized second critical point contradicts thermodynamics and clarifies the correct interpretation of liquid-liquid phase transitions in pure liquids.

Findings

The second critical point hypothesis violates the Gibbs phase rule.

Simulations claiming SCP are flawed due to non-compliance with thermodynamic limits.

A new concept is proposed to explain liquid-liquid phase transitions in single-component liquids.

Abstract

In the past decade, a literary phrase "No man's land" has been flooded in the scientific papers. The expression is used to describe a meta-stable region in the phase-diagram that cannot be accessed by experiments. It has been claimed based on the molecular dynamics (MD) simulation that there is a critical point, or the second critical point (SCP), in the "no man's land," and it has created a big dispute in the field of science. It is proved in the present paper that the hypothesis of SCP is completely against the rigorous theorem of thermodynamics, referred as the Gibbs phase rule. The reason why the simulations have found SCP erroneously is merely because the method violates the requirement which all the statistical-mechanics treatments should satisfy to reproduce the thermodynamics. That is the thermodynamic limit. It is clarified what is the identity of the "liquid-liquid phase transition" and SCP in pure liquids, discovered by the simulations and by some experiments. In order to explain the physics of liquid-liquid phase transition observed experimentally in single component liquids, a new concept is proposed.