Fourier transform microwave spectroscopy of the 13C- and 18O-substituted tropolone. Proton tunneling effect for the isotopic species with the asymmetric potential wells.

ABSTRACT

Fourier-transform microwave spectroscopy has been applied for the 13C/18O-substituted tropolone to observe tunneling-rotation transitions as well as pure rotational transitions. The tunneling-rotation transitions were observed between the 13C-4 and -6 forms as well as between 13C-3 and -7, between 13C-1 and -2, and between 18O-8 and -9 (we denote these tunneling pairs as 13C-46, etc., below) although they have an asymmetric tunneling potential due to the difference in the zero point energy (ZPE). From the observed tunneling splittings ΔEij (0.9800-1.6824 cm-1), the differences in ZPE Δij for the 13C-46, -37, -12, and 18O-89 species are derived to be -0.1104, 0.5652, -1.3682, and 1.3897 cm-1 to agree well with the DFT calculation. The state mixing ratio of the tunneling states decreases drastically from (44%56%) to (8.7%91.3%) for 13C-46 and 18O-89 with an increase in the asymmetry Δij of the tunneling potential function. The observed tunneling-rotation interaction constants Fij decrease from 16.001 to 9.224 cm-1 as the differences in ZPE Δij increase, while the diagonal tunneling-rotation interaction constants Fu increase from 1.767 to 13.70 cm-1, explained well by the mixing ratio of the tunneling states.