2065-73-8Relevant academic research and scientific papers
Domino Tunneling
Schreiner, Peter R.,Wagner, J. Philipp,Reisenauer, Hans Peter,Gerbig, Dennis,Ley, David,Sarka, János,Császár, Attila G.,Vaughn, Alexander,Allen, Wesley D.
, p. 7828 - 7834 (2015)
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).
Precision measurement of the quadrupole coupling and chemical shift tensors of the deuterons in α-calcium formate
Schmitt, Heike,Zimmermann,Koerner,Stumber,Meinel,Haeberlen
, p. 65 - 77 (2001)
Using calcium formate, α-Ca(DCOO)2, as a test sample, we explore how precisely deuteron quadrupole coupling (QC) and chemical shift (CS) tensors Q and σ can currently be measured. The error limits, ±0:09 kHz for the components of Q and ±0:06 ppm for those of σ, are at least three times lower than in any comparable previous experiment. The concept of a new receiver is described. A signal/noise ratio of 100 is realized in single-shot FT spectra. The measurement strategies and a detailed error analysis are presented. The precision of the measurement of Q is limited by the uncertainty of the rotation angles of the sample and that of σ by the uncertainty of the phase correction parameters needed in FT spectroscopy. With a 4-sigma confidence, it is demonstrated for the first time that the unique QC tensor direction of a deuteron attached to a carbon deviates from the bond direction; the deviation found is (1:2±0:3°). Evidence is provided for intermolecular QC contributions. In terms of Q, their size is roughly 4 kHz. The deuteron QC tensors in α-Ca(DCOO)2 (two independent deuteron sites) are remarkable in three respects. For deuterons attached to sp2 carbons, first, the asymmetry factors η and, second, the quadrupole coupling constants CQ, are unusually small, η1 = 0:018; η2 = 0:011, and CQ1 = (151:27±0:06) kHz, CQ2 = (154:09±0:06) kHz. Third, the principal direction associated with the largest negative QC tensor component lies in and not, as usual, perpendicular to the molecular plane. A rationalization is provided for these observations. The CS tensors obtained are in quantitative agreement with the results of an earlier, less precise, line-narrowing multiple-pulse study of α-Ca(HCOO)2. The assignment proposed in that work is confirmed. Finally we argue that a further 10-fold increase of the measurement precision of deuteron QC tensors, and a 2-fold increase of that of CS tensors, should be possible. We indicate the measures that need to be taken.
