Differential Excitation Spectroscopy (DES) is a new pump-probe detection technique (patent-pending) which characterizes molecules based on a multi-dimensional parameterization of the rovibrational excited state structure, pump and probe interrogation frequencies, as well as the lifetimes of the excited states. Under appropriate conditions, significant modulation of the ground state can result. DES results provide a unique, simple mechanism to probe various molecules. In addition, the DES multi-dimensional parameterization provides an identification signature that is highly unique and has demonstrated high levels of immunity from interferents, providing significant practical value for high-specificity material identification. Ammonium nitrate (AN) and urea nitrate (UN) are both components commonly used in IEDs; the ability to reliably detect these chemicals is key to finding, identifying and defeating IEDs. AN and UN are complicated materials, having a number of different phases and because they are molecular crystals, there are a number of different types of interactions between the constituent atoms which must be characterized in order to understand their DES behavior. Ab initio calculations were performed on both AN and UN for various rovibrational states up to J’ ≤ 3 and validated experimentally, demonstrating good agreement between theory and experiment and the very specific responses generated.