Is It Possible to Follow the Structural Evolution of Water in “No-Man’s Land” Using a Pulsed-Heating Procedure?

Ribeiro, Ingrid de Almeida; Koning, Maurice de; Molinero, Valeria

doi:10.1021/acs.jpclett.1c04106

Cited by 3 publications

(6 citation statements)

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“…HQW was prepared by transiently heating the water film to T max ≈ 300 K, using pulsed laser heating. However, due to the finite cooling rate of the experimental technique and rapid equilibration of mildly supercooled water, we expect that HQW represents the quenched structure of water at ∼235 K and not the quenched structure at 300 K. 34,35 Recent MD simulations using the TIP4P/ICE model and a similar heating and cooling protocol to our pulsed heating experiments found that the structure of the quenched film did not change for T max > 260 K. 73 Using the temperature of maximum density scaling suggested by Limmer and Chandler for liquid water models, 74 260 K for TIP4P/ICE corresponds to ∼244 K for real water, 75 which is in reasonable agreement with the observations. Due to the nature of our measurements, the HDL-and LDL-like composition of the prepared HQW remains unknown; however, MD simulations suggest that there is substantial annealing of the prepared HQW toward LDA-like basins during the cooling from 300 K to the base temperature.…”

Section: The Journal Of Physical Chemistry Bmentioning

confidence: 75%

“…Using the temperature of maximum density scaling suggested by Limmer and Chandler for liquid water models, 260 K for TIP4P/ICE corresponds to ∼244 K for real water, which is in reasonable agreement with the observations. Due to the nature of our measurements, the HDL- and LDL-like composition of the prepared HQW remains unknown; however, MD simulations suggest that there is substantial annealing of the prepared HQW toward LDA-like basins during the cooling from 300 K to the base temperature …”

Section: Experimental Methodsmentioning

confidence: 99%

“…Although Geissler and co-workers have shown that temperature-dependent vibrational spectra can contain “artificial” isosbestic points that do not necessarily imply multiple species, , by collecting all spectra at 70 K we were able to remove this ambiguity from our interpretation of the spectral changes. In addition, the spectra of the kinetically arrested films are related to the inherent structures explored in MD simulations, ,,,, particularly at temperatures below ∼235 K where recent simulations with the TIP4P/ICE model indicated that the structure factor of water at steady state when prepared by pulsed heating was nearly equivalent to the structure factor of the inherent states of isothermally prepared water samples …”

Section: Experimental Methodsmentioning

confidence: 99%

“…Due to the nature of our measurements, the HDL-and LDL-like composition of the prepared HQW remains unknown; however, MD simulations suggest that there is substantial annealing of the prepared HQW toward LDA-like basins during the cooling from 300 K to the base temperature. 73 Liquid Structure via RAIRS. The structural changes of the supercooled water were monitored with the FTIR spectrometer, as was carried out previously.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…In addition, the spectra of the kinetically arrested films are related to the inherent structures explored in MD simulations, 3,4,46,88,89 particularly at temperatures below ∼235 K 29 where recent simulations with the TIP4P/ICE model indicated that the structure factor of water at steady state when prepared by pulsed heating was nearly equivalent to the structure factor of the inherent states of isothermally prepared water samples. 73 Two-Temperature Protocol. To investigate the out-ofequilibrium properties in transiently heated water, twotemperature jump heating sequences, reminiscent of the seminal work of Kovacs, 56,58 were implemented, as shown schematically in Figure 1.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

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Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Kringle

Kay

2023

J. Phys. Chem. B

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Understanding the properties of supercooled water is important for developing a comprehensive theory for liquid water and amorphous ices. Because of rapid crystallization for deeply supercooled water, experiments on it are typically carried out under conditions in which the temperature and/or pressure are rapidly changing. As a result, information on the structural relaxation kinetics of supercooled water as it approaches (metastable) equilibrium is useful for interpreting results obtained in this experimentally challenging region of phase space. We used infrared spectroscopy and the fast time resolution obtained by transiently heating nanoscale water films to investigate relaxation kinetics (aging) in supercooled water. When the structural relaxation of the water films was followed using a temperature jump protocol analogous to the classic experiments of Kovacs, similar memory effects were observed. In particular, after suitable aging at one temperature, water’s structure displayed an extremum versus the number of heat pulses upon changing to a second temperature before eventually relaxing to a steady-state structure characteristic of that temperature. A random double well model based on the idea of dynamic heterogeneity in supercooled water accounts for the observations.

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Section: The Journal Of Physical Chemistry Bmentioning

confidence: 75%

Section: Experimental Methodsmentioning

confidence: 99%

Section: Experimental Methodsmentioning

confidence: 99%

Section: ■ Experimental Methodsmentioning

confidence: 99%

Section: ■ Experimental Methodsmentioning

confidence: 99%

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Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Kringle

Kay

2023

J. Phys. Chem. B

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Nucleation and growth of crystalline ices from amorphous ices

Tonauer

Fidler

Giebelmann

et al. 2023

The Journal of Chemical Physics

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We here review mostly experimental and some computational work devoted to nucleation in amorphous ices. In fact, there are only a handful of studies in which nucleation and growth in amorphous ices are investigated as two separate processes. In most studies, crystallization temperatures T x or crystallization rates R JG are accessed for the combined process. Our Review deals with different amorphous ices, namely, vapor-deposited amorphous solid water (ASW) encountered in many astrophysical environments; hyperquenched glassy water (HGW) produced from μm-droplets of liquid water; and low density amorphous (LDA), high density amorphous (HDA), and very high density amorphous (VHDA) ices produced via pressure-induced amorphization of ice I or from high-pressure polymorphs. We cover the pressure range of up to about 6 GPa and the temperature range of up to 270 K, where only the presence of salts allows for the observation of amorphous ices at such high temperatures. In the case of ASW, its microporosity and very high internal surface to volume ratio are the key factors determining its crystallization kinetics. For HGW, the role of interfaces between individual glassy droplets is crucial but mostly neglected in nucleation or crystallization studies. In the case of LDA, HDA, and VHDA, parallel crystallization kinetics to different ice phases is observed, where the fraction of crystallized ices is controlled by the heating rate. A key aspect here is that in different experiments, amorphous ices of different “purities” are obtained, where “purity” here means the “absence of crystalline nuclei.” For this reason, “preseeded amorphous ice” and “nuclei-free amorphous ice” should be distinguished carefully, which has not been done properly in most studies. This makes a direct comparison of results obtained in different laboratories very hard, and even results obtained in the same laboratory are affected by very small changes in the preparation protocol. In terms of mechanism, the results are consistent with amorphous ices turning into an ultraviscous, deeply supercooled liquid prior to nucleation. However, especially in preseeded amorphous ices, crystallization from the preexisting nuclei takes place simultaneously. To separate the time scales of crystallization from the time scale of structure relaxation cleanly, the goal needs to be to produce amorphous ices free from crystalline ice nuclei. Such ices have only been produced in very few studies.

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Structural relaxation of water during rapid cooling from ambient temperatures

Kringle

Kay

2023

The Journal of Chemical Physics

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Experiments investigating the properties of deeply supercooled liquid water are needed to develop a comprehensive understanding of water’s anomalous properties. One approach involves transiently heating nanoscale water films into the supercooled region for several nanoseconds at a time and then interrogating the water films after they have quenched to cryogenic temperatures. To relate the results obtained with this approach to other experiments and simulations on supercooled water, it is important to understand how closely the quenched structure tracks the (metastable) equilibrium structure of water as a function of the transient heating temperature. A key step involves quantifying the extent to which water that is transiently heated to ambient temperatures [hyperquenched water (HQW)] subsequently relaxes toward the structure of low-density amorphous (LDA) ice as it cools. We analyzed the infrared reflection–absorption spectra of LDA, HQW, and crystalline ice films to determine their complex indices of refraction. With this information, we estimate that HQW retains ∼50%–60% of a structural motif characteristic of water at high temperatures with the balance comprised of a low-temperature motif. This result, along with results from x-ray diffraction experiments on water and amorphous ices, allows one to quantify the fraction of the high-temperature motif at approximately zero pressure as a function of temperature from 150 to 350 K.

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Is It Possible to Follow the Structural Evolution of Water in “No-Man’s Land” Using a Pulsed-Heating Procedure?

Abstract: The anomalous increase in compressibility and heat capacity of supercooled water has been attributed to its structural transformation of into a fourcoordinated liquid. Experiments revealed that κ T and C p peak at T W thermo ≈ 229 K [Kim et al.

Cited by 3 publications

References 43 publications

Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Nucleation and growth of crystalline ices from amorphous ices

Structural relaxation of water during rapid cooling from ambient temperatures

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