Evaluation of photodissociation spectroscopy as a structure elucidation tool for isolated clusters: A case study of Ag and Au

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Resolving the structure of clusters in the gas phase often requires the comparison of experimental data to quantum chemical calculations. Herein, we present the variation of a straightforward approach, in which photodissociation spectra of isolated clusters are compared to optical response calculations in order to elucidate cluster structures. Our absorption spectra were measured using a newly built longitudinal beam depletion spectroscopy apparatus and recorded in the photon energy range pω = 1.9-3.5 eV. Cluster geometries were obtained using the unbiased Birmingham Cluster Genetic Algorithm coupled with density functional theory, while the optical response was calculated in the framework of time-dependent density functional theory. Experiments and excited state calculations are in excellent agreement using long-range corrected exchange correlation functionals for both ground and excited state calculations. Our methodology indicates a contribution of Y shaped Au whereas for Ag only the ground state isomer has to be considered to explain the experimental absorption spectrum. Our extended methodology shows two nearly degenerate isomers of Au probably being present in the molecular beam and therefore shows promise for the further structure determination of pure and binary transition-metal clusters.


Original languageEnglish
Pages (from-to)19715-19723
Number of pages9
JournalPhysical Chemistry Chemical Physics
Issue number45
Publication statusPublished - 7 Dec 2013