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On the heat of formation of carbonyl fluoride, CF2O

J. Chem. Phys. 105, 9781 (1996); doi:10.1063/1.472848

Issue Date: 8 December 1996

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Robert L. Asher, Evan H. Appelman, and Branko Ruscic
Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439-4831
In light of the recent controversy surrounding its heat of formation, CF2O was reexamined by photoionization mass spectrometry. In particular, the CO+ fragment ion yield curve from CF2O was interpreted in terms of a retarded CO++F2 process, and a more facile two-step fragmentation to CO++2F. The former process produces a weak, slowly growing tail region without a clear onset, while the latter occurs at higher energy and causes a pronounced growth with a conspicuous onset, which was found to occur at <=20.87+0.03/–0.07 eV at 0 K by fitting with a model curve that incorporates ``fluctuations'' associated with second-generation fragments. This onset leads to DeltaH<sub>f</sub><sup>[degree]</sup> 298(CF2O) >=–149.1+1.4/–0.7 kcal/mol, and indicates that the older experimental values for this quantity are too low by at least 3–4 kcal/mol. While the F2 elimination is retarded by competition with lower energy processes, the two-step process derives its strength from the FCO+ fragment, which assumes the role of a pseudoparent. Thus, the onset of CO++2F is expected to appear reasonably close to the thermochemical threshold. Such an interpretation indicates that recently calculated ab initio values of –145.3±1.7 kcal/mol and –145.6±1.0 kcal/mol are very likely too high by 3–4 kcal/mol. In addition, the adiabatic ionization potential of CF2O was refined to 13.024±0.004 eV, while the 0 K appearance potential of the FCO+ fragment was found by fitting to be <=14.752±0.005 eV. Together with the suggested value for DeltaH<sub>f</sub><sup>[degree]</sup>(CF2O), these two onsets lead to DeltaH<sub>f</sub><sup>[degree]</sup> 298(CF2O+)=151.2+1.4/–0.7 kcal/mol and DeltaH<sub>f</sub><sup>[degree]</sup> 298(FCO+)=173.5+1.4/–0.7 kcal/mol. ©1996 American Institute of Physics.
History: Received 19 July 1996; accepted 3 September 1996
Permalink: http://link.aip.org/link/?JCPSA6/105/9781/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.60.Cx
    Physical Chemistry Chemical thermodynamics Enthalpies of combustion, reaction, and formation
  • 33.15.Ta
    Molecular properties and interactions with photons Properties of molecules and molecular ions Mass spectra
  • 33.15.Ry
    Molecular properties and interactions with photons Properties of molecules and molecular ions Ionization potentials, electron affinities, molecular core binding energy
  • YEAR: 1996

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ISSN:
0021-9606 (print)   1089-7690 (online)
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