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Issue 39, 2015
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Gas-phase VUV photoionisation and photofragmentation of the silver deuteride nanocluster [Ag10D8L6]2+ (L = bis(diphenylphosphino)methane). A joint experimental and theoretical study

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Abstract

The bis(diphenylphosphino)methane (L = Ph2PCH2PPh2) ligated silver deuteride nanocluster dication, [Ag10D8L6]2+, has been synthesised in the condensed phase via the reaction of bis(diphenylphosphino)methane, silver nitrate and sodium borodeuteride in the methanol : chloroform (1 : 1) mixed solvent system. The photoionisation and photofragmentation of this mass-selected cluster were studied using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. At 15.5 eV the main ionic products observed are [Ag10D8L5]2+, [Ag10D8L4]2+, [Ag10D8L6]3+˙, [Ag9D8L4]2+˙, and [AgL2]+. The later two products arise from fragmentation of [Ag10D8L6]3+˙. An analysis of the yields of these product ions as a function of the photon energy reveals the onset for the formation of [AgL2]+ and [Ag9D8L4]2+˙ is around 2 eV higher than that for ionisation to produce [Ag10D8L5]3+˙. The onset of ionisation energy of [Ag10D8L6]2+ was determined to be 9.3 ± 0.3 eV from a fit of the yield of the product ion, [Ag10D8L6]3+˙, as a function of the VUV photon energy. DFT calculations at the RI-PBE/RECP-def2-SVP level of theory were carried out to search for a possible structure of the cluster and to estimate its vertical and adiabatic ionisation energies. The calculated lowest energy structure of the [Ag10D8L6]2+ nanocluster contains a symmetrical bicapped square antiprism as a silver core in which hydrides are located as a mix of triangular faces and edges. Four of the bisphosphines bind to the edges of the cluster core as bidentate ligands, the remaining two bisphosphines bind via a single phosphorus donor atom to each of the apical silver atoms. The DFT calculated adiabatic ionisation energy for this structure is 8.54 eV, in satisfactory agreement with experiment.

Graphical abstract: Gas-phase VUV photoionisation and photofragmentation of the silver deuteride nanocluster [Ag10D8L6]2+ (L = bis(diphenylphosphino)methane). A joint experimental and theoretical study

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Publication details

The article was received on 26 Feb 2015, accepted on 20 Mar 2015 and first published on 01 Apr 2015


Article type: Paper
DOI: 10.1039/C5CP01160D
Citation: Phys. Chem. Chem. Phys., 2015,17, 25772-25777
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    Gas-phase VUV photoionisation and photofragmentation of the silver deuteride nanocluster [Ag10D8L6]2+ (L = bis(diphenylphosphino)methane). A joint experimental and theoretical study

    S. Daly, M. Krstić, A. Giuliani, R. Antoine, L. Nahon, A. Zavras, G. N. Khairallah, V. Bonačić-Koutecký, P. Dugourd and R. A. J. O'Hair, Phys. Chem. Chem. Phys., 2015, 17, 25772
    DOI: 10.1039/C5CP01160D

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