Thermal Conductivity of Solid Triphenyl Phosphite.

The thermal conductivity, , of solid triphenyl phosphite was measured by using the transient hot-wire method, and its temperature and pressure dependencies were analyzed to understand heat transfer processes in the solid polymorphic phases, as well as in the glass and the exotic glacial state. Phase transformations and the structural order of the phases are discussed, and a transitional pressure-temperature diagram of triphenyl phosphite is presented. The thermal conductivity of both the crystalline and disordered states is described within the theory of two-channel heat transfer by phonons and diffusons in dielectric solids.

Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals.

We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (<30 K) specific heat of the molecular crystal benzophenone and those of several of its fully ordered bromine derivatives. Subsequently, by means of theoretical first-principles methods based on density functional theory, we estimate the corresponding phonon dispersions and vibrational density of states.

Heat capacity anomalies of the molecular crystal 1-fluoro-adamantane at low temperatures.

Disorder-disorder phase transitions are rare in nature. Here, we present a comprehensive low-temperature experimental and theoretical study of the heat capacity and vibrational density of states of 1-fluoro-adamantane (CHF), an intriguing molecular crystal that presents a continuous disorder-disorder phase transition at T = 180 K and a low-temperature tetragonal phase that exhibits fractional fluorine occupancy. It is shown that fluorine occupancy disorder in the low-T phase of 1-fluoro-adamantane gives rise to the appearance of low-temperature glassy features in the corresponding specific heat (i.

Low-Temperature Heat Capacity Anomalies in Ordered and Disordered Phases of Normal and Deuterated Thiophene.

We measured the specific heat of normal (CHS) and deuterated (CDS) thiophene in the temperature interval of 1 ≤ , K ≤ 25. CHS exhibits a metastable phase II and a stable phase V, both with frozen orientational disorder (OD), whereas CDS exhibits a metastable phase II, which is analogous to the OD phase II of CHS and a fully ordered stable phase V. Our measurements demonstrate the existence of a large bump in the heat capacity of both stable and metastable CDS and CHS phases at temperatures of ∼10 K, which significantly departs from the expected Debye temperature behavior of ≈ .

Glassy Anomalies in the Low-Temperature Thermal Properties of a Minimally Disordered Crystalline Solid.

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.

Thermodynamic and Kinetic Fragility of Freon 113: The Most Fragile Plastic Crystal.

We present a dynamic and thermodynamic study of the orientational glass former Freon 113 (1,1,2-trichloro-1,2,2-trifluoroethane, CCl_{2}F-CClF_{2}) 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.

Thermal Conductivity of Triphenyl Phosphite's Liquid, Glassy, and Glacial States.

The thermal conductivity κ and heat capacity per unit volume ρCp of triphenyl phosphite (TPP) were measured under different pressure and temperature conditions, and with time during the sluggish liquid to glacial state transformation at temperatures about 15 K above the glass transition temperature. As the transformation slowly proceeds during several hours, ρCp decreases monotonically from that of the liquid state to a value close to that of the vitrified state. Concurrently, κ increases nonmonotonically with an intermediate local maximum followed by a minimum, before the final rise to a higher κ.

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

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.

Glassy Dynamics versus Thermodynamics: The Case of 2-Adamantanone.

The heat capacity and thermal conductivity of the monoclinic and the fully ordered orthorhombic phases of 2-adamantanone (C10H14O) 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(ω) vibrational frequency distributions measured by means of inelastic neutron scattering.

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

We investigated through noncommercial calorimetry and elastoacoustic Brillouin experiments the phase diagram of n-butanol and measured the specific heat and the thermal conductivity in a wide low-temperature range for its three different states, namely, glass, crystal, and the so-called "glacial" states. The main aim of the work was to shed light on the controversial issue of these allegedly polyamorphic transitions found in some molecular glass-forming liquids, first reported to occur in triphenyl phosphite and later in n-butanol. Our experimental results show that the obtained glacial state in n-butanol is not a homogenous, amorphous state, but rather a mixture of two different coexisting phases, very likely the (frustrated) crystal phase embedded in a disordered, glassy phase.

Thermal conductivity of tetrahydrofuran hydrate.

The thermal conductivity of tetrahydrofuran hydrate has been measured in the temperature region 2-220 K by the steady-state potentiometric method. The temperature dependence of the thermal conductivity exhibits behavior typical of amorphous substances. It is shown that above 100 K the mean free path of the phonons is considerably smaller than the lattice parameter and is no longer dependent on temperature.