Veldeman Nele, Janssens Ewald, Hansen Klavs, De Haeck Jorg, Silverans Roger E, Lievens Peter
Laboratorium voor Vaste-Stoffysica en Magnetisme & INPAC--Institute for Nanoscale Physics and Chemistry, K U Leuven, B-3001, Leuven, Belgium.
Faraday Discuss. 2008;138:147-62; discussion 211-23, 433-4. doi: 10.1039/b705920e.
Size dependent stabilities, fragmentation pathways and dissociation energies of a series of gas phase cationic doped gold clusters, Au(n)X+ (3 < or = n < or = 20; X = Y, Er and Nb), and pure Au(n)+ clusters were investigated in photofragmentation experiments. Size dependent stability patterns were obtained and the branching between monomer and dimer evaporation was studied. For bare gold, the competing neutral monomer and dimer evaporation channels were found to be in agreement with earlier studies. For doped clusters, monomer evaporation is the most likely fragmentation channel with the exception of Au18Y+ and Au20Y+ for which gold dimer evaporation is also observed. Relations between the evaporative activation energies and both the experimental abundances and the fragment yield were derived based on unimolecular rate constants. The dissociation energies from this analysis show an odd-even staggering and enhanced stabilities for certain cluster sizes, in agreement with simple electronic shell model predictions.
在光解离实验中研究了一系列气相阳离子掺杂金簇Au(n)X⁺(3≤n≤20;X = Y、Er和Nb)以及纯Au(n)⁺簇的尺寸依赖性稳定性、碎片化途径和解离能。获得了尺寸依赖性稳定性模式,并研究了单体蒸发和二聚体蒸发之间的分支情况。对于裸金,发现竞争性的中性单体和二聚体蒸发通道与早期研究一致。对于掺杂簇,除了Au18Y⁺和Au20Y⁺(也观察到金二聚体蒸发)外,单体蒸发是最可能的碎片化通道。基于单分子速率常数推导了蒸发活化能与实验丰度和碎片产率之间的关系。该分析得出的解离能显示出奇偶交错以及某些簇尺寸的稳定性增强,这与简单电子壳层模型的预测一致。