Spectroscopy and Photochemical Dynamics of the CF<sub>3</sub>S Radical

Powers, D. E.; Pushkarsky, Michael B.; Yang, Min-Chieh; Miller, Terry A.

doi:10.1021/jp972202w

Cited by 14 publications

(18 citation statements)

References 38 publications

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“…As mentioned above, this state is similar to the Ã 2 A 1 excited state of CH 3 O, which is known to undergo predissociation to CH 3 + O when six or more quanta are excited in the C-O stretch; 47 this corresponds to 3791 cm -1 of vibrational excitation in the upper state. 49 The 3 0 6 transition in CH 3 O exhibits a shorter fluorescence lifetime than lower-energy 3 0 n transitions, 50 consistent with the onset of predissociation for the ν 3 ) 6 upper level. The predissociation results from a crossing between the bound Ã 2 A 1 state and several repulsive states leading to CH 3 + O.…”

Section: Discussionsupporting

confidence: 56%

Photodissociation Dynamics of the Ethoxy Radical (C₂H₅O)

2000

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Photodissociation of the ethoxy (C 2 H 5 O) radical is investigated using photofragment translational spectroscopy. The ethoxy radical is generated by photodetachment of C 2 H 5 O -and subsequently dissociated by photon absorption in the range of 270-220 nm; no dissociation is seen at higher wavelengths. The photofragment yield (PFY) spectrum is structureless but exhibits abrupt increases in intensity at 260 and 225 nm. The product mass distribution shows that C 2 H 5 O dissociates into the vinyl radical (C 2 H 3 ) and H 2 O throughout the entire absorption band. We propose that these products are formed by isomerization and dissociation on electronically excited surfaces rather than by internal conversion to the ground state. The translational energy P(E T ) distributions for this channel are largely insensitive to photon energy. However, at the two highest photon energies (5.51 and 5.96 eV), a new feature appears at E T e 0.3 eV, which is assigned as production of an excited state of C 2 H 3 .

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Section: Discussionsupporting

confidence: 56%

Photodissociation Dynamics of the Ethoxy Radical (C₂H₅O)

2000

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“…In cases of doubt, we were able to verify that the observed features were not hot bands using the fluorescence depletion technique. 24,27 This approach immediately resolved some of the remaining assignment questions and aided in identifying some new, weak cold features (such as the transitions involving two quanta of e symmetry modes).…”

Section: Vibrational Assignments Of Thementioning

confidence: 99%

“…An additional three members of the progression have been observed using the fluorescence depletion technique 24 and have been included in our analysis in Section III C. Where we do not wish to distinguish between the components of the multiplets we shall use the notation, (ν 2 + ν 3 ) m , to denote a given member of the progression.…”

Section: A Symmetric Modesmentioning

confidence: 99%

“…Dispersed fluorescence and SEP studies can be used to get a handle on the vibrational structure in the ground state but it is necessary to know the vibrations in the excited A state used in these studies, to interpret the X state structure. In a later paper 24 we will present photofragmentation studies on methoxy that reveal quite mode and frequency dependent photochemistry. The analysis of these results would be impossible without the excited state assignments presented herein.…”

Section: Introductionmentioning

confidence: 99%

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Rovibronic analysis of the laser induced fluorescence excitation spectrum of the jet-cooled methoxy radical

Powers

Pushkarsky

Miller

1997

The Journal of Chemical Physics

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The laser induced fluoresence excitation spectrum for the A 2 A 1 ↔ X 2 E transition of the methoxy radical has been reinvestigated. An extensive set of vibrational levels has been assigned with the aid of increased vibrational and rotational cooling. Many of these vibrational assignments are confirmed by rotational analysis of bands involving both the symmetric and asymmetric fundamentals of the A state as well as vibrations containing two quanta of the e modes. Although parts of the vibrational structure have been assigned previously, several discrepancies are identified and corrected. Vibrational frequencies have been obtained for all the modes in the A 2 A 1 state of the molecule. The Fermi resonance that exists between ν 3 and ν 2 has been investigated and interaction constants describing it have been obtained.

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“…electronic transition in three of the members of this family: The simplest perfluoroalkoxy radical is trifluoromethoxy, CH 3 O (13,14), CH 3 S (15), and the origin band of CF 3 O CF 3 O, and thus has been the most studied (1)(2)(3)(4)(5)(6)8). Fran- (8).…”

Section: Introductionmentioning

confidence: 99%