Liquid-Liquid Transition in the Molecular Liquid Triphenyl Phosphite

Tanaka, Hajime; Kurita, Rei; Mataki, Hiroshi

doi:10.1103/physrevlett.92.025701

Cited by 196 publications

(282 citation statements)

References 14 publications

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“…[10][11][12][13] There are some striking similarities between the slushy state of supercooled glycerol and the glacial state of TPP. For example, the rheological experiments on the glacial state of TPP shows that the maximum G′ is order of 10 6 Pa, 12 close to 10 7 Pa of the slushy phase of glycerol. Both moduli are far below their respective crystalline moduli.…”

Section: Discussionmentioning

confidence: 99%

Aging and Solidification of Supercooled Glycerol

et al. 2010

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We experimentally investigate the solidification of supercooled glycerol during aging that has recently been observed by Zondervan et al. We find that a slow cooling at 5 K/h prior to the aging is required for solidification to take place. Furthermore, we show that the time of onset depends strongly on the aging temperature which we varied between 220 and 240 K. The nature of the solid phase remains unclear. The experiments show that upon heating the solid glycerol melts at the crystal melting point. However, rheology experiments in the plate-plate geometry revealed the growth of a soft, slushlike phase that is distinct from a crystal grown by seeding at the same aging temperature. The slushlike glycerol grows from a nucleation point at almost the same speed as a seeded crystal quenched to the same temperature, but its shear modulus is almost 2 orders of magnitude lower than the crystal phase, which we measure independently. While solidification was reproducible in the Couette geometry, it was not in the plate-plate geometry.

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Section: Discussionmentioning

confidence: 99%

Aging and Solidification of Supercooled Glycerol

et al. 2010

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“…A first-order transition has been reported to occur in TPP at ambient pressure a few degrees Kelvin above T g (40)(41)(42). To our knowledge, a liquid-to-liquid transition occurring below the conventional T g has not been previously shown.…”

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confidence: 86%

Physical vapor deposition as a route to hidden amorphous states

Dawson

Kearns

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

106

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Stable glasses of indomethacin (IMC) were prepared by using physical vapor deposition. Wide-angle X-ray scattering measurements were performed to characterize the average local structure. IMC glasses prepared at a substrate temperature of 0.84 Tg (where Tg is the glass transition temperature) and a deposition rate of 0.2 nm/s show a broad, high-intensity peak at low q values that is not present in the supercooled liquid or melt-quenched glasses. When annealed slightly above Tg, the new WAXS pattern transforms into the melt-quenched glass pattern, but only after very long annealing times. For a series of samples prepared at the lowest deposition rate, the new local packing arrangement is present only for deposition temperatures below Tg ؊20 K, suggesting an underlying first-order liquid-to-liquid phase transition.entropy ͉ glass ͉ liquid-liquid transition ͉ supercooled ͉ X-ray scattering I f a liquid is cooled to just below its melting point, one of two outcomes will be observed. If the liquid readily forms crystal nuclei, then crystals will form and grow. Otherwise, the system will remain in the now metastable liquid state. In the absence of crystallization, further cooling of this supercooled liquid will result in slower dynamics, and eventually, the dynamics will become so slow that the supercooled liquid cannot maintain its equilibrium state (1). At this glass transition temperature (T g ), the system properties deviate from the properties of the supercooled liquid, and a glass is formed.Whereas the liquid-to-crystal transition is a first-order phase transition, the supercooled liquid-to-glass transition is a kinetic event based on relaxation times growing rapidly as the temperature is decreased. A great deal of recent work has been concentrated on understanding the nature of slow dynamics in supercooled liquids (2-11). As a liquid is cooled at lower rates, more time is given for the system to find equilibrium, and thus, T g decreases. For many organic liquids, T g decreases 3-4 K for every order-of-magnitude decrease in the cooling rate. Because there is a practical limit as to how slowly a sample can be cooled, a glass always forms upon cooling (if crystallization does not occur).What if one could cool a supercooled liquid extremely slowly such that equilibrium was always maintained? There are good reasons to believe that something interesting must occur. In 1948, Kauzmann discussed the consequences of very slow cooling for the entropy of a supercooled liquid, which identified the so-called Kauzmann entropy crisis (12). For some liquids, if the entropy is extrapolated to low temperature, it becomes equal to that of the crystal not too far below the conventional T g ; further extrapolation leads to a negative entropy above absolute zero in violation of the third law of thermodynamics. Because this is impossible, it is generally assumed that the extrapolation that produces this crisis must be incorrect, and thus something interesting must occur when a supercooled liquid is cooled very slowly. Several theories...

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“…Indeed, for the highly nonequilibrium path that we follow, it is not evident how the LDA-to-HDA transformation should proceed, i.e., whether it should exhibit spontaneous nucleation, as in equilibrium liquid-to-crystal first-order phase transitions, or if it should exhibit spinodal decomposition, with no distinct phase separation. Experiments performed by Tanaka and collaborators with triphenylphosphite (TPP) 76 and n-butanol, 77 as well as mixtures of glycerol and water 78 (where LDL and HDL have same composition), indicate the existence of a LLPT. In all these works, it was observed that, in some cases, the LLPT exhibited spontaneous nucleation, while in others, it showed spinodal decomposition.…”

Section: B Structure Of Lda and Hdamentioning

confidence: 99%

Pressure-induced transformations in computer simulations of glassy water

Chiu

Starr

Giovambattista

2013

The Journal of Chemical Physics

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Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and highdensity amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a lowdensity and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water. © 2013 AIP Publishing LLC.

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Liquid-Liquid Transition in the Molecular Liquid Triphenyl Phosphite

Cited by 196 publications

References 14 publications

Aging and Solidification of Supercooled Glycerol

Aging and Solidification of Supercooled Glycerol

Physical vapor deposition as a route to hidden amorphous states

Pressure-induced transformations in computer simulations of glassy water

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