Unraveling the spectroscopy of coupled intramolecular tunneling modes:A study of double proton transfer in the formic-acetic acid complex

Tayler, Michael C.D. and Ouyang, Bin and Howard, Brian J. (2011) Unraveling the spectroscopy of coupled intramolecular tunneling modes:A study of double proton transfer in the formic-acetic acid complex. Journal of Chemical Physics, 134 (5). ISSN 0021-9606

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Abstract

The rotational spectrum of the hetero dimer comprising doubly hydrogen-bonded formic acid and acetic acid has been recorded between 4 and 18 GHz using a pulsed-nozzle Fourier transform microwave spectrometer. Each rigid-molecule rotational transition is split into four as a result of two concurrently ongoing tunneling motions, one being proton transfer between the two acid molecules, and the other the torsion/rotation of the methyl group within the acetyl part. We present a full assignment of the spectrum J 1 to J 6 for the ground vibronic states. The transitions are fitted to within a few kilohertz of the observed frequencies using a molecule-fixed effective rotational Hamiltonian for the separate A and E vibrational species of the G12 permutation-inversion symmetry group. Interpretation of the motion problem uses an internal-vibration and overall-rotation angular momentum coupling scheme and full sets of rotational and centrifugal distortion constants are determined. The tunneling frequencies of the proton-transfer motion are measured for the ground A and E methyl rotation states as 250.4442(12) and -136.1673(30) MHz, respectively. The slight deviation of the latter tunneling frequency from being one half of the former, as simple theory otherwise predicts, is due to different degrees of mixing in wavefunctions between the ground and excited states.

Item Type:
Journal Article
Journal or Publication Title:
Journal of Chemical Physics
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1600/1606
Subjects:
ID Code:
135594
Deposited By:
Deposited On:
22 Jul 2019 09:45
Refereed?:
Yes
Published?:
Published
Last Modified:
19 Aug 2020 05:36