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Issue 45, 2013
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Evaluation of photodissociation spectroscopy as a structure elucidation tool for isolated clusters: a case study of Ag4+ and Au4+

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Abstract

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 ℏω = 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 Au4+ whereas for Ag4+ only the ground state isomer has to be considered to explain the experimental absorption spectrum. Our extended methodology shows two nearly degenerate isomers of Au4+ probably being present in the molecular beam and therefore shows promise for the further structure determination of pure and binary transition-metal clusters.

Graphical abstract: Evaluation of photodissociation spectroscopy as a structure elucidation tool for isolated clusters: a case study of Ag4+ and Au4+

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Publication details

The article was received on 22 May 2013, accepted on 30 Aug 2013 and first published on 02 Sep 2013


Article type: Paper
DOI: 10.1039/C3CP52160E
Phys. Chem. Chem. Phys., 2013,15, 19715-19723

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    Evaluation of photodissociation spectroscopy as a structure elucidation tool for isolated clusters: a case study of Ag4+ and Au4+

    A. Shayeghi, R. L. Johnston and R. Schäfer, Phys. Chem. Chem. Phys., 2013, 15, 19715
    DOI: 10.1039/C3CP52160E

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