Laser-excitation spectrum of supersonically cooled bromofluorocarbene in the gas phase

Schlachta, Richard; Lask, G.; Bondybey, V. E.

doi:10.1016/0009-2614(91)90318-4

Cited by 9 publications

(5 citation statements)

References 18 publications

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“…Table reports the calculated adiabatic transition energies, T 00 , for the Ã( 1 A′′) ← X̃( 1 A′) transition of the bromocarbenes obtained at the MRCI+Dav/cc-pVTZ level (including vibrational zero-point corrections) along with recent experimental and computational results. Experimental values are available for all the bromocarbenes except CIBr. ,,, The experimental T 00 value for CFBr listed in Table is based on a recent reanalysis of the Ã( 1 A′′) ← X̃( 1 A′) transition, which led to an increase in the band origin from the previous value of 20 906 cm −1 to the value of 23 271 cm −1 . Also, for CBr 2 , the experimental result of 15 279 cm −1 for T 00 reported in Table is based on a reassignment of the Ã 1 A′′−X̃ 1 A′ system, which increased the band origin relative to the previous experimental value of 15 093 cm −1 …”

Section: Resultsmentioning

confidence: 99%

Multireference Configuration Interaction Study of Bromocarbenes

et al. 2011

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Multireference configuration interaction (MRCI) calculations of the lowest singlet X(1A') and triplet ã((3)A'') states as well as the first excited singlet Ã((1)A'') state have been performed for a series of bromocarbenes: CHBr, CFBr, CClBr, CBr(2), and CIBr. The MRCI calculations were performed with correlation consistent basis sets of valence triple-ζ plus polarization quality, employing a full-valence active space of 18 electrons in 12 orbitals (12 and 9, respectively, for CHBr). Results obtained include equilibrium geometries and harmonic vibrational frequencies for each of the electronic states, along with ã((3)A'') ← X((1)A') singlet-triplet gaps and Ã((1)A'') ← X((1)A') transition energies. Comparisons have been made with previous computational and experimental results where available. The MRCI calculations presented in this work provide a comprehensive series of results at a consistent high level of theory for all of the bromocarbenes.

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Section: Resultsmentioning

confidence: 99%

Multireference Configuration Interaction Study of Bromocarbenes

et al. 2011

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“…Between the ͑0,6,0͒ and ͑0,7,0͒ bands are a series of transitions that are assigned positively as the LIF spectrum of CFBr. 23,24 The frequencies of these transitions are secure and provide a second reference point. The measured absolute wave number of these CFBr transitions vary by less than 1 cm Ϫ1 from the previously published values and provide some assurance that the spectrum has remained calibrated after Ͼ6000 cm Ϫ1 of scanning.…”

Section: Resultsmentioning

confidence: 99%

“…To date, the electronic spectroscopy of several halogenated carbenes has been investigated, including HCF, 2-7 CH 2 , 8,9 CHCl, 6,10 CHBr, 11,12 CF 2 , [13][14][15][16][17] CFCl, 18,19 CFBr, [20][21][22][23][24] and CCl 2 . 25 Clean production of these molecules in situ is difficult and thus only CH 2 ͑Refs.…”

Section: Introductionmentioning

confidence: 99%

Characterization of the Ã(1A″) state of HCF by laser induced fluorescence spectroscopy

Schmidt

Bacskay

Kable

1999

The Journal of Chemical Physics

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The laser-induced fluorescence spectrum, Renner-Teller effect, and molecular quantum beats in the Ã 2 Π i -X̃ 2 Π i transition of the jet-cooled HCCSe free radical An extensive experimental exploration of the Ã ( 1 AЉ)←X ( 1 AЈ) transition of supersonically cooled fluoromethylene has been performed using laser induced fluorescence spectroscopy. Several new bending vibrational bands are reported, which provide the harmonic frequency and anharmonicity constant for this vibration and lead to an estimate of the height of the barrier to linearity as 6400Ϯ500 cm Ϫ1 . Assignment of the vibrational hot-band structure leads to the first measurement of the Ã state CF stretching frequency as 3 Јϭ1260 cm Ϫ1 and tentatively the CH stretching frequency as 1 Јϭ2852 cm Ϫ1 . The AЈ rotational constant increases strongly with increasing quanta of bending vibration, which indicates that the molecular structure is becoming more linear. Consideration of only the average bond angle, calculated from ab initio data for this state, is insufficient to account for the change in AЈ. The coupling of a-axis rotation with bending vibration must be included. A number of other dynamical effects were observed in the spectra, including lifetime shortening and disappearance of rotational transitions with KЈу1. These were explained in terms of the Renner-Teller interaction between the X and Ã states.

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“…A later result found the origin to be at 20 906 cm -1 (478 nm) using CFBr 3 as the carbene precursor and a technique that combines dc discharge with pulsed supersonic expansion cooling of the products. 383…”

Section: Bromofluorocarbenementioning

confidence: 99%