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We present a dynamic and thermodynamic study of the orientational glass former Freon 113 (1,1,2-trichloro-1,2,2-trifluoroethane, CCl2F-CClF2) in order to analyze its kinetic and thermodynamic fragilities. Freon 113 displays internal molecular degrees of freedom that promote a complex energy landscape. Experimental specific heat and its microscopic origin, the vibrational density of states from inelastic neutron scattering, together with the orientational dynamics obtained by means of dielectric spectroscopy have revealed the highest fragility value, both thermodynamic and kinetic, found for this orientational glass former. The excess in both Debye-reduced specific heat and density of states (boson peak) evidences the existence of glassy low-energy excitations. We demonstrate that early proposed correlations between the boson peak and the Debye specific heat value are elusive as revealed by the clear counterexample of the studied case.

The low-temperature thermal and transport properties of an unusual kind of crystal exhibiting minimal molecular positional and tilting disorder have been measured. The material, namely, low-dimensional, highly anisotropic pentachloronitrobenzene has a layered structure of rhombohedral parallel planes in which the molecules execute large-amplitude in-plane as well as concurrent out-of-plane librational motions. Our study reveals that low-temperature glassy anomalies can be found in a system with minimal disorder due to the freezing of (mostly in-plane) reorientational jumps of molecules between equivalent crystallographic positions with partial site occupation. Our findings will pave the way to a deeper understanding of the origin of the above-mentioned universal glassy properties at low temperature.

The heat capacity and thermal conductivity of the monoclinic and the fully ordered orthorhombic phases of 2-adamantanone (CHO) have been measured for temperatures between 2 and 150 K. The heat capacities for both phases are shown to be strikingly close regardless of the site disorder present in the monoclinic crystal which arises from the occupancy of three nonequivalent sites for the oxygen atom. The heat capacity curves are also well accounted for by an evaluation carried out within the harmonic approximation in terms of the g vibrational frequency distributions measured by means of inelastic neutron scattering. Such spectral functions show however a significant excess of low frequency modes for the crystal showing statistical disorder. In contrast, large differences are found for the thermal conductivity which contrary to what could be expected, shows the substitutionally disordered crystal to exhibit better heat transport properties than the fully ordered orthorhombic phase. Such an anomalous behavior is understood from examination of the crystalline structure of the orthorhombic phase which leads to very strong scattering of heat-carrying phonons due to grain boundary effects able to yield a largely reduced value of the conductivity as well as to a plateau-like feature at intermediate temperatures which contrasts with a bell-shaped maximum shown by data pertaining the disordered crystal. The relevance of the present findings within the context of glassy dynamics of the orientational glass state is finally discussed.

© 2015 AIP Publishing LLC. The thermal conductivity, specific heat, and specific volume of the orientational glass former 1,1,2-trichloro-1,2,2-trifluoroethane (CCl2F–CClF2, 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 (CCl2F–CCl2F, 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 phonon-phonon scattering, that dominate thermal transport in that temperature range.

© 2014 Elsevier B.V. All rights reserved. The thermal conductivity of CBrnCl4 -n,(n = 0,1,2) and 2-adamantanone (C10H14O) crystals which exhibit substitutional disorder has been measured for temperatures between 2 K and 150 K. Such temperatures comprise signatures of dynamical processes involving the site occupancy of the chlorine and bromine atoms for CBrnCl4 -n,(n = 0,1,2) and the oxygen atom for (C10H14O), as it has been revealed by both, calorimetry and spectroscopic techniques. The data analysis is carried out in terms of several phonon scattering channels contributing to a resistive relaxation rate which can be represented by two contributions due to propagating phonons whose mean-free path exceeds half the phonon wavelength as well as a term attributed to localized short wavelength modes. The implications of the present findings for studies pertaining to glassy dynamics are briefly discussed.

The thermal conductivity κ(T ) of the fully ordered stable phase II, the metastable phase III, the orientationally disordered (plastic) phase I, as well as the nonergodic orientational glass (OG) phase, of the glass former cyclohexanol (C6H11OH) has been measured under equilibrium vapor pressure within the 2–200 K temperature range. The main emphasis is here focused on the influence of the conformational disorder upon the thermal properties of this material. Comparison of results with those regarding cyanoclyclohexane (C6H11CN), a chemically related compound, serves to quantify the role played by the terminal groups -OH and -CN on the phonon scattering processes. The picture that emerges shows that motions of such groups do play a minor role as scattering centers, both within the low-temperature orientationally ordered phases as well as in the OG states. The results are analyzed within the Debye-Peierls relaxation time model for isotropic solids comprising mechanisms for long-wave phonon scattering within the OG and orientational ordered low-temperature phases, as well as others arising from localized short-wavelength vibrational modes as pictured by the Cahill-Pohl model. By means of complementary neutron and Raman scattering we show that in the OG state the energy landscapes for both compounds are very similar., Postprint (published version)

The thermal conductivity κ(T) of the fully ordered stable phase II, the metastable phase III, the orientationally disordered (plastic) phase I, as well as the nonergodic orientational glass (OG) phase, of the glass former cyclohexanol (C 6H 11OH) has been measured under equilibrium vapor pressure within the 2-200 K temperature range. The main emphasis is here focused on the influence of the conformational disorder upon the thermal properties of this material. Comparison of results with those regarding cyanoclyclohexane (C 6H 11CN), a chemically related compound, serves to quantify the role played by the terminal groups -OH and -CN on the phonon scattering processes. The picture that emerges shows that motions of such groups do play a minor role as scattering centers, both within the low-temperature orientationally ordered phases as well as in the OG states. The results are analyzed within the Debye-Peierls relaxation time model for isotropic solids comprising mechanisms for long-wave phonon scattering within the OG and orientational ordered low-temperature phases, as well as others arising from localized short-wavelength vibrational modes as pictured by the Cahill-Pohl model. By means of complementary neutron and Raman scattering we show that in the OG state the energy landscapes for both compounds are very similar. © 2012 American Physical Society.

Postprint (published version)

The thermal conductivity k(T) of the orientational glass state of 1,2-difluoro-1,1,2,2-tetrachloroethane (CFCl2-CFCl2, Freon 112) and cyanocyclohexane (C6H11CN) has been measured under equilibrium pressure within the temperature range 2-100 K. The results show that the soft-potential model is able to account for low-temperature data and, indeed, quantitative agreement of all data considered is found within this realm. The details beyond such temperatures are heavily dependent on chemical details and a large plateau is observed for Freon 112 which is rationalized in terms of resonant scattering of phonons by simple oscillators. Such a view is given additional support by the presence of a strong low-frequency feature in the generalized frequency spectrum of the former material as proven by inelastic neutron-scattering spectroscopy. ©2010 The American Physical Society

The thermal conductivity of two molecular glasses (ethanol and 1-propanol) decrease with increasing temperature up to their glass transitions at Tg 97 and 98 K, respectively. Within their supercooled liquid phases, the conductivity increases with rising temperature up to a maximum which roughly coincides with the liquidus (or melting temperatures Tm 159 K and Tm 149 K, respectively). From there on, the conductivity decreases with increasing temperature, a behavior common to most liquids examined so far, exception made of liquid water. The origin of the rather different dependencies with temperature of thermal transport is understood as a competition between phonon-assisted and diffusive transport effects which are amenable to experiments using high resolution quasielastic neutron scattering and visible and ultraviolet Brillouin light-scattering spectroscopies. © 2007 The American Physical Society.

The thermal conductivity of all three disordered solid phases of ethyl alcohol has been measured. That for the orientationally disordered bcc phase is found to be remarkably close to that for the structurally amorphous solid, especially at low temperatures. The results, which emphasize the role of orientational disorder in phonon scattering, are discussed with the aid of computer simulations on single-crystalline models of both bcc and monoclinic crystals. © 2006 The American Physical Society.