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Zeitschriftenartikel:

G. Argüello, H. Grothe, M. Kronberg, H. Willner, H. Mack:
"IR and Visible Absorption Spectrum of the Fluoroformyloxyl Radical, FCO2, Isolated in Inert Gas Matrices";
Journal of Physical Chemistry, 99 (1995), S. 17525 - 17533.



Kurzfassung englisch:
Vacuum flash pyrolysis of bis(fluoroformyl) peroxide, FC(O)OOC(O)F, diluted in N2, Ar, or Ne, yields on subsequent quenching of the products in a matrix at 10, 14, or 6 K, respectively, the fluoroformyloxyl radical, FCO2, in the X2B2 ground state. It has been possible to record its infrared spectrum and to identify all bands by their photochemical behavior for the first time. The assignment of the six fundamental vibrations on the basis of C2v symmetry (a1 1475, 960, 519; bl 1098,474, b2 735 cm-1; Ne matrix) was achieved by a normal coordinate analysis taking into account additional data of 18O- or 13C-labeled FCO2. The experimental fundamental vibrations and the structural parameters derived from the vibrational data are compared to the results of ab initio and DFT (density functional theory) calculations. The visible spectrum of FCO2 isolated in a neon matrix agrees with the known gas phase spectrum. The origin of the B2A1 - X2B2 transition is observed at 13103 cm-1, and four fundamentals at 1607, 1117, 839, and 611 cm-1 are detected due to the excited state species (B2A1). In a fast reaction with NO, the FCO2 radical quantitatively forms FNO and C02. The anticipated intermediate FC(0)ONO is not observed.


"Offizielle" elektronische Version der Publikation (entsprechend ihrem Digital Object Identifier - DOI)
http://dx.doi.org/10.1021/j100049a010

Elektronische Version der Publikation:
http://pubs.acs.org/doi/pdf/10.1021/j100049a010


Erstellt aus der Publikationsdatenbank der Technischen Universitšt Wien.