Domino Tunneling

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

Research output: Contribution to journalArticle

22 Citations (Scopus)

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 (t1/2 = 30-50 h) and slow (t1/2 > 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. (Graph Presented).

Original languageEnglish
Pages (from-to)7828-7834
Number of pages7
JournalJournal of the American Chemical Society
Volume137
Issue number24
DOIs
Publication statusPublished - Jun 24 2015

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Oxalic Acid
Oxalic acid
Mechanical Phenomena
Infrared radiation
Least-Squares Analysis
Theoretical Models
Kinetics
Isomerization
Cryogenics
Irradiation
Mathematical models
Molecules
Experiments

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Schreiner, P. R., Wagner, J. P., Reisenauer, H. P., Gerbig, D., Ley, D., Sarka, J., ... Allen, W. D. (2015). Domino Tunneling. Journal of the American Chemical Society, 137(24), 7828-7834. https://doi.org/10.1021/jacs.5b03322

Domino Tunneling. / Schreiner, Peter R.; Wagner, J. Philipp; Reisenauer, Hans Peter; Gerbig, Dennis; Ley, David; Sarka, János; Császár, A.; Vaughn, Alexander; Allen, Wesley D.

In: Journal of the American Chemical Society, Vol. 137, No. 24, 24.06.2015, p. 7828-7834.

Research output: Contribution to journalArticle

Schreiner, PR, Wagner, JP, Reisenauer, HP, Gerbig, D, Ley, D, Sarka, J, Császár, A, Vaughn, A & Allen, WD 2015, 'Domino Tunneling', Journal of the American Chemical Society, vol. 137, no. 24, pp. 7828-7834. https://doi.org/10.1021/jacs.5b03322
Schreiner PR, Wagner JP, Reisenauer HP, Gerbig D, Ley D, Sarka J et al. Domino Tunneling. Journal of the American Chemical Society. 2015 Jun 24;137(24):7828-7834. https://doi.org/10.1021/jacs.5b03322
Schreiner, Peter R. ; Wagner, J. Philipp ; Reisenauer, Hans Peter ; Gerbig, Dennis ; Ley, David ; Sarka, János ; Császár, A. ; Vaughn, Alexander ; Allen, Wesley D. / Domino Tunneling. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 24. pp. 7828-7834.
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