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- Esmaeildoost, Niloofar, et al.
(författare)
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Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water
- 2021
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 155:21, s. 214501-214501
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Tidskriftsartikel (refereegranskat)abstract
- 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 Å-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 (q2). We found that q2 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 q2 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.
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| 2. |
- Amann-Winkel, Katrin, et al.
(författare)
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Liquid-liquid phase separation in supercooled water from ultrafast heating of low-density amorphous ice
- 2023
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Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 14:1
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Tidskriftsartikel (refereegranskat)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 mu s. Obtaining experimental evidence of a liquid-liquid phase transition in supercooled water is challenging due to the rapid crystallization. Here the authors drive low-density amorphous ice to the conditions of liquid-liquid coexistence using ultrafast laser heating and observe the liquid-liquid phase transition with femtosecond x-ray laser pulses.
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| 3. |
- Ladd-Parada, Marjorie, 1985-, et al.
(författare)
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Following the Crystallization of Amorphous Ice after Ultrafast Laser Heating
- 2022
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 126:11, s. 2299-2307
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Tidskriftsartikel (refereegranskat)abstract
- 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 (Isd), 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 (Ih) was also observed, suggesting that within our timeframe, Isd starts annealing into Ih. 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.
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| 4. |
- Li, Hailong, et al.
(författare)
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Long-Range Structures of Amorphous Solid Water
- 2021
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 125:48, s. 13320-13328
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Tidskriftsartikel (refereegranskat)abstract
- High-energy X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) of amorphous solid water (ASW) were studied during vapor deposition and the heating process. From the diffraction patterns, the oxygen–oxygen pair distribution functions (PDFs) were calculated up to the eighth coordination shell and an r = 23 A°. The PDF of ASW obtained both during vapor deposition at 80 K as well as the subsequent heating are consistent with that of low-density amorphous ice. The formation and temperature-induced collapse of micropores were observed in the XRD data and in the FTIR measurements, more specifically, in the OH stretch and the dangling mode. Above 140 K, ASW crystallizes into a stacking disordered ice, Isd. It is observed that the fourth, fifth, and sixth peaks in the PDF, corresponding to structural arrangements between 8 and 12 Å, are the most sensitive to the onset of crystallization.
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| 9. |
- Späh, Alexander, 1989-
(författare)
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X-Ray Investigations of the Liquid-Liquid Critical Point Hypothesis in Supercooled Water
- 2020
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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