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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Photoelectron spectroscopy and density functional theory studies of (FeS)(m)H- (m=2-4) cluster anions: effects of the single hydrogen
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Photoelectron spectroscopy and density functional theory studies of (FeS)(m)H- (m=2-4) cluster anions: effects of the single hydrogen

机译：光电子光谱和密度函数理论研究（FES）（M）H-（M = 2-4）簇阴离子：单氢的影响

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Single hydrogen containing iron hydrosulfide cluster anions (FeS)(m)H- (m = 2-4) are studied by photo-electron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by Density Functional Theory (DFT) calculations. The structural properties, relative energies of different spin states and isomers, and the first calculated vertical detachment energies (VDEs) of different spin states for these (FeS)(m)H- (m = 2-4) cluster anions are investigated at various reasonable theory levels. Two types of structural isomers are found for these (FeS)(m)H- (m = 2-4) clusters: (1) the single hydrogen atom bonds to a sulfur site (SH-type); and (2) the single hydrogen atom bonds to an iron site (FeH-type). Experimental and theoretical results suggest such available different SH- and FeH-type structural isomers should be considered when evaluating the properties and behavior of these single hydrogen containing iron sulfide clusters in real chemical and biological systems. Compared to their related, respective pure iron sulfur (FeS)(m)(-) clusters, the first VDE trend of the diverse type (FeS)(m)H-0,1(-) (m = 1-4) clusters can be understood through (1) the different electron distribution properties of their highest singly occupied molecular orbital employing natural bond orbital analysis (NBO/HSOMO), and (2) the partial charge distribution on the NBO/HSOMO localized sites of each cluster anion. Generally, the properties of the NBO/HSOMOs play the principal role with regard to the physical and chemical properties of all the anions. The change of cluster VDE from low to high is associated with the change in nature of their NBO/HSOMO from a dipole bound and valence electron mixed character, to a valence p orbital on S, to a valence d orbital on Fe, and to a valence p orbital on Fe or an Fe-Fe delocalized valence bonding orbital. For clusters having the same properties for NBO/HSOMOs, the partial charge distributions at the NBO/HSOMO localized sites additionally affect their VDEs: a more negative or less positive localized charge distribution is correlated with a lower first VDE. The single hydrogen in these (FeS)(m)H- (m = 2-4) cluster anions is suggested to affect their first VDEs through the different structure types (SH- or FeH-), the nature of the NBO/HSOMOs at the local site, and the value of partial charge number at the local site of the NBO/HSOMO.
机译：通过3.492eV（355nm）和4.661eV（266nm）光子能量，通过光 - 电子光谱（PE）研究了含有铁氢硫化氢簇阴离子（FES）（M）（M）H-（M = 2-4）和4.661eV（266nm）光子能量，通过密度泛函理论（DFT）计算。针对各种结构特性，不同旋转状态和异构体的相对能量，不同旋转状态的不同旋转状态的不同旋转状态（m）h-（m = 2-4）簇阴离子进行研究合理的理论水平。发现两种类型的结构异构体用于这些（FES）（M）H-（M）H-（M = 2-4）簇：（1）单个氢原子与硫位点（SH型）; （2）对铁部位（FEH型）的单氢原子键。实验和理论结果表明，在评估真实化学和生物系统中这些单一氢硫化铁簇的性质和行为时，应考虑这种可用的不同SH和FEH型结构异构体。与其相关的各种纯铁硫（FES）（M）（ - ）簇相比，多种类型（FES）（M）H-0,1（ - ）（M = 1-4）簇的第一VDE趋势通过（1）可以理解（1）其最高单独占用的分子轨道采用天然键轨道分析（NBO / Hsomo）的不同电子分布性能，以及（2）每个簇阴离子的NbO / Hsomo局部位点上的部分电荷分布。通常，NBO / HSOMOS的性质在所有阴离子的物理和化学性质方面发挥了主要作用。从低到高的簇VDE的变化与偶极子/ hsomo的性质的变化与偶极子和价电子混合特性，在s的价P轨道上，对Fe的价D轨道，以及a价P轨道在Fe或Fe-Fe疏散价键合轨道上。对于具有与NBO / HSOMOS具有相同性质的簇，NBO / HSOMO局部位置处的部分电荷分布另外影响其VDE：更负面或更少的正局部电荷分布与下部第一VDE相关。这些（FES）（M）（M）H-（M = 2-4）簇阴离子中的单一氢被提出通过不同的结构类型（SH-OR FEH-），NBO / HSOMOS的性质影响它们的第一VDE本地站点，以及NBO / HSOMO当地站点的部分电荷数的值。

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