We prepared bulk samples of supercooled liquid water under pressure by isochoric heating of high-density amorphous ice to temperatures of 205 ± 10 kelvin, using an infrared femtosecond laser. Because the sample density is preserved during the ultrafast heating, we could estimate an initial internal pressure of 2.5 to 3.5 kilobar in the high-density liquid phase. After heating, the sample expanded rapidly, and we captured the resulting decompression process with femtosecond x-ray laser pulses at different pump-probe delay times. A discontinuous structural change occurred in which low-density liquid domains appeared and grew on time scales between 20 nanoseconds to 3 microseconds, whereas crystallization occurs on time scales of 3 to 50 microseconds. The dynamics of the two processes being separated by more than one order of magnitude provides support for a liquid-liquid transition in bulk supercooled water.
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.
Amorphous ice is
commonly used as a noncrystalline matrix for protecting
sensitive biological samples in cryogenic electron microscopy (cryo-EM).
The amorphization process of water is complex, and at least two amorphous
states of different densities are known to exist, high- and low-density
amorphous ices (HDA and LDA). These forms are considered to be the
counterparts of two distinct liquid states, namely, high- and low-density
liquid water. Herein, we investigate the HDA to LDA transition using
electron diffraction and cryo-EM. The observed phase transition is
induced by the impact of electrons, and we discuss two different mechanisms,
namely, local heating and beam-induced motion of water molecules.
The temperature increase is estimated by comparison with X-ray scattering
experiments on identically prepared samples. Our results suggest that
HDA, under the conditions used in our cryo-EM measurements, is locally
heated above its glass-transition temperature.
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