Abstract

Rotational spectra of CF 3COOH…HCOOH and CF 3COOH…CH 3COOH bimolecules have been studied between 7 and 13 GHz with a pulsed nozzle beam Fourier transform spectrometer. The determination of a partial substitution structure of the former has been attempted from the analysis of 16 isotopomers. Deuteration of the hydrogen bonds has failed to locate the hydrogen nuclei in the hydrogen bonds. This has been attributed to a minute increase of the distance between the centers-of-mass of the monomer units. The rotational spectrum of CF 3COOH…CH 3COOH has shown splittings due to the internal rotation of the methyl group. The A state has been fitted to a rigid rotor Hamiltonian while the internal rotation parameters have been derived from the E–A state splittings by direct diagonalization of the Hamiltonian matrix. The internal rotation barrier of 97.2 (15) cm −1 is significantly lower than in the monomeric acetic acid.

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