JILA, NIST and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, United States.
J Phys Chem A. 2011 Apr 14;115(14):3006-15. doi: 10.1021/jp200797v. Epub 2011 Mar 21.
Irradiation of AuCl(4)(-) and AuCl(2)(OH)(2)(-) in the gas-phase using ultraviolet light (220-415 nm) leads to their dissociation. Observed fragment ions for AuCl(4)(-) are AuCl(3)(-) and AuCl(2)(-) and for AuCl(2)(OH)(2)(-) are AuCl(2)(-) and AuClOH(-). All fragment channels correspond to photoreduction of the gold atom to either Au(II) or Au(I) depending on the number of neutral ligands lost. Fragment branching ratios of AuCl(4)(-) are observed to be highly energy dependent and can be explained by comparison of the experimental data to calculated threshold energies obtained using density functional theory. The main observed spectral features are attributed to ligand-to-metal charge transfer transitions. These results are discussed in the context of the molecular-level mechanisms of Au(III) photochemistry.
用紫外光（220-415nm）辐照气相中的 AuCl(4)(-)和 AuCl(2)(OH)(2)(-)会导致它们的解离。对于 AuCl(4)(-)，观察到的碎片离子为 AuCl(3)(-)和 AuCl(2)(-)，对于 AuCl(2)(OH)(2)(-)，观察到的碎片离子为 AuCl(2)(-)和 AuClOH(-)。所有的碎片通道都对应于金原子的光还原，还原产物取决于失去的中性配体的数量，可以是 Au(II)或 Au(I)。AuCl(4)(-)的碎片分支比高度依赖于能量，可以通过将实验数据与使用密度泛函理论计算得到的理论阈值能量进行比较来解释。主要观察到的光谱特征归因于配体到金属的电荷转移跃迁。这些结果在 Au(III)光化学的分子水平机制的背景下进行了讨论。
