Ultrafast vibrational energy redistribution in cyclotrimethylene trinitramine (RDX)

The microscopic mechanism of the energy transfer in cyclotrimethylene trinitramine (RDX) is of particular importance for the study of the energy release process in high-energy materials. In this work, an effective vibrational Hamiltonian based on normal modes (NMs) has been introduced to study the energy transfer process of RDX. The results suggest that the energy redistribution in RDX can be characterized as an ultrafast process with a time scale of 25 fs, during which the energy can be rapidly localized to the -NNO2 twisting mode (vNNO2), the N-N stretching mode (vN-N), and the C-H stretching mode (vC-H). Here, the vNNO2 and vN-N modes are directly related to the cleavage and dissociation of the N-N bond in RDX and, therefore, can be referred to as "active modes." More importantly, we found that the energy can be rapidly transferred from the vC-H mode to the vNNO2 mode due to their strong coupling. From this perspective, the vC-H mode can be regarded as an "energy collector" that plays a pivotal role in supplying energy to the "active modes." In addition, the bond order analysis shows that the dissociation of the N-N bonds of RDX follows a combined twisting and stretching path along the N-N bond. This could be an illustration of the further exothermic decomposition triggered by the accumulation of vibrational energy. The present study reveals the microscopic mechanism for the vibrational energy redistribution process of RDX, which is important for further investigation of the energy transfer process in high-energy materials.