Chemical bonding in Uranium-based materials: A local vibrational mode case study of Cs2UO2Cl4 and UCl4 crystals

The Local Vibrational Mode Analysis, initially applied to diverse molecular systems, was extended to periodic systems in 2019. This work introduces an enhanced version of the LModeA software, specifically designed for the comprehensive analysis of two and three-dimensional periodic structures. Notably, a novel interface with the Crystal package was established, enabling a seamless transition from molecules to periodic systems using a unified methodology. Two distinct sets of uranium-based systems were investigated: (i) the evolution of the Uranyl ion (UO (Formula presented.)) traced from its molecular configurations to the solid state, exemplified by Cs (Formula presented.) UO (Formula presented.) Cl (Formula presented.) and (ii) Uranium tetrachloride (UCl (Formula presented.)) in both its molecular and crystalline forms. The primary focus was on exploring the impact of crystal packing on key properties, including IR and Raman spectra, structural parameters, and an in-depth assessment of bond strength utilizing local mode perspectives. This work not only demonstrates the adaptability and versatility of LModeA for periodic systems but also highlights its potential for gaining insights into complex materials and aiding in the design of new materials through fine-tuning.