RESUMEN
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. Our results reveal two possible mechanisms for the emergence of the BP-like anomaly: (i) acoustic-optic phonon avoided crossing, which gives rise to a pseudo-van Hove singularity in the acoustic phonon branches, and (ii) piling up of low-frequency optical phonons, which are quasi degenerate with longitudinal acoustic modes and lead to a surge in the vibrational density of states at low energies.
RESUMEN
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 (C10H15F), 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.e., "boson peak" -BP-) and vibrational density of states. We identify the inflation of low-energy optical modes as the main responsible for the appearance of such glassy heat-capacity features and propose a straightforward correlation between the first localized optical mode and maximum BP temperature for disordered molecular crystals (either occupational or orientational). Thus, the present study provides new physical insights into the possible origins of the BP appearing in disordered materials and expands the set of molecular crystals in which "glassy-like" heat-capacity features have been observed.
RESUMEN
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. The properties of the ultimately formed glacial state depend on the thermal history, which implies that the state formed under these conditions is a heterogeneous mixture of nanocrystals and mainly amorphous-like solid, and that the relative amount and microstructure depend on the conditions of the transformation. The nonmonotonic changes in phonon propagation during the liquid to glacial transformation suggest microstructural changes which are consistent with a liquid-liquid transformation and sluggish growth of nanocrystals within amorphous-like solid domains. The isobaric thermal conductivity of the as-formed glacial state shows a reversible step increase, just prior to crystallization on heating, which deviates from the typical behavior of glasses, liquids, and crystals. An increase in pressure shifts the step to higher temperatures and suppresses crystallization, which reveals another reversible rise in κ and Cp. These results show that increased molecular mobility in the glacial state increases and suggest reduced thermal resistance at boundaries or that the motions carry heat.
RESUMEN
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.