Liquid-liquid transitions under pressure: Theoretical simulations suggest that deeply supercooled water undergoes a transition between high- and low-density forms, but this transition is difficult to study experimentally because it occurs under conditions in which ice crystallization is extremely rapid. Kim et al. combined x-ray lasers for rapid structure determination with infrared femtosecond pulses for rapid heating of amorphous ice layers formed at about 200 kelvin. The heating process created high-density liquid water at increased pressures. As the layer expanded and decompressed, low-density liquid domains appeared and grew on time scales between 20 nanoseconds and 3 microseconds, which was much faster than competing ice crystallization. Science , this issue p. 978

Knowledge of the temperature dependence of the isobaric specific heat (C_p) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in C_p exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid–liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ∼15-µm diameter droplets in vacuum enabled us to reach a temperature down to ∼228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in C_p, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The C_p maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the C_p measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K. Significance The importance of molecular understanding of the structure, dynamics. and properties of liquid water is recognized in many scientific disciplines. Here, we study experimentally the structure and thermodynamics of bulk liquid water as it is supercooled by evaporation down to ∼228 K. The unique aspect of this work is the use of ultrafast calorimetry that enables us to determine the specific-heat capacity of water to unprecedentedly low temperatures. The observed maximum of about 218 J/mol/K at 229 K is consistent with the liquid–liquid critical point model and supports a proposed fragile-to-strong transition at ∼220 K to explain the steep decrease in the estimated self-diffusion coefficient below 235 K.

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.

X-ray free-electron lasers (XFELs) with megahertz repetition rate can provide novel insights into structural dynamics of biological macromolecule solutions. However, very high dose rates can lead to beam-induced dynamics and structural changes due to radiation damage. Here, we probe the dynamics of dense antibody protein (Ig-PEG) solutions using megahertz X-ray photon correlation spectroscopy (MHz-XPCS) at the European XFEL. By varying the total dose and dose rate, we identify a regime for measuring the motion of proteins in their first coordination shell, quantify XFEL-induced effects such as driven motion, and map out the extent of agglomeration dynamics. The results indicate that for average dose rates below 1.06 kGy μs⁻¹ in a time window up to 10 μs, it is possible to capture the protein dynamics before the onset of beam induced aggregation. We refer to this approach as correlation before aggregation and demonstrate that MHz-XPCS bridges an important spatio-temporal gap in measurement techniques for biological samples.

Using time-resolved wide-angle X-ray scattering, we investigated the early stages (10 μs–1 ms) of crystallization of supercooled water, obtained by the ultrafast heating of high- and low-density amorphous ice (HDA and LDA) up to a temperature T = 205 K ± 10 K. We have determined that the crystallizing phase is stacking disordered ice (I_sd), with a maximum cubicity of χ = 0.6, in agreement with predictions from molecular dynamics simulations at similar temperatures. However, we note that a growing small portion of hexagonal ice (I_h) was also observed, suggesting that within our timeframe, I_sd starts annealing into I_h. The onset of crystallization, in both amorphous ice, occurs at a similar temperature, but the observed final crystalline fraction in the LDA sample is considerably lower than that in the HDA sample. We attribute this discrepancy to the thickness difference between the two samples.