Aqueous Fe2S2 cluster: structure, magnetic coupling, and hydration behaviour from Hubbard U density functional theory

作者：Terranova Umberto^*; de Leeuw Nora H

来源：Physical Chemistry Chemical Physics, 2014, 16(26): 13426-13433.

DOI：10.1039/c4cp00984c

We present a DFT + U investigation of the all-ferrous Fe2S2 cluster in aqueous solution. We determine the value of U by tuning the geometry of the cluster in the gas-phase to that obtained by the highly accurate CCSD(T) method. When the optimised value of U is employed for the aqueous Fe2S2 cluster (Fe2S2(aq)), the resulting geometry agrees well with the X-ray diffraction structure, while the magnetic coupling is in line with the estimate from Mossbauer data. Molecular dynamics trajectories predict Fe2S2(aq) to be stable in water, regardless of the introduction of U. However, significant differences arise in the geometry, hydration, and exchange constant of the solvated clusters.

• 出版日期2014