Gas-Phase Structural and Optical Properties of Homo- and Heterobimetallic Rhombic Dodecahedral Nanoclusters [Ag14-nCun(C CtBu)(12)X]( ) (X = CI and Br): Ion Mobility, VUV and UV Spectroscopy, and DFT Calculations

Steven Daly; Chang Min Choi; Athanasios Zavras; Marjan Krstic; Fabien Chirot; Timothy U Connell; Spencer J Williams; Paul S Donnelly; Rodolphe Antoine; Alexandre Giuliani; Vlasta Bonaseic-Koutecky; Philippe Dugourd; Richard AJ O'Hair

Journal article

Gas-Phase Structural and Optical Properties of Homo- and Heterobimetallic Rhombic Dodecahedral Nanoclusters [Ag14-nCun(C CtBu)(12)X]( ) (X = CI and Br): Ion Mobility, VUV and UV Spectroscopy, and DFT Calculations

Steven Daly, Chang Min Choi, Athanasios Zavras, Marjan Krstic, Fabien Chirot, Timothy U Connell, Spencer J Williams, Paul S Donnelly, Rodolphe Antoine, Alexandre Giuliani, Vlasta Bonaseic-Koutecky, Philippe Dugourd, Richard AJ O'Hair

JOURNAL OF PHYSICAL CHEMISTRY C | AMER CHEMICAL SOC | Published : 2017

DOI: 10.1021/acs.jpcc.7b02663

Abstract

The rhombic dodecahedral nanocluster [Ag14(C≡CtBu)12Cl]+, which has been structurally characterized using X-ray crystallography, was transferred to the gas phase using electrospray ionization, where it was characterized by ion mobility (IM), vacuum ultraviolet (VUV), and ultraviolet (UV) spectroscopies in conjunction with DFT calculations. IM reveals a single peak, and modeling of the collision cross-section with the X-ray structure suggests that the cluster maintains its condensed phase structure upon transfer to the gas phase. The VUV spectra exhibit rich fragmentation, including: photoionization to give [Ag14(C≡CtBu)12Cl]2+• with an onset of 8.84 ± 0.08 eV; cluster fission fragmentation v..

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University of Melbourne Researchers

Richard O'Hair Author Chemistry

Spencer Williams Author Chemistry

Paul Donnelly Author Chemistry

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Grants

Awarded by Australian Research Council

Awarded by SOLEIL

Awarded by European Research Council under the European Union's Seventh Framework Programme (FP7)

Funding Acknowledgements

R.A.J.O., S.J.W., and P.D. thank the Australian Research Council for financial support (DP150101388). SOLEIL support is acknowledged under project no. 20150734. We also thank the general technical staff of SOLEIL for running the facility. A.Z. acknowledges the award of an Australian Postgraduate Ph.D. Scholarship. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013 Grant Agreement No. 320659). V.B.-K. and M.K. acknowledge Prof. Miroslav Radman at MedILS and Split-Dalmatia County for kind support. We thank George Khairallah for discussions.