RESUMEN
The formation mechanism and stability of silicon oxide clusters observed in the ablation of SiO targets at 266 nm were investigated by time-of-flight mass spectrometry, laser-induced fluorescence (LIF), and DFT calculations. Neutral and positively charged Si(n)(+/0) and Si(n)O(m)H(0,1)(+) clusters were identified in the plume, but neutral Si(n)O(m) could not be observed. The time distribution of SiO in the plume measured by postionization with an ArF laser (Delta lambda approximately 1 nm, tau approximately 14 ns) and mass spectrometric detection was compared with that obtained by LIF with narrowband dye laser selective excitation of one specific rovibronic transition in SiO. Postionization leads to a multicomponent distribution that extends up to times near 100 micros after ablation, whereas LIF measurements obtain time distributions shorter than 20 micros. DFT calculations of several Si(n)O(m)(0/+) were performed, showing that one photon absorption of the postionization laser makes available low-energy dissociation channels of the neutrals, whereas two photon absorption is required for ionization. DFT calculations were carried out for stoichiometric H-containing clusters Si(n)O(n)H(+) (n = 1-4). For n = 1,2, the optimized geometries involve bonding of hydrogen to one oxygen atom in the clusters; for n = 3 and 4, the structures containing H-Si bonds are more stable.
RESUMEN
The interaction of SF(5)CF(3) with vacuum-UV radiation has been investigated by photon induced fluorescence spectroscopy. Total fluorescence yield and dispersed fluorescence spectra of SF(5)CF(3) were recorded in the 200-1000 nm fluorescence window. In all cases, the fluorescence spectra resemble those of CF(3)X (X = H, F, Cl, and Br) molecules. At photon energies below 20 eV, the emission is attributed to the excited CF(3) and CF(2) fragments. The threshold for the CF(3) emission is 10.2 +/- 0.2 eV, giving an upper limit estimate for the SF(5)-CF(3) bond dissociation energy of 3.9 +/- 0.3 eV. The excitation functions of the CF(3) and CF(2) emissions were measured in the photon energy range 13.6-27.0 eV. The resonant structures observed in SF(5)CF(3) are attributed to electronic transitions from valence to Rydberg orbitals, following similar assignments in CF(3)X molecules. The photoabsorption spectrum of SF(5)CF(3) shows features at the same energies, indicating a strong contribution from Rydberg excitations.