Chemical bonding in Uranium-based materials: A local vibrational mode case study of Cs 2 UO 2 Cl 4 and UCl 4 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 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.

Unveiling the Role of Spin Currents on the Giant Rashba Splitting in Single-Layer WSe2.

The Rashba spin splitting in uniaxial, inversion-asymmetric materials has attracted considerable interest for spintronic applications. The most widely used theoretical framework to model such states is Kohn-Sham density functional theory (DFT) in combination with standard (semi)local exchange-correlation density functional approximations (DFAs). However, in the presence of spin-orbit coupling, DFT misses contributions due to modification of the many-body interaction by spin currents J⃗. Inclusion of the latter effects requires a spin current DFT (SCDFT) formulation, which is seldom considered. We investigate the giant Rashba splitting in single-layer WSe2, and we quantify the effect of including spin currents in DFAs of the SCDFT. Crucially, we show that SCDFT allows fully capturing the giant Rashba band splitting in single-layer WSe2, otherwise previously systematically underestimated by standard (semi)local DFAs within the DFT framework. We find the inclusion of J⃗ on the DFA increases the Rashba splitting by about 20%.