Abstract Series of MOx− (M = Cu, Ag, and Au; x = 1–3) complexes and one solitary kind of AgO5− were generated using a magnetron sputter cluster source, and their reactions with additional O2 were studied by combining a low temperature flow reactor and a time-of-flight mass spectrometer. The structures and bonding characters of these complexes were explored according to the observed reaction channels and systematic DFT calculations, in which OAgO−, OAg(η1-O2)−, and (η1-O3)Ag (η1-O2)− were newly observed complexes. The structure (η1-O3)Ag (η1-O2)− was further confirmed using the molecule tagging infrared photodissociation spectroscopy. The theoretical binding energies of oxygen species in MOx− (M = Cu, Ag, and Au; x = 1–3, and 5) are consistent with the experimental observations, which clearly show a cooperative effect of bonding interactions of various oxygen species on the Cu, Ag and Au anions. The contributions of (n-1)d, ns, and np components of the IB metals to their bonding interactions were discussed, which account for the above cooperative effect as well as the much stronger Cu–O bonds than corresponding Ag–O and Au–O bonds in MOx−.

中文翻译：

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IB族金属阴离子上各种氧物种的协同键合相互作用

摘要 使用磁控溅射簇源生成了一系列 MOx−（M = Cu、Ag 和 Au；x = 1-3）配合物和一种单独的 AgO5−，并通过结合低温度流动反应器和飞行时间质谱仪。根据观察到的反应通道和系统的 DFT 计算探索了这些配合物的结构和键合特性，其中新观察到 OAgO−、OAg(η1-O2)− 和 (η1-O3)Ag (η1-O2)−复合体。使用分子标记红外光解光谱进一步证实了结构 (η1-O3)Ag (η1-O2)-。MOx− 中氧物质的理论结合能（M = Cu、Ag 和 Au；x = 1-3 和 5）与实验观察一致，这清楚地表明了各种氧物种的键合相互作用对 Cu、Ag 和 Au 阴离子的协同作用。讨论了 IB 金属的 (n-1)d、ns 和 np 组分对其键合相互作用的贡献，这解释了上述协同效应以及比相应的 Ag-O 和 Au 强得多的 Cu-O 键MOx− 中的-O 键。