Thermal properties and Brillouin-scattering study of glass, crystal, and “glacial” states in n-butanol

Hassaine, Merzak; Riobóo, R. J. Jiménez; Sharapova, I. V.; Korolyuk, O. A.; Кривчиков, А. И.; Ramos, M. A.

doi:10.1063/1.3258645

Cited by 38 publications

(76 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Each scenario captures a certain feature of the glacial phase, but fails in explaining all of the experimental results in a consistent manner. Similar situations are often seen in other candidates of LLTs, such as l-butanol [LLT (13) vs. microcrystallization (40)(41)(42)(43)], confined water [LLT (5) vs. other phenomena (44)(45)(46)], and aqueous solutions [LLT (6, 7) vs. microcrystallization (8,28,47,48)]. For TPP, however, some pieces of experimental evidence supportive of the LLT scenario rather than the microcrystallization scenario have recently been reported (11,12).…”

mentioning

confidence: 92%

Microscopic identification of the order parameter governing liquid–liquid transition in a molecular liquid

Murata

Tanaka

2015

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

View full text Add to dashboard Cite

A liquid-liquid transition (LLT) in a single-component substance is an unconventional phase transition from one liquid to another. LLT has recently attracted considerable attention because of its fundamental importance in our understanding of the liquid state. To access the order parameter governing LLT from a microscopic viewpoint, here we follow the structural evolution during the LLT of an organic molecular liquid, triphenyl phosphite (TPP), by timeresolved small-and wide-angle X-ray scattering measurements. We find that locally favored clusters, whose characteristic size is a few nanometers, are spontaneously formed and their number density monotonically increases during LLT. This strongly suggests that the order parameter of LLT is the number density of locally favored structures and of nonconserved nature. We also show that the locally favored structures are distinct from the crystal structure and these two types of orderings compete with each other. Thus, our study not only experimentally identifies the structural order parameter governing LLT, but also may settle a longstanding debate on the nature of the transition in TPP, i.e., whether the transition is LLT or merely microcrystal formation.liquid-liquid transition | order parameter | X-ray scattering | locally favored structure | transition kinetics L iquid-liquid transition (LLT) is an intriguing phenomenon in which a liquid transforms into another one via a first-order transition. This means that there can be more than two liquid states for a single-component substance. Despite its counterintuitive nature, there have recently been many pieces of experimental and numerical evidence for the existence of LLT, for various liquids such as water (1-5), aqueous solutions (6-8), triphenyl phosphite (9-12), l-butanol (13), phosphorus (14), silicon (15, 16), germanium (17), and Y 2 O 3 -Al 2 O 3 (18,19). This suggests that the LLT may be rather universally observed for various types of liquids. However, none of the LLTs reported so far is free from criticisms (20, 21), mainly because these LLTs take place under experimentally difficult conditions [e.g., at high temperature and pressure (14,15,(17)(18)(19)] or in a supercooled state below the melting point (1-3, 5-7, 9, 10), where the transition is inevitably contaminated by microcrystal formation. The latter is not limited to experiments but arises in numerical simulations, often causing many controversies vs. crystallization (26-28)]. For ST2 water, however, this issue has recently been settled by an extensive simulation study by Palmer et al. (4).One of the hottest and long-standing debates is on the nature of the transition found in a molecular liquid, triphenyl phosphite (TPP), by Kivelson and his coworkers (29). The transition is very easy to access experimentally, because it takes place at ambient pressure and at a temperature range between 230 and 210 K and the transformation speed is slow enough to follow the kinetics. Since the finding of this transition (29, 30), many researchers thus have been inte...

show abstract

mentioning

confidence: 92%

Microscopic identification of the order parameter governing liquid–liquid transition in a molecular liquid

Murata

Tanaka

2015

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

View full text Add to dashboard Cite

show abstract

“…Although several experimental works have been published on TPP [13][14][15][16][17][18][19][21][22][23] and, to a lesser extent, on n-butanol [18,20,24], the very nature of this allegedly new "glacial state" remains controversial. In our previous works, we have investigated [25,26] through calorimetric, thermal conductivity, Brillouin-scattering and X-ray diffraction experiments the phase diagram of n-butanol, studying its three different states, namely glass, crystal and so-called "glacial" states. Our experimental results showed that the obtained "glacial state" in n-butanol is not a homogenous, amorphous state, but rather a mixture of two different coexisting phases: an ensemble of (frustrated) nanocrystallites embedded in a disordered phase.…”

Section: Introductionmentioning

confidence: 99%

Low-temperature properties of glassy and crystalline states of n-butanol

Кривчиков

Hassaine

Sharapova

et al. 2011

Journal of Non-Crystalline Solids

Self Cite

View full text Add to dashboard Cite

“…34 For higher temperatures (20-260 K), we followed a quasi-adiabatic continuous method previously implemented, which has been successfully employed in glass-forming liquids above liquid-N 2 temperatures and in solids above liquid-He temperatures. [34][35][36] In this quasi-adiabatic continuous method, the heat capacity is determined from a dual (cooling + heating) experiment, typically using rates around ±1 K/min, being the distinctive behavior of the sample cell between both runs which provides the measurement of its heat capacity. 34,36 The heat capacity of the empty cell is measured in a different run to subtract the addenda contribution.…”

Section: Methodsmentioning

confidence: 99%

Thermal properties of halogen-ethane glassy crystals: Effects of orientational disorder and the role of internal molecular degrees of freedom

Vdovichenko

Кривчиков

Korolyuk

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

The thermal conductivity, specific heat, and specific volume of the orientational glass former 1,1,2-trichloro-1,2,2-trifluoroethane (CCl 2 F-CClF 2 , F-113) have been measured under equilibrium pressure within the low-temperature range, showing thermodynamic anomalies at ca. 120, 72, and 20 K. The results are discussed together with those pertaining to the structurally related 1,1,2,2-tetrachloro-1,2-difluoroethane (CCl 2 F-CCl 2 F, F-112), which also shows anomalies at 130, 90, and 60 K. The rich phase behavior of these compounds can be accounted for by the interplay between several of their degrees of freedom. The arrest of the degrees of freedom corresponding to the internal molecular rotation, responsible for the existence of two energetically distinct isomers, and the overall molecular orientation, source of the characteristic orientational disorder of plastic phases, can explain the anomalies at higher and intermediate temperatures, respectively. The soft-potential model has been used as the framework to describe the thermal properties at low temperatures. We show that the low-temperature anomaly of the compounds corresponds to a secondary relaxation, which can be associated with the appearance of Umklapp processes, i.e., anharmonic phononphonon scattering, that dominate thermal transport in that temperature range. C 2015 AIP Publishing LLC. [http://dx

show abstract

Thermal properties and Brillouin-scattering study of glass, crystal, and “glacial” states in n-butanol

Cited by 38 publications

References 34 publications

Microscopic identification of the order parameter governing liquid–liquid transition in a molecular liquid

Microscopic identification of the order parameter governing liquid–liquid transition in a molecular liquid

Low-temperature properties of glassy and crystalline states of n-butanol

Thermal properties of halogen-ethane glassy crystals: Effects of orientational disorder and the role of internal molecular degrees of freedom

Contact Info

Product

Resources

About