Response to Comment on “Maxima in the thermodynamic response and correlation functions of deeply supercooled water”

Caupin et al. have raised several issues regarding our recent paper on maxima in thermodynamic response and correlation functions in deeply supercooled water. We show that these issues can be addressed without affecting the conclusion of the paper.113Ysciescopu

Melting Domain Size and Recrystallization Dynamics of Ice Revealed by Time-Resolved X-ray Scattering

The phase transition between water and ice is ubiquitous and one of the most important phenomena in nature. Here, we performed time-resolved x-ray scattering experiments capturing the melting and recrystallization dynamics of ice. The ultrafast heating of ice I is induced by an IR laser pulse and probed with an intense x-ray pulse, which provided us with direct structural information on different length scales. From the wide-angle x-ray scattering (WAXS) patterns, the molten fraction, as well as the corresponding temperature at each delay, were determined. The small-angle x-ray scattering (SAXS) patterns, together with the information extracted from the WAXS analysis, provided the time-dependent change of the size and the number of the liquid domains. The results show partial melting (~13 %) and superheating of ice occurring at around 20 ns. After 100 ns, the average size of the liquid domains grows from about 2.5 nm to 4.5 nm by the coalescence of approximately six adjacent domains. Subsequently, we capture the recrystallization of the liquid domains, which occurs on microsecond timescales due to the cooling by heat dissipation and results to a decrease of the average liquid domain size

X-Ray Investigations of the Liquid-Liquid Critical Point Hypothesis in Supercooled Water

This thesis presents experimental x-ray scattering studies on supercooled liquid water. A liquid-liquid transition between two structurally distinct configurations has been found in deeply supercooled water, indicating the existence of a liquid- liquid critical point. The experiments were performed at large-scale x-ray facilities, mostly using free electron x-ray lasers including PAL-XFEL in Korea, SACLA in Japan, LCLS in the USA, SwissFEL in Switzerland and European XFEL in Germany, as well as using synchrotrons including APS in the USA, PETRA III in Germany and ESRF in France. Two conceptually different experimental approaches have been used to investigate the metastable phase of supercooled water. The first approach is based on rapid evaporative cooling of μm-sized water droplets that are injected into a vacuum chamber. Using this method, supercooled liquid water samples with temperatures down to approximately 227 K have been obtained, with the lowest temperature limited by homogeneous ice crystallization occurring after just a few milliseconds. In a second approach, structurally arrested high-pressure and therefore high-density amorphous ice samples are heated by an ultrafast infrared laser pulse. The fast heating melts the ice into a corresponding high-density liquid. At short time delays between the heating laser pulse and a subsequent x-ray probe pulse, the supercooled liquefied sample still experiences the high internal pressure of the initial state. At longer pump-probe delay times the supercooled water sample releases its internal pressure through structural relaxation. Hence, varying the pump-probe delay allows to probe the sample at different pressures. Together, these two approaches have been used to access a region within the metastable phase diagram of supercooled water that has previously been inaccessible. Using elastic x-ray scattering measurements as a structural probe of the liquid, we identified the existence of a liquid-liquid phase transition in deeply supercooled water. The observed phase transition is interpreted as the transition between a high-density and a low-density liquid phase. At high pressure this phase transition is discontinuous or first-order like, featuring a characteristic double-peak feature in the observed x-ray scattering intensity of the first diffraction maxima. At ambient pressure, however, we observe a continuous shift of the first diffraction maxima that is consistent with a continuous or second-order phase transition between the two liquids. Further evidence of a continuous phase transition at ambient pressure is seen in the temperature dependent maxima of the measured correlation length, isothermal compressibility and heat capacity, which indicate the existence of a Widom line. In summary, the experiments support the existence of a liquid-liquid critical point where the experimentally observed Widom line and phase coexistence line would both meet. The main result, however, is the first experimental observation of a liquid-liquid transition within a pure liquid.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 7: Manuscript. Paper 8: Manuscript. Paper 9: Manuscript. Paper 10: Manuscript.</p

Fünf Punkte, warum Lärm in Schulen kein Luxusproblem ist

Schulunterricht soll mit Diktaten, Gruppenarbeiten und Referaten den Lernerfolg sichern. Trotz allen Wandels der äußeren Formen von Schulen und Schulräumen bleibt Sprache jedoch die Konstante bei der Wissensvermittlung. 45-70% einer Schulstunde vergehen damit, dass gesprochen und zugehört wird. Eine gute Akustik in Klassenräumen ist also keine Option, sondern eine Notwendigkeit, wenn Lernfortschritt und Chancengleichheit in Schulen ernst genommen werden

Temperature-Independent Nuclear Quantum Effects on the Structure of Water

Nuclear quantum effects (NQEs) have a significant influence on the hydrogen bonds in water and aqueous solutions and have thus been the topic of extensive studies. However, the microscopic origin and the corresponding temperature dependence of NQEs have been elusive and still remain the subject of ongoing discussion. Previous x-ray scattering investigations indicate that NQEs on the structure of water exhibit significant temperature dependence [Phys. Rev. Lett. 94, 047801 (2005)]. Here, by performing wide-angle x-ray scattering of H2O and D2O droplets at temperatures from 275 K down to 240 K, we determine the temperature dependence of NQEs on the structure of water down to the deeply supercooled regime. The data reveal that the magnitude of NQEs on the structure of water is temperature independent, as the structure factor of D2O is similar to H2O if the temperature is shifted by a constant 5 K, valid from ambient conditions to the deeply supercooled regime. Analysis of the accelerated growth of tetrahedral structures in supercooled H2O and D2O also shows similar behavior with a clear 5 K shift. The results indicate a constant compensation between NQEs delocalizing the proton in the librational motion away from the bond and in the OH stretch vibrational modes along the bond. This is consistent with the fact that only the vibrational ground state is populated at ambient and supercooled conditions.116sciescopu

Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water

The structural changes of water upon deep supercooling were studied through wide-angle x-ray scattering at SwissFEL. The experimental setup had a momentum transfer range of 4.5 angstrom(-1), which covered the principal doublet of the x-ray structure factor of water. The oxygen-oxygen structure factor was obtained for temperatures down to 228.5 +/- 0.6 K. Similar to previous studies, the second diffraction peak increased strongly in amplitude as the structural change accelerated toward a local tetrahedral structure upon deep supercooling. We also observed an anomalous trend for the second peak position of the oxygen-oxygen structure factor (q(2)). We found that q(2) exhibits an unprecedented positive partial derivative with respect to temperature for temperatures below 236 K. Based on Fourier inversion of our experimental data combined with reference data, we propose that the anomalous q(2) shift originates from that a repeat spacing in the tetrahedral network, associated with all peaks in the oxygen-oxygen pair-correlation function, gives rise to a less dense local ordering that resembles that of low-density amorphous ice. The findings are consistent with that liquid water consists of a pentamer-based hydrogen-bonded network with low density upon deep supercooling. (C) 2021 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).11Ysciescopu

Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry

Knowledge of the temperature dependence of the isobaric specific heat (Cp) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in Cp 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 Cp, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The Cp maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the Cp measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.QC 20220317</p