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Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.

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 Re₂X₈^2- (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 Re₂X₈^2- clusters have cube-like structures of D_4h symmetry with two Re atoms encapsulated in halogen framework. The reasonable agreement between the simulated and experimental photoelectron spectrum of the Re₂Cl₈^2- cluster supports strongly the reliability of our computational strategy. The chemical bonding analysis reveals that the ? bond is the pivotal factor for the ground-state Re₂X₈^2- (X?=?F, Cl, Br, I) clusters to maintain D_4h symmetric cube-like structures, and the enhanced stability of Re₂Cl₈^2- is mainly attributed to the chemical bonding of 5d orbital of Re atoms and 3p orbital of Cl atoms.

SUBMITTER: Zhang LH

PROVIDER: S-EPMC5928166 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.

Zhang Li Huan LH Xia Xin Xin XX Sun Wei Guo WG Lu Cheng C Kuang Xiao Yu XY Le Chen Bo B Maroulis George G

Scientific reports 20180430 1

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-test ...[more]

PMID: 29713044

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Project description:A central issue in understanding redox properties of iron-sulfur proteins is determining the factors that tune the reduction potentials of the Fe-S clusters. Recently, Solomon and coworkers have shown that the Fe-S bond covalency of protein analogs measured by %L, the percent ligand character of the Fe 3d orbitals, from ligand K-edge X-ray absorption spectroscopy (XAS) correlates with the electrochemical redox potentials. Also, Wang and coworkers have measured electron detachment energies for iron-sulfur clusters without environmental perturbations by gas-phase photoelectron spectroscopy (PES). Here the correlations of the ligand character with redox energy and %L character are examined in [Fe(4)S(4)L(4)](2-) clusters with different ligands by broken symmetry density functional theory (BS-DFT) calculations using the B3LYP functional together with PES and XAS experimental results. These gas-phase studies assess ligand effects independently of environmental perturbations and thus provide essential information for computational studies of iron-sulfur proteins. The B3LYP oxidation energies agree well with PES data, and the %L character obtained from natural bond orbital analysis correlates with XAS values, although it systematically underestimates them because of basis set effects. The results show that stronger electron-donating terminal ligands increase %L(t), the percent ligand character from terminal ligands, but decrease %S(b), the percent ligand character from the bridging sulfurs. Because the oxidized orbital has significant Fe-L(t) antibonding character, the oxidation energy correlates well with %L(t). However, because the reduced orbital has varying contributions of both Fe-L(t) and Fe-S(b) antibonding character, the reduction energy does not correlate with either %L(t) or %S(b). Overall, BS-DFT calculations together with XAS and PES experiments can unravel the complex underlying factors in the redox energy and chemical bonding of the [4Fe-4S] clusters in iron-sulfur proteins.

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Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.

Publications

Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.

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