2002
DOI: 10.1021/jp014431v
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Vibrationally Mediated Photodissociation of Jet-Cooled CH3CF2Cl:  A Probe of Energy Flow and Bond Breaking Dynamics

Abstract: A double resonance scheme was employed to photodissociate jet-cooled CH 3 CF 2 Cl in a time-of-flight mass spectrometer. First, the molecule was promoted to the second (3ν CH ) or third (4ν CH ) methyl overtone by direct IR excitation. Subsequently, a UV laser beam at ∼235 nm was used to both dissociate the molecule and tag the Cl 2 P 3/2 [Cl] and Cl 2 P 1/2 [Cl*] photofragments by (2 + 1) resonantly enhanced multiphoton ionization. The photofragment action spectra revealed multiple peak structures in both ove… Show more

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Cited by 14 publications
(14 citation statements)
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“…Nonetheless, the general appearance of the features and the relative intensities of Cl and Cl à in the different bands of the action spectra seem to be comparable. This agrees with the behavior encountered in the VMP of CHF 2 Cl and CHFCl 2 [23,24], but differs from that observed in VMP of CH 3 Cl [14], where the action spectra of 35 Cl à and 37 Cl à were different. Moreover, the band Fig.…”
Section: Resultssupporting
confidence: 81%
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“…Nonetheless, the general appearance of the features and the relative intensities of Cl and Cl à in the different bands of the action spectra seem to be comparable. This agrees with the behavior encountered in the VMP of CHF 2 Cl and CHFCl 2 [23,24], but differs from that observed in VMP of CH 3 Cl [14], where the action spectra of 35 Cl à and 37 Cl à were different. Moreover, the band Fig.…”
Section: Resultssupporting
confidence: 81%
“…Since the combined energy used in the VMP of CH 2 Cl 2 , $51 180 cm À1 , is only slightly less than that used in the 193 nm photodissociation, 51 813 cm À1 , it seems unreasonable that the difference in energy led to the variation in the branching ratio. It should be noted that an increase in the branching into Cl à was also observed in the VMP of other chlorine containing molecules, including CH 3 Cl, CHD 2 Cl, CH 3 CF 2 Cl, and CH 3 CFCl 2 [15,16,23,24], but not in that of CHF 2 Cl [26]. Therefore, the alteration of the branching ratio is probably due to the varied non-adiabatic dynamics in VMP, which determines the fragment spin-orbit splitting during the departure from the molecule.…”
Section: Resultsmentioning
confidence: 69%
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