Analysis of laser-induced fluorescence spectra of the (″)–(″) transition with calculated Franck–Condon factors of CH2CFO

Yamaguchi, Makoto; Furubayashi, Masashi; Inomata, Satoshi; Washida, Nobuaki

doi:10.1016/s0009-2614(98)01188-9

Cited by 6 publications

(7 citation statements)

References 24 publications

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“…4͑a͔͒, which is consistent with calculations demonstrating that the primary geometry change between the X and B states is elongation of the CO bond. 3 In fact, nearly all the new features in the PFY spectrum, i.e., those beyond 32 570 cm Table II are supported by a simulation using a Dunham-type expansion,…”

Section: Analysis a Photofragment Yield Spectrummentioning

confidence: 80%

“…3 Several recent experimental and theoretical studies [1][2][3] have focused on the B 2 AЉ←X 2 AЉ transition, for which T 0 ϭ29 867 cm Ϫ1 ͑3.70 eV͒. 2 Furubayashi et al 1 reported a vibrationally-resolved laser-induced fluorescence ͑LIF͒ excitation spectrum of CH 2 CFO over the range of 29 870-32 570 cm Ϫ1 .…”

Section: Introductionmentioning

confidence: 99%

“…2 Calculations of optimized geometries and vibrational frequencies for the X and B states of CH 2 CFO using the complete active space self-consistent field ͑CASSCF͒ method established that the observed band was the result of exciting the B state. 3 Spectral assignments, aided by measured dispersed fluorescence spectra, revealed excitation of the 3 ͑C-O stretch͒, 4 ͑CHH scissor͒, 5 ͑C-F stretch͒, 6 (CH 2 rock͒, 7 ͑C-C stretch͒, 8 ͑FCO bend͒, and 9 ͑CCO bend͒ modes of the B state. 1,6 The LIF study by Furubayashi et The heats of formation used to obtain the heats of reaction for channels ͑1͒-͑3͒, ͑5͒, and ͑6͒ are listed in Table I, while the heat of reaction for channel ͑4͒ is obtained from the theoretical work by Cao et al 7 The energy level diagram for CH 2 CFO and these product channels is presented in Fig.…”

Section: Introductionmentioning

confidence: 99%

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Photodissociation spectroscopy and dynamics of the CH2CFO radical

Hoops

Gascooke

Kautzman

et al. 2004

The Journal of Chemical Physics

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The photodissociation spectroscopy and dynamics resulting from excitation of the B 2 AЉ←X 2 AЉ transition of CH 2 CFO have been examined using fast beam photofragment translational spectroscopy. The photofragment yield spectrum reveals vibrationally resolved structure between 29 870 and 38 800 cm Ϫ1, extending ϳ6000 cm Ϫ1 higher in energy than previously reported in a laser-induced fluorescence excitation spectrum. At all photon energies investigated, only the CH 2 FϩCO and HCCOϩHF fragment channels are observed. Both product channels yield photofragment translational energy distributions that are characteristic of a decay mechanism with a barrier to dissociation. Using the barrier impulsive model, it is shown that fragmentation to CH 2 FϩCO products occurs on the ground state potential energy surface with the isomerization barrier between CH 2 CFO and CH 2 FCO governing the observed translational energy distributions.

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Section: Analysis a Photofragment Yield Spectrummentioning

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photodissociation spectroscopy and dynamics of the CH2CFO radical

Hoops

Gascooke

Kautzman

et al. 2004

The Journal of Chemical Physics

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“…Ab initio calculations were performed with the Gaussian 98 W program using a 6-31 G* basis set. Optimized geometries of the ground (X̃ 2 A‘ ‘) and excited B̃ 2 A‘ ‘ state for the cis -CHClCHO, trans -CHClCHO, and CH 2 CClO radicals were calculated by the CASSCF method as described previously . Vibrational frequencies at optimized geometries were obtained from analytically calculated force constant matrices.…”

Section: Resultsmentioning

confidence: 99%

Laser-Induced Fluorescence of the CHClCHO Radical and Reaction of Oxygen Atoms with Halogenated Ethylenes

et al. 2001

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A new laser-induced fluorescence spectrum has been observed in the region 320−360 nm. Since this spectrum is observed when reacting oxygen atoms with chlorinated ethylenes such as CH2CHCl, CH2CCl2, CHClCHCl, and CHClCHF and also when chlorine atoms react with chloroacetaldehyde, the fluorescing molecules are identified as cis- and trans-2 chlorovinoxy radicals (cis- and trans-CHClCHO). From an analysis of the laser-induced single vibronic level fluorescence, some of the vibrational frequencies can be assigned for the ground electronic state (X̃ 2A‘ ‘): ν3(CO str) = 1567, ν4(CH rock.) = 1380, ν5(CH rock.) = 1309, ν6(CC str) = 1060, ν7(CCl str) = 820, ν8(CCO bend.) = 677, and ν9(CCCl bend.) = 220 cm-1 for cis-CHClCHO; ν3 = 1581, ν4 = 1379, ν5 = 1267, ν6 = 1145, ν7 = 942, ν8 = 472, and ν9 = 324 cm-1 for trans-CHClCHO. Some of the vibrational frequencies for the excited B̃2A‘ ‘ state also are assigned. These vibrational assignments are supported by ab initio calculations. The calculated geometries of the cis- and trans-CHClCHO radicals are planar in the ground state and slightly nonplanar in the excited state. Radiative lifetimes of the excited cis- and trans-CHClCHO radicals are also reported. The experimental results showed that the C−C−O skeleton and spectroscopic character of the cis- and trans-CHClCHO are closer to those of CH2CHO than to those of CH2CFO. The mechanisms of the O + halogenated ethylene reactions are discussed.

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“…In contrast to this, due to the strong C–F bond, fluorinated alkoxy radicals are the major products of the photochemical decompositions of fluorinated alkyl nitrites. Among the fluorinated alkoxy radicals, trifluoromethoxy (CF 3 O) and β-monofluoroethoxy (CH 2 F–CH 2 O), and the unsaturated 1-fluorovinoxy (CH 2 CFO) − and cis - and trans -1,2-difluorovinoxy radicals (CFHCFO) were studied by LIF spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Revealing Long-Range Substituent Effects in the Laser-Induced Fluorescence and Dispersed Fluorescence Spectra of Jet-Cooled CH_xF_3–xCH₂O (x = 1, 2, 3) Radicals

et al. 2019

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The B ̃−X ̃laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the atmospherically important β-monofluoro ethoxy (MFEO), β,β-difluoro ethoxy (DFEO), and β,β,β-trifluoro ethoxy (TFEO) radicals were recorded with vibronic resolution under jet-cooled conditions. To simulate the spectra, Franck−Condon factors were obtained from quantum chemical computations carried out at the CAM-B3LYP/6-311++G(d,p) level of theory. The simulations reproduce well both the LIF and DF spectra. Both conformers (G and T) of MFEO and one (G) of the two conformers of DFEO contribute to the LIF spectrum. A comparison between the experimental and calculated spectra confirms the expected longrange field effects of the CH x F 3−x group on electronic transition energies and bond strengths, especially in the excited electronic (B ̃) state. Although TFEO has only one conformer, its LIF spectrum is highly congested, which is attributed to the interaction between CO stretch and the −CF 3 internal rotation.

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Analysis of laser-induced fluorescence spectra of the (″)–(″) transition with calculated Franck–Condon factors of CH2CFO

Cited by 6 publications

References 24 publications

Photodissociation spectroscopy and dynamics of the CH2CFO radical

Photodissociation spectroscopy and dynamics of the CH2CFO radical

Laser-Induced Fluorescence of the CHClCHO Radical and Reaction of Oxygen Atoms with Halogenated Ethylenes

Revealing Long-Range Substituent Effects in the Laser-Induced Fluorescence and Dispersed Fluorescence Spectra of Jet-Cooled CH_xF_3–xCH₂O (x = 1, 2, 3) Radicals

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Analysis of laser-induced fluorescence spectra of the (″)–(″) transition with calculated Franck–Condon factors of CH2CFO

Cited by 6 publications

References 24 publications

Photodissociation spectroscopy and dynamics of the CH2CFO radical

Photodissociation spectroscopy and dynamics of the CH2CFO radical

Laser-Induced Fluorescence of the CHClCHO Radical and Reaction of Oxygen Atoms with Halogenated Ethylenes

Revealing Long-Range Substituent Effects in the Laser-Induced Fluorescence and Dispersed Fluorescence Spectra of Jet-Cooled CHxF3–xCH2O (x = 1, 2, 3) Radicals

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Revealing Long-Range Substituent Effects in the Laser-Induced Fluorescence and Dispersed Fluorescence Spectra of Jet-Cooled CH_xF_3–xCH₂O (x = 1, 2, 3) Radicals