Modulating intermolecular interactions and vibrational energy transfer in energetic systems with external electric fields

Abstract

The controllable application and property modulation of energetic materials is a long-standing challenge, as their macroscopic behavior fundamentally depends on structures formed by microscopic intermolecular interactions and the accompanying vibrational energy transfer (VET). Here, we present the regulatory capability of external electric fields (EEFs) toward intermolecular interactions and VET in energetic systems. First-principles structural studies confirm that EEFs applied parallel or antiparallel to the system dipole reshape binding properties by modulating intermolecular interaction contributions. Furthermore, first-principles molecular dynamics simulations reveal that fields aligned with the dipole promote vibrational energy accumulation on intermolecular N–N trigger bonds. This phenomenon, driven by field-induced reshaping of potential energy surfaces, is evidenced by short-time Fourier transform VET spectra of excited C–H vibrations. Our findings highlight that EEFs can manipulate intermolecular interactions by influencing molecular dipoles at the atomic level, thereby providing a potential feasible pathway for property modulation in energetic molecular systems.