摘要：

The electronic properties of copper cyanide cluster anions[Cun(CN)m;n=1–6,m=1–6]were studied using photoelectron spectroscopy (PES) with a magnetic-bottle type electron spectrometer. Both the anions and the cations of theCun(CN)mcluster were generated by laser vaporization of a molded copper cyanide rod in a He carrier gas. In the mass spectra, abundant clusters were produced at the composition of(n,m)=(n,n+1;n=16)and(n,n;n=4and 5) for the anions, whereas more abundant clusters were observed at (n,n1;n=19)for the cations. The stability ofCun(CN)n+1andCun(CN)n1+clusters is attributed to their electronic structure, where ionicCu+andCNare linked alternately in a linear geometry. The PES spectra of theCun(CN)manions show that the(n,n+1)clusters exhibit an extremely large EA of above 4.5 eV, while the EA's of the less abundant(n,n)clusters increase monotonously with cluster size from 1.3 eV(n=1)to 3.12 eV(n=6),except forn=4and 5. Together with theoretical calculations by the density functional theory (DFT), two different linear isomers have been found for(n,n)clusters, where CN takes a opposite direction toward Cu. ForCu4(CN)4andCu5(CN)5,moreover, the PES spectra show two components of distinctly different peak shape, suggesting that a ring isomer should coexist with the linear ones.

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