Theoretical and experimental study of the C-H stretching overtones of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12 hexaazaisowurtzitane (CL20).

An understanding of how molecular environment and structure are reflected in optical absorption spectra offers a number of advantages, such as improved detection of materials or providing an easy means of distinguishing crystal polymorphs of the same molecular solid. This study advances this understanding by comparing near IR laser photoacoustic absorption measurements of the first C-H stretch overtones around 5975 cm(-1) of β-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL20) to simulated spectra using density functional calculations and the local mode model of C-H stretches. The calculations reveal that accounting for movement of charge throughout the model crystal unit cell with a pure quantum mechanical method in the calculation of the transition dipole moment is critical to matching the experimental data. Vibrational modes in a given molecule induce movement of charge in neighboring molecules, such that calculation of the transition dipole moment had to include the entire crystal unit cell. Movement of charge across the periodic boundary conditions (PBC) of the model needs to be accounted for to calculate a spectrum validated by the experimental measurement. The Hirshfeld population analysis minimizes discontinuities for movement of charge across the PBC.