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Schreiner PR, Wagner JP, Reisenauer HP, et al. Domino Tunneling. J Am Chem Soc. 2015;137(24):7828-34doi: 10.1021/jacs.5b03322.
Schreiner, P. R., Wagner, J. P., Reisenauer, H. P., Gerbig, D., Ley, D., Sarka, J., Császár, A. G., Vaughn, A., & Allen, W. D. (2015). Domino Tunneling. Journal of the American Chemical Society, 137(24), 7828-34. https://doi.org/10.1021/jacs.5b03322
Schreiner, Peter R, et al. "Domino Tunneling." Journal of the American Chemical Society vol. 137,24 (2015): 7828-34. doi: https://doi.org/10.1021/jacs.5b03322
Schreiner PR, Wagner JP, Reisenauer HP, Gerbig D, Ley D, Sarka J, Császár AG, Vaughn A, Allen WD. Domino Tunneling. J Am Chem Soc. 2015 Jun 24;137(24):7828-34. doi: 10.1021/jacs.5b03322. Epub 2015 Jun 15. PMID: 26027801.
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J Am Chem Soc. 2015 Jun 24;137(24):7828-34. doi: 10.1021/jacs.5b03322. Epub 2015 Jun 15.

Domino Tunneling.

Journal of the American Chemical Society

Peter R Schreiner, J Philipp Wagner, Hans Peter Reisenauer, Dennis Gerbig, David Ley, János Sarka, Attila G Császár, Alexander Vaughn, Wesley D Allen

Affiliations

  1. ?Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany.
  2. ‡Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University, PO Box 32, Budapest 112, Hungary, H-1518.
  3. §MTA-ELTE Complex Chemical Systems Research Group, Eötvös University, Budapest, Pázmány Péter Sétány 1/A, Hungary, H-1117.
  4. ?Center for Computational Quantum Chemistry and Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.

PMID: 26027801 DOI: 10.1021/jacs.5b03322

Abstract

Matrix-isolation experiments near 3 K and state-of-the-art quantum chemical computations demonstrate that oxalic acid [1, (COOH)2] exhibits a sequential quantum mechanical tunneling phenomenon not previously observed. Intensities of numerous infrared (IR) bands were used to monitor the temporal evolution of the lowest-energy O-H rotamers (1cTc, 1cTt, 1tTt) of oxalic acid for up to 19 days following near-infrared irradiation of the matrix. The relative energies of these rotamers are 0.0 (1cTc), 2.6 (1cTt), and 4.0 (1tTt) kcal mol(-1). A 1tTt → 1cTt → 1cTc isomerization cascade was observed with half-lives (t1/2) in different matrix sites ranging from 30 to 360 h, even though the sequential barriers of 9.7 and 10.4 kcal mol(-1) are much too high to be surmounted thermally under cryogenic conditions. A general mathematical model was developed for the complex kinetics of a reaction cascade with species in distinct matrix sites. With this model, a precise, global nonlinear least-squares fit was achieved simultaneously on the temporal profiles of nine IR bands of the 1cTc, 1cTt, and 1tTt rotamers. Classes of both fast (t(1/2) = 30-50 h) and slow (t(1/2) > 250 h) matrix sites were revealed, with the decay rate of the former in close agreement with first-principles computations for the conformational tunneling rates of the corresponding isolated molecules. Rigorous kinetic and theoretical analyses thus show that a "domino" tunneling mechanism is at work in these oxalic acid transformations.

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