Interactions of Molecular Titanium Oxides TiO_x (x = 1–3) with Carbon Dioxide in Cluster Anions

Abstract

We study small titanium oxide-CO cluster anions in vacuo to understand the fundamental interactions between TiO and CO in the presence of an excess electron. Infrared spectra of [TiO (CO) ] ( x = 1-3, y > 1) were obtained using photodissociation spectroscopy and assigned through quantum chemistry calculations, identifying the formation of carbonato, oxalato, oxo, η-(O,O), and carbonyl ligands in the core ions of these clusters, with carbonato ligands being the dominant ligand species.

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

“…He binding to metal oxide cations can be as strong as 12 kJ mol À1 (see, fore xample, [Al 3 O 4 ,He 3 ] + )o r higher( e.g.,[ FeO 2 ,H e] + )a nd leads to spectral shifts of up to % 20 cm À1 . [83,85] In dications these effects can be rather strong ([HCCl,He] 2 + ) [86] but do not necessarilyn eed to be more pronounced ([C 7 H 6 ,He] 2 + ). [70] Interestingly,t he prototypical large amplitude motion in protonated methane is predicted to remain nearly unperturbed by He-tagging.…”

Infrared Spectroscopy of Size‐Selected Hydrated Carbon Dioxide Radical Anions CO2.−(H2O)n (n=2–61) in the C−O Stretch Region

“…formation was found in the reactions with 3‐butyn‐1‐ol as well as with HNO 3. The groups of Weber and Duncan have established a significant amount of data based on the infrared photodissociation spectroscopy of carbon dioxide solvated metal centers M +/− (CO 2 ) n (M=Au, Ag, Co, Ni, Cu, Mg, Fe, Si, V, Al, Bi, TiO), where CO 2 is activated by charge transfer to form the carbon dioxide radical anion CO 2 .− or the oxalate dianion C 2 O 4 2− . Mackenzie et al.…”

The ratio law of the structure evolution and stability for TinOm (n = 3–18, m = 1–2n) clusters

“…Owing to its technological importance, numerous experimental and theoretical investigations have been carried out on isolated titanium oxide clusters to correlate their structures and properties with their bulk counterparts. [6][7][8][9][10][11][12][13][14][15][16][17][18] Yu and Freas produced isolated positive titanium/oxygen clusters by sputtering titanium dioxide powder and titanium foil (exposed to oxygen) with an energetic xenon atom beam (~8 keV). [7] The form of titanium/oxygen cluster ions from their results is [TinO2n-δ] + , where n equals 1 to 8 and δ ranges from 0 to 4.…”