Jiang Ling, Xu Qiang
National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577, Japan.
J Phys Chem A. 2006 Oct 12;110(40):11488-93. doi: 10.1021/jp064129s.
Reactions of laser-ablated silver atoms with carbon monoxide molecules in solid argon and neon have been investigated using matrix-isolation IR spectroscopy. Small silver cluster carbonyls, (AgCO)2 and AgnCO (n=2-4), as well as mononuclear silver carbonyls, Ag(CO)2 and Ag(CO)3, are generated upon sample annealing in the argon experiments and are characterized on the basis of the isotopic substitution, the CO concentration change, and the comparison with theoretical predictions. However, these polynuclear carbonyls are absent from the neon experiments. Density functional theory calculations have been performed on these silver carbonyls and the corresponding ligand-free silver clusters, which support the identification of these silver carbonyls from the matrix IRspectrum. A terminal CO has been found in the most stable structures of (AgCO)2, Ag2CO, Ag3CO, and Ag4CO. Furthermore, a plausible reaction mechanism has been proposed to account for the formation of the (AgCO)2 and AgnCO (n=2-4) molecules.
利用基质隔离红外光谱法研究了激光烧蚀的银原子与固态氩和氖中的一氧化碳分子的反应。在氩气实验中，通过样品退火生成了小的银簇羰基化合物(AgCO)2和AgnCO（n = 2 - 4）以及单核银羰基化合物Ag(CO)2和Ag(CO)3，并根据同位素取代、CO浓度变化以及与理论预测的比较对其进行了表征。然而，在氖气实验中没有这些多核羰基化合物。对这些银羰基化合物和相应的无配体银簇进行了密度泛函理论计算，这支持了从基质红外光谱中识别这些银羰基化合物。在(AgCO)2、Ag2CO、Ag3CO和Ag4CO的最稳定结构中发现了一个端基CO。此外，还提出了一个合理的反应机理来解释(AgCO)2和AgnCO（n = 2 - 4）分子的形成。
