ABSTRACT
The vibrational and thermodynamic properties of energetic materials (EMs) are critical to understand their structure responses at finite temperature. In this work, the zero-point energy and temperature effects are incorporated into dispersion-corrected density functional theory to improve the calculated accuracy for vibrational responses and thermodynamic behaviors of 3-nitro-1,2,4-triazole-5-one (NTO). Based on temperature-dependent Raman spectroscopy, the emergence and disappearance of new peaks as well as discontinuous Raman shifts indicate the distinct changes of molecular configuration and intermolecular interactions within the temperature of 250-350 K. From Hirshfeld surface and structure analysis, the subtle changes of intermolecular hydrogen bonds (HBs) related with the shrinkage of thermal expansion coefficient, are treated as an essential step of a potential structural transformation of NTO. Moreover, the calculated heat capacity, entropy and bulk moduli could reflect the softening behavior of NTO and further enrich the thermodynamic data set of EMs. These results demonstrate the evolution of NTO molecules controlled by non-covalent interactions and provide vital insights into the thermodynamic behaviors at finite temperature.