Aqueous Fe2S2 cluster: structure, magnetic coupling, and hydration behaviour from Hubbard U density functional theory.
Aqueous Fe2S2 cluster: structure, magnetic coupling, and hydration behaviour from Hubbard U density functional theory.
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DOI：
10.1039/c4cp00984c
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发表时间：
2014-06
期刊：
影响因子：
--
通讯作者：
U. Terranova;N. D. de Leeuw
中科院分区：
文献类型：
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作者：
U. Terranova;N. D. de Leeuw
我们提出了水溶液中全亚铁Fe2S2簇的DFT + U研究。我们通过调整气相团簇的几何形状来确定U的值，该几何形状由高精度的CCSD(T)方法获得。当优化U值用于Fe2S2水溶液团簇（Fe2S2(aq)）时，得到的几何形状与x射线衍射结构吻合较好，而磁耦合与Mössbauer数据的估计一致。分子动力学轨迹预测，无论u的引入与否，Fe2S2（aq）在水中都是稳定的。然而，在溶剂化簇的几何形状、水合作用和交换常数方面存在显著差异。
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 Mössbauer 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.