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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structural and Electronic Properties of Reduced Transition Metal Oxide Clusters, M3O8 and M3O8 - (M ) Cr, W), from Photoelectron Spectroscopy and Quantum Chemical Calculations
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Structural and Electronic Properties of Reduced Transition Metal Oxide Clusters, M3O8 and M3O8 - (M ) Cr, W), from Photoelectron Spectroscopy and Quantum Chemical Calculations

机译：还原过渡金属氧化物簇M3O8和M3O8-（M）Cr，W）的结构和电子性质，通过光电子能谱和量子化学计算得出

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摘要

We report a comparative study of reduced transition metal oxide clusters, M3O8 - (M ) Cr, W) anions and their neutrals, via anion photoelectron spectroscopy (PES) and density functional theory (DFT) and molecular orbital theory (CCSD(T)) calculations. Well-resolved PES spectra are obtained for M3O8 - (M ) Cr, W) at 193 and 157 nm photon energies. Different PES spectra are observed for M ) Cr versus M ) W. Extensive DFT and CCSD(T) calculations are performed to locate the ground and low-lying excited states for the neutrals and anions. The ground states of Cr3O8 and Cr3O8 - are predicted to be the 3B2 and 4B2 states of a C2V structure, respectively, revealing ferromagnetic spin coupling for Cr 3d electrons. In contrast, the ground states of W3O8 and W3O8 - are predicted to be the 1A′ state (Cs symmetry) and the 2A1 state (C2V symmetry), respectively, showing metal-metal d-d bonding in the anion. The current cluster geometries are in qualitative agreement with prior DFT studies at the PBE level for M ) Cr and the B3LYP level for M ) W. The BP86 and PW91 functionals significantly outperform the B3LYP functional for the Cr species, in terms of relative energies, electron detachment energies, and electronic excitation energies, whereas the B3LYP functional is better for the W species. Accurate heats of formation for the ground states of M3O8 are calculated from the clustering energies and the heats of formation of MO2 and MO3. The energetics have been used to predict redox reaction thermochemistry.
机译：我们通过阴离子光电子能谱（PES），密度泛函理论（DFT）和分子轨道理论（CCSD（T））报告了还原型过渡金属氧化物簇，M3O8-（M Cr，W）阴离子及其中性元素的比较研究计算。对于M3O8-（M Cr，W），在193和157 nm光子能量下获得了良好分辨的PES光谱。对于M）Cr与M）W，观察到了不同的PES光谱。进行了广泛的DFT和CCSD（T）计算，以找到中性和阴离子的基态和低激发态。 Cr3O8和Cr3O8-的基态分别预测为C2V结构的3B2和4B2状态，揭示了Cr 3d电子的铁磁自旋耦合。相反，预测W3O8和W3O8-的基态分别为1A'状态（Cs对称）和2A1状态（C2V对称），显示阴离子中的金属-金属d-d键。当前的簇几何形状与先前的DFT研究在M）Cr的PBE级别和M）W的B3LYP级别上定性一致。就相对能量而言，BP86和PW91的官能团明显优于Cr物种的B3LYP官能团，电子离解能和电子激发能，而B3LYP的功能对W物种更好。 M3O8的基态的精确形成热是根据聚集能以及MO2和MO3的形成热来计算的。该能量学已用于预测氧化还原反应的热化学。

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