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

Abstract 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.