Chemical bonding in Uranium-based materials: A local vibrational mode case study of Cs [Formula: see text] UO [Formula: see text] Cl [Formula: see text] and UCl [Formula: see text] crystals

Filippo Bodo; Alessandro Erba; Elfi Kraka; Renaldo T Moura Jr

doi:10.1002/jcc.27311

Chemical bonding in Uranium-based materials: A local vibrational mode case study of Cs $_{2}$ UO $_{2}$ Cl $_{4}$ and UCl $_{4}$ crystals

J Comput Chem. 2024 May 30;45(14):1130-1142. doi: 10.1002/jcc.27311. Epub 2024 Jan 26.

Authors

Filippo Bodo^{1

2}, Alessandro Erba², Elfi Kraka¹, Renaldo T Moura Jr^{1

3}

Affiliations

¹ Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, Dallas, Texas, USA.
² Dipartimento di Chimica, Università di Torino, Torino, Italy.
³ Department of Chemistry and Physics, Center of Agrarian Sciences, Federal University of Paraiba, Areia, Brazil.

PMID: 38279637
DOI: 10.1002/jcc.27311

Abstract

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 $_{2}^{2 +}$ ) traced from its molecular configurations to the solid state, exemplified by Cs $_{2}$ UO $_{2}$ Cl $_{4}$ and (ii) Uranium tetrachloride (UCl $_{4}$ ) 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.

Keywords: bond strength; chemical bonding; crystalline systems; local vibrational mode analysis; uranium‐based materials.