The Electron‐Density Distribution of UCl₄ and Its Topology from X‐ray Diffraction.

Cossard, Alessandro; Gianopoulos, Christopher G.; Desmarais, Jacques K.; Casassa, Silvia; Gatti, Carlo; Erba, Alessandro; Pinkerton, A. Alan

The chemistry of 5f ${5f}$ electrons in actinide complexes and materials is still poorly understood and represents a serious challenge and opportunity for experiment and theory. The study of the electron density distribution of the ground state of such systems through X‐ray diffraction represents a unique opportunity to quantitatively investigate different chemical bonding interactions at once, but was considered "almost impossible" on heavy‐atom systems, until very recently. Here, we present a combined experimental and theoretical investigation of the electron density distribution in UCl_4 crystals and comparison with the previously reported spin density distribution from polarized neutron diffraction. All approaches provide a consistent picture in terms of electron and spin density distribution, and chemical bond characterization. More importantly, the synergy between experiments and quantum‐mechanical calculations allows to highlight the remarkable sensitivity of X‐ray diffraction to 5f ${5f}$ electrons in materials.

ATOMS in molecules theory; ELECTRON distribution; ELECTRON density; NEUTRON diffraction; ELECTRON spin

Angewandte Chemie, 2025, Vol 137, Issue 1, p1

0044-8249

Academic Journal

10.1002/ange.202413883