Many-body effects in the optical absorption of lithium azide (LiN3)

Until recently most of the understanding achieved for solid explosives has been obtained using various semi-empirical approaches due to a major role of excitonic effects in the mechanisms of decomposition. Nevertheless, during the last two decades, thanks to the ongoing progress in iterative computational methods, the inclusion of the electron-hole interaction in ab initio calculations has become a standard approach in solid-state theory. In this paper, the electronic structure and optical properties of bulk lithium azide are investigated, taking into account the electron-hole interaction via the Bethe-Salpeter equation (BSE). Here, we employ the kernel polynomial method (KPM), which significantly reduces the computational cost compared to direct diagonalization methods. The calculations of the imaginary part of the polarization dependent dielectric function including excitonic effects are reported for the first time. Then, we show a density map of the two-particle wave function and propose an alternative interpretation of the initial stages of the externally triggered chemical decomposition, based on the analysis of two-particle states near the absorption edge.