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1. On the liquid demixing of water + elastin-like polypeptide mixtures: bimodal re-entrant phase behaviour

   https://doi.org/10.1039/d0cp05013j  

   Lindeboom, Tom; Zhao, Binwu; Jackson, George; Hall, Carol K.; Galindo, Amparo (March 2021, Physical Chemistry Chemical Physics)

   null (Ed.)

   Water + elastin-like polypeptides (ELPs) exhibit a transition temperature below which the chains transform from collapsed to expanded states, reminiscent of the cold denaturation of proteins. This conformational change coincides with liquid–liquid phase separation. A statistical-thermodynamics theory is used to model the fluid-phase behavior of ELPs in aqueous solution and to extrapolate the behavior at ambient conditions over a range of pressures. At low pressures, closed-loop liquid–liquid equilibrium phase behavior is found, which is consistent with that of other hydrogen-bonding solvent + polymer mixtures. At pressures evocative of deep-sea conditions, liquid–liquid immiscibility bounded by two lower critical solution temperatures (LCSTs) is predicted. As pressure is increased further, the system exhibits two separate regions of closed-loop of liquid–liquid equilibrium (LLE). The observation of bimodal LCSTs and two re-entrant LLE regions herald a new type of binary global phase diagram: Type XII. At high-ELP concentrations the predicted phase diagram resembles a protein pressure denaturation diagram; possible “molten-globule”-like states are observed at low concentration. 

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2. Modeling colloidal interactions that predict equilibrium and non-equilibrium states

   https://doi.org/10.1063/5.0086650  

   Ryu, Brian K.; Fenton, Scott M.; Nguyen, Tuan T.; Helgeson, Matthew E.; Zia, Roseanna N. (June 2022, The Journal of Chemical Physics)

   Modulating the interaction potential between colloids suspended in a fluid can trigger equilibrium phase transitions as well as the formation of non-equilibrium “arrested states,” such as gels and glasses. Faithful representation of such interactions is essential for using simulation to interrogate the microscopic details of non-equilibrium behavior and for extrapolating observations to new regions of phase space that are difficult to explore in experiments. Although the extended law of corresponding states predicts equilibrium phases for systems with short-ranged interactions, it proves inadequate for equilibrium predictions of systems with longer-ranged interactions and for predicting non-equilibrium phenomena in systems with either short- or long-ranged interactions. These shortcomings highlight the need for new approaches to represent and disambiguate interaction potentials that replicate both equilibrium and non-equilibrium phase behavior. In this work, we use experiments and simulations to study a system with long-ranged thermoresponsive colloidal interactions and explore whether a resolution to this challenge can be found in regions of the phase diagram where temporal effects influence material state. We demonstrate that the conditions for non-equilibrium arrest by colloidal gelation are sensitive to both the shape of the interaction potential and the thermal quench rate. We exploit this sensitivity to propose a kinetics-based algorithm to extract distinct arrest conditions for candidate potentials that accurately selects between potentials that differ in shape but share the same predicted equilibrium structure. The algorithm selects the candidate that best matches the non-equilibrium behavior between simulation and experiments. Because non-equilibrium behavior in simulation is encoded entirely by the interparticle potential, the results are agnostic to the particular mechanism(s) by which arrest occurs, and so we expect our method to apply to a range of arrested states, including gels and glasses. Beyond its utility in constructing models, the method reveals that each potential has a quantitatively distinct arrest line, providing insight into how the shape of longer-ranged potentials influences the conditions for colloidal gelation. 

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3. Liquid-liquid phase separation in supercooled water from ultrafast heating of low-density amorphous ice

   https://doi.org/10.1038/s41467-023-36091-1  

   Amann-Winkel, Katrin; Kim, Kyung Hwan; Giovambattista, Nicolas; Ladd-Parada, Marjorie; Späh, Alexander; Perakis, Fivos; Pathak, Harshad; Yang, Cheolhee; Eklund, Tobias; Lane, Thomas J.; et al (December 2023, Nature Communications)

   Abstract Recent experiments continue to find evidence for a liquid-liquid phase transition (LLPT) in supercooled water, which would unify our understanding of the anomalous properties of liquid water and amorphous ice. These experiments are challenging because the proposed LLPT occurs under extreme metastable conditions where the liquid freezes to a crystal on a very short time scale. Here, we analyze models for the LLPT to show that coexistence of distinct high-density and low-density liquid phases may be observed by subjecting low-density amorphous (LDA) ice to ultrafast heating. We then describe experiments in which we heat LDA ice to near the predicted critical point of the LLPT by an ultrafast infrared laser pulse, following which we measure the structure factor using femtosecond x-ray laser pulses. Consistent with our predictions, we observe a LLPT occurring on a time scale < 100 ns and widely separated from ice formation, which begins at times >1 μs. 

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4. Triple critical point and emerging temperature scales in SU(N) ferromagnetism at large N

   https://doi.org/10.1016/j.nuclphysb.2024.116748  

   Polychronakos, Alexios P; Sfetsos, Konstantinos (December 2024, Nuclear Physics B)

   The non-Abelian ferromagnet recently introduced by the authors, consisting of atoms in the fundamental representation of , is studied in the limit where becomes large and scales as the square root of the number of atoms . This model exhibits additional phases, as well as two different temperature scales related by a factor . The paramagnetic phase splits into a "dense" and a "dilute" phase, separated by a third-order transition and leading to a triple critical point in the scale parameter and the temperature, while the ferromagnetic phase exhibits additional structure, and a new paramagnetic-ferromagnetic metastable phase appears at the larger temperature scale. These phases can coexist, becoming stable or metastable as temperature varies. A generalized model in which the number of -equivalent states enters the partition function with a nontrivial weight, relevant, e.g., when there is gauge invariance in the system, is also studied and shown to manifest similar phases, with the dense-dilute phase transition becoming second-order in the fully gauge invariant case. 

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5. Spectral phase transitions in optical parametric oscillators

   https://doi.org/10.1038/s41467-021-21048-z  

   Roy, Arkadev; Jahani, Saman; Langrock, Carsten; Fejer, Martin; Marandi, Alireza (February 2021, Nature Communications)

   Abstract Driven nonlinear resonators provide a fertile ground for phenomena related to phase transitions far from equilibrium, which can open opportunities unattainable in their linear counterparts. Here, we show that optical parametric oscillators (OPOs) can undergo second-order phase transitions in the spectral domain between degenerate and non-degenerate regimes. This abrupt change in the spectral response follows a square-root dependence around the critical point, exhibiting high sensitivity to parameter variation akin to systems around an exceptional point. We experimentally demonstrate such a phase transition in a quadratic OPO. We show that the divergent susceptibility of the critical point is accompanied by spontaneous symmetry breaking and distinct phase noise properties in the two regimes, indicating the importance of a beyond nonlinear bifurcation interpretation. We also predict the occurrence of first-order spectral phase transitions in coupled OPOs. Our results on non-equilibrium spectral behaviors can be utilized for enhanced sensing, advanced computing, and quantum information processing. 

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