The CF 3 S radical has been investigated using the LIF and fluorescence depletion techniques. The vibrational structure of the first excited A 2 A 1 state has been assigned. The photodissociation process at energies above the origin of the A state has been characterized by fluorescence temporal decay and fluorescence depletion spectroscopy. Above the photodissociation threshold the ratio of the rates for the competing processes of emission and dissociation varies strongly with both energy and vibrational mode.
The A -2 electronic transition of CF3O was observed in a supersonic jet using laser-induced fluorescence.Rotational analysis of the high-resolution spectrum of the origin band is consistent with CF30 having C3" symmetry in both its ground and excited electronic states. The lowest level is best described as *E312 with residual unquenched electronic angular momentum, leading to a significant spin-arbit splitting.
Electronic spectroscopy of the 3 d Rydberg states of NO-Rg ( Rg = Ne , Ar , Kr , Xe ) van der Waals complexesThe laser induced fluorescence spectra of the thiohydroxyl radical inert gas complexes, R•SH ͑RϭNe, Ar, and Kr͒ are reported. The spectra of numerous isotopomers involving 32 S, 34 S, 84 Kr, 86 Kr, 1 H, and 2 H have been observed. By using isotopic shifts of the heavy atoms, and other observations, the overwhelming majority of the 60 observed vibronic transitions have been assigned as originating from the vibrationless level of the X 2 ⌸ state and terminating on specific vibrational levels (v SH , v b k , v s ) of the à 2 ⌺ ϩ state, where nominally v s is the R-SH stretch, v SH is the SH monomer stretch, and v b k is the bending vibration. Vibrational frequencies, e , and anharmonicities, e x e , for many of the modes are obtained, as well as dissociation energies ͑assuming a simple model͒ for both the à and X states of the R•SH complexes.
The natural lifetimes of a large number of the vibrational levels of the excited à 2Σ+ electronic state of the family of rare gas complexes, R⋅SH (R=Ne, Ar, and Kr) and their deuterides, are reported. It is well known that the natural lifetime of the à 2Σ+ state of isolated SH/D is markedly shortened by a photofragmentation process. Our results for the complexes show that the rare gas atom plays an important role in inhibiting this process. From a classical model of the molecular system we are able to explain the trends observed in our lifetime data. The data from the R⋅SD complexes where for some vibrational levels the deuterium atom appears to be trapped between the rare gas and sulfur atoms allows us to establish a radiative lifetime for these complexes and the SH/D monomer.
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