Abstract
Dirhenium halide dianions received considerable attention in past decades due to the unusual metal–metal quadruple bond. The systematic structural evolution of dirhenium halide clusters has not been sufficiently studied and hence is not well-understood. In this work, we report an in-depth investigation on the structures and electronic properties of doubly charged dirhenium halide clusters Re2X82− (X = F, Cl, Br, I). Our computational efforts rely on the well-tested unbiased CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) method combined with density functional theory calculations. We find that all ground-state Re2X82− clusters have cube-like structures of D4h symmetry with two Re atoms encapsulated in halogen framework. The reasonable agreement between the simulated and experimental photoelectron spectrum of the Re2Cl82− cluster supports strongly the reliability of our computational strategy. The chemical bonding analysis reveals that the δ bond is the pivotal factor for the ground-state Re2X82− (X = F, Cl, Br, I) clusters to maintain D4h symmetric cube-like structures, and the enhanced stability of Re2Cl82− is mainly attributed to the chemical bonding of 5d orbital of Re atoms and 3p orbital of Cl atoms.
Highlights
The electronic absorption spectrum of Re2F82− relying on multiconfigurational quantum chemical calculations
There has been no systematic work on Re2X82− (X = F, Cl, Br and I) clusters until now, so the following questions attract our interests: (i) It is not clear whether Re2X82− clusters are characterized by the same molecular geometry as Re2X82− dianions in crystals. (ii) Does the chemical bonding in Re2X82− clusters differ from that of dianions in crystals? (iii) What is the relative stability of Re2X82− clusters? we turn our attention to the systematic study of lowest-energy geometries and electronic structures of Re2X82− (X = F, Cl, Br, I) clusters
As a first step of our study on the structural evolution of Re2X82− clusters, we perform a search for the the low-energy structures of Re2X82− (X = F, Cl, Br, I) by means of the CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) code combined with DFT calculations
Summary
The electronic absorption spectrum of Re2F82− relying on multiconfigurational quantum chemical calculations. Preetz et al.[31] reported measurements of the resonance Raman spectrum of (Bu4N)2Re2I8, while Cotton et al.[32] studied its crystal structure until a few years later. (ii) Does the chemical bonding in Re2X82− clusters differ from that of dianions in crystals? We turn our attention to the systematic study of lowest-energy geometries and electronic structures of Re2X82− (X = F, Cl, Br, I) clusters. As a first step of our study on the structural evolution of Re2X82− clusters, we perform a search for the the low-energy structures of Re2X82− (X = F, Cl, Br, I) by means of the CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) code combined with DFT (density functional theory) calculations. We get the ground-state structures of Re2X82− clusters from the above calculations and subsequently investigate their relative stabilities and chemical bonding. A detailed presentation of the computational method is described
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