ABSTRACT
The interaction of free cationic silicon oxide clusters, Si x O y + (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 Si x O y H2 + (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 Si x O y H z + 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 Si x O y H2 + clusters in low silica astrophysical environments could thus potentially be detected via their signature Si-O band using the James Webb space telescope.
ABSTRACT
Silicates are ubiquitously found as small dust grains throughout the universe. These particles are frequently subject to high-energy processes and subsequent condensation in the interstellar medium (ISM), where they are broken up into many ultrasmall silicate fragments. These abundant molecular-sized silicates likely play an important role in astrochemistry. By approximately mimicking silicate dust grain processing occurring in the diffuse ISM by ablation/cooling of a Mg/Si source material in the presence of O2, we observed the creation of stable clusters based on discrete pyroxene monomers (MgSiO3 +), which traditionally have only been considered possible as constituents of bulk silicate materials. Our study suggests that such pyroxene monomer-based clusters could be highly abundant in the ISM from the processing of larger silicate dust grains. A detailed analysis, by infrared multiple-photon dissociation (IR-MPD) spectroscopy and density functional theory (DFT) calculations, reveals the structures and properties of these monomeric silicate species. We find that the clusters interact strongly with oxygen, with some stable cluster isomers having a silicate monomeric core bound to an ozone-like moiety. The general high tendency of these monomeric silicate species to strongly adsorb O2 molecules also suggests that they could be relevant to the observed and unexplained depletion of oxygen in the ISM. We further find clusters where a Mg atom is bound to the MgSiO3 monomer core. These species can be considered as the simplest initial step in monomer-initiated nucleation, indicating that small ionized pyroxenic clusters could also assist in the reformation of larger silicate dust grains in the ISM.
