Laser-induced fluorescence excitation and dispersed fluorescence spectroscopy of the Ã(1B1)–X̃(1A1) transition of dichlorocarbene

Guss, Joseph S.; Richmond, Craig; Nauta, Klaas; Kable, Scott H.

doi:10.1039/b413391a

Cited by 19 publications

(29 citation statements)

References 52 publications

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“…The spectroscopy of the electronic transition A 1 B 1 ← X 1 A 1 of the dichlorocarbene radical, CCl 2 , has been extensively studied to derive its physical and chemical properties . The values of the harmonic and anharmonic constants are well defined .…”

Section: Introductionmentioning

confidence: 99%

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Gómez

D'Accurso

Manzano

et al. 2014

Int J of Chemical Kinetics

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The rate constant of the reaction between CCl2 radicals and HCl was experimentally determined. The CCl2 radicals were obtained by infrared multiphoton dissociation of CDCl3. The time dependence of the CCl2 radicals' concentration in the presence of HCl was determined by laser‐induced fluorescence. The experimental conditions allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C2Cl4 and to the reaction with HCl to form CHCl3. The rate constant for the self‐recombination reaction was determined to be in the high‐pressure regime. The value obtained at 300 K was (5.7 ± 0.1) × 10−13 cm3 molecule−1 s−1, whereas the value of the rate constant measured for the reaction with HCl was (2.7 ± 0.1) × 10−14 cm3 molecule−1 s−1.

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Section: Introductionmentioning

confidence: 99%

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Gómez

D'Accurso

Manzano

et al. 2014

Int J of Chemical Kinetics

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“…[12][13][14] Panels ͑a͒ and ͑b͒ of Fig. In order to gauge the degree of internal excitation of the CCl 2 precursor, laser fluorescence excitation spectra were recorded in its Ã 1 B 1 -X 1 A 1 band system.…”

Section: A the CCL 2 Parent Moleculementioning

confidence: 99%

“…[58][59][60][61] This species could be detected only when the pyrolysis beam source heater and photolysis laser were on. It should be noted that Clouthier and Karolczak, 12 Guss et al, 14 Morley et al, 38 and Kohn et al 47 have also used a flash pyrolysis molecular beam source for spectroscopic and photodissociation dynamics studies of CCl 2 . Figure 3 presents a comparison of the dependence of the CCl signal for 193 nm photodissociation and the CCl 2 signal, the latter for excitation of the ground vibronic and X ͑0,1,0͒ levels, upon the pyrolysis heater current.…”

Section: B the CCL Photofragmentmentioning

confidence: 99%

Dynamics of the 193nm photodissociation of dichlorocarbene

Shin

Dagdigian

2006

The Journal of Chemical Physics

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The dynamics of the 193 nm photodissociation of the CCl2 molecule have been investigated in a molecular beam experiment. The CCl2 parent molecule was generated in a molecular beam by pyrolysis of CHCl3, and both CCl2 and the CCl photofragment were detected by laser fluorescence excitation. The 193 nm attenuation cross section was estimated from the reduction of the CCl2 signal as a function of the photolysis laser fluence. The internal state distribution of the CCl photofragment was derived from analysis of laser fluorescence excitation spectra in the A 2Delta-X 2Pi band system. Most of the energy available to the CCl(X 2Pi)+Cl fragments appears as translational energy. The CCl fragment rotational energy is much less than predicted in an impulsive model. The excited electronic state appears to dissociate indirectly, through coupling with a repulsive state arising from the ground-state CCl(X 2Pi)+Cl asymptote. The identity of the initially excited electronic state is discussed on the basis of what is known about the CCl2 electronic states.

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“…14 and 15 and references in these papers͒ and some new work on the spectroscopy of symmetric and mixed dihalospecies has also been published recently. 16,17 The electronic spectrum of chloromethylene has also received considerable attention since the original report of its observation in 1966. 12 As for all simple substituted methylenes, its spectrum exhibits the effects of Renner-Teller coupling between the Ã and X states, which correlate with a degenerate 1 ⌬ state at the linear configuration, and anharmonic resonances and spin-orbit coupling between the singlet and triplet manifolds.…”

Section: Introductionmentioning

confidence: 99%

Hot bands in jet-cooled and ambient temperature spectra of chloromethylene

Wang

Bird

et al. 2006

The Journal of Chemical Physics

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Rotationally resolved spectra of several bands lying to the red of the origin of the A(1)A" - X (1)A' band system of chloromethylene (HCCl), were recorded by laser absorption spectroscopy in ambient temperature and jet-cooled samples. The radical was made by excimer laser photolysis of dibromochloromethane, diluted in inert gas, at 193 nm. The jet-cooled sample showed efficient rotational but less vibrational cooling. Analysis showed that the observed bands originate in the (upsilon(1),upsilon(2),upsilon(3)) = (010), (001), and (011) vibrational levels of the ground electronic state of the radical, while the upper-state levels involved were (000), (010), (001), and (011). Vibrational energies and rotational constants describing the rotational levels in the lower-state vibrational levels were determined by fitting to combination differences. The analysis also resulted in a reevaluation of the C-Cl stretching frequency in the excited state and we find E(001)' = 13 206.57 or 926.17 cm(-1) above the A(1)A" (000) rotationless level for HC(35)Cl. Scaled ab initio potential energy surfaces for the A and X states were used to compute the transition moment surface and thereby the relative intensities of different vibronic transitions, providing additional support for the assignments and permitting the prediction of the shorter wavelength spectrum. All the observed upper state levels showed some degree of perturbation in their rotational energy levels, particularly in K(a) = 1, presumably due to coupling with near-resonant vibrationally excited levels of the ground electronic state. Transitions originating in the low-lying a(3)A" were also predicted to occur in the same wavelength region, but could not be identified in the spectra.

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Laser-induced fluorescence excitation and dispersed fluorescence spectroscopy of the Ã(¹B₁)–X̃(¹A₁) transition of dichlorocarbene

Cited by 19 publications

References 52 publications

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Dynamics of the 193nm photodissociation of dichlorocarbene

Hot bands in jet-cooled and ambient temperature spectra of chloromethylene

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Laser-induced fluorescence excitation and dispersed fluorescence spectroscopy of the Ã(1B1)–X̃(1A1) transition of dichlorocarbene

Cited by 19 publications

References 52 publications

Determination of the Rate Constant of the Reaction of CCl2 with HCl

Determination of the Rate Constant of the Reaction of CCl2 with HCl

Dynamics of the 193nm photodissociation of dichlorocarbene

Hot bands in jet-cooled and ambient temperature spectra of chloromethylene

Contact Info

Product

Resources

About

Laser-induced fluorescence excitation and dispersed fluorescence spectroscopy of the Ã(¹B₁)–X̃(¹A₁) transition of dichlorocarbene

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Determination of the Rate Constant of the Reaction of CCl₂ with HCl