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Publication Citation: A Microwave Study of Hydrogen-Transfer-Triggered Methyl-Group Rotation in 5-Methyltropolone

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Author(s): Vadim V. Ilyushin; Emily A. Cloessner; Yung-Ching Chou; Laura B. Picraux; Jon T. Hougen; Richard Lavrich;
Title: A Microwave Study of Hydrogen-Transfer-Triggered Methyl-Group Rotation in 5-Methyltropolone
Published: November 10, 2010
Abstract: We present here the first experimental and theoretical study of the microwave spectrum of 5-methyltropolone, which can be visualized as a 7-membered aromatic carbon ring with a five-membered hydrogen-bonded cyclic structure at the top and a methyl group at the bottom. The molecule exhibits two large-amplitude motions, an intramolecular hydrogen transfer and a methyl torsion. The former motion is particularly interesting because transfer of the hydrogen atom from the hydroxyl to the carbonyl group induces a tautomerization in the molecule, which then triggers a 60 internal rotation of the methyl group. Measurements were carried out by Fourier-transform microwave spectroscopy in the 8 GHz to 24 GHz frequency range. Theoretical analysis was carried out using a tunneling-rotational Hamiltonian based on a G12m extended-group theoretical formalism. Our global fit of 1015 transitions to 20 molecular parameters gave a root-mean-square deviation of 1.5 kHz. Tunneling splittings associated with a hypothetical pure hydrogen transfer motion and with a pure methyl-top internal rotation motion were determined to be 1310 MHz and 885 MHz, respectively.
Citation: Journal of Molecular Spectroscopy
Volume: 133
Pages: 9 pp.
Keywords: Hydrogen Transfer; Internal Rotation; Large-Amplitude Motion; Microwave Spectrum; Tunneling Hamiltonian; Tunneling Splittings
Research Areas: Physics, Chemical Physics, Molecular Spectroscopy
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