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cc by (c) Donato, Andreu A. de et al., 2024
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/229521

Gas-Phase Production of Hydroxylated Silicon Oxide Cluster Cations: Structure, Infrared Spectroscopy, and Astronomical Relevance

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The interaction of free cationic silicon oxide clusters, SixOy+ (x = 2–5, y ≥ x), with dilute water vapor, was investigated in a flow tube reactor. Product mass distributions indicate cluster size-dependent dissociative water adsorption. To probe the structure and vibrational spectra of the resulting SixOyH2+ (x = 2–4) clusters, we employed infrared multiple photon dissociation spectroscopy and density functional theory calculations. The planar rhombic cluster core of the disilicon oxides (x = 2) appears to be retained upon dissociative adsorption of one H2O unit, whereas a significant structural transformation of the tri- and tetra-silicon oxides (x = 3 and 4) is induced, resulting in an increased coordination of the Si atoms and more 3D cluster structures. In an astronomical context, we discuss the potential relevance of SixOyHz+ clusters as seeds for dust nucleation and catalysts for carbon-based chemistry in diffuse or translucent interstellar clouds, where all the necessary conditions for producing these species are found. In the produced clusters, the frequency of the isolated silanol Si–OH stretching vibrational mode is considerably blue-shifted compared to that in hydroxylated bulk silica and small inorganic compounds. This mode has a characteristic frequency range between 1200 cm–1 (8.3 μm) and 1090 cm–1 (9.2 μm) and is associated with the anomalously small Si–OH bond lengths in these ionised species. In infrared observations such high frequency Si–O stretching modes are usually associated with a pure bulk silica component of silicate cosmic dust. The presence of SixOyH2+ clusters in low silica astrophysical environments could thus potentially be detected via their signature Si−O band using the James Webb space telescope.

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DONATO, Andreu A. de, et al. Gas-Phase Production of Hydroxylated Silicon Oxide Cluster Cations: Structure, Infrared Spectroscopy, and Astronomical Relevance. ACS Earth and Space Chemistry. 2024. Vol. 8, num. 6, pags. 1154-1164. ISSN 2472-3452. [consulted: 25 of May of 2026]. Available at: https://hdl.handle.net/2445/229521

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