Probing the structural evolution of Cu_N~-, N=9-20, through a comparisonof computed electron removal energies and experimental photoelectronspectra

摘要

Computed electron removal energies for Cu_N~- clusters, N=9-20, are presented for the threelowest-energy isomers obtained from extensive, unbiased searches for the minimum energy structure at each size. The density functional theory (DFT) computations make use of a schemeintroduced by Jellinek and Acioli (JA) [J. Chem. Phys. 118, 7783 (2003)] that obtains electron removal energies from DFT orbital energies using corrections based on DFT total energies. Thecomputed removal energies are compared with the measured photoelectron spectra (PES) for Cu_N~-. The patterns of computed removal energies are shown to be isomer specific for clusters in this sizerange. By matching the computed removal energies to the observed PES, the isomers responsible forthe PES are identified. The results of the JA scheme are compared to those obtained using otherDFT-based methods.