Coherent Tunneling Phenomena in Tropolone

and A14/A0 = 1.93. Good convergence was obtained for the lower vibrational frequencies but converged Ay splittings could not be obtained for the OH/CH stretching frequencies. 

The most recent publications on the S -Sq transition of TRN(OH) are by Braca-monte and Vacarro ]37, 38], who applied their polarization resolved DFWM spectroscopy method [37] to TRN vapor at its room temperature sublimation pressure. This remarkable nonlinear spectroscopic method simplifies the spectrum by allowing Q branch (A/ = 0) transitions to be observed with greatly diminished R and P branch (AJ = 1) signal and, with rotation of a polarization element, vice versa. This selective nonlinear optical technique also produces a large reduction in the signal generated by hot bands, as noted in the above discussion for MA. How- 

Tropolone is easily deuterated and the Sj-Sq fluorescence excitation spectrum of jet-cooled TRN(OD) was reported by Sekiya et al. [40]. The observed doublet separation, DS = 2 cm 1, is near the 2.2 cm value reported by Alves and Hollis [22], and about 10% of the value observed for TRN(OH). Presently the only available experimental estimate for the ZP tunneling splitting of Sq TRN(OD) is Ao 0.17 cm 1 [80] obtained using a chloroform solvent and NMR spectroscopy to measure the deuteron spin-lattice relaxation time. 

Hameka and de la Vega [85] presented a theoretical description of the ZP energy levels and probability density functions for a particle in a slightly asymmetric double-well PEF. They analyzed the model behavior in terms of two basic parameters  

S (the energy offset between the two PEF minima), and A (the tunneling splitting that occurs for the limiting equal double-well PEF - namely at 5 = 0). Equations presented by Hameka and de la Vega are easily combined [39, 82] into the equation ( A)2 + A, where is the splitting of the ZP energy levels in the PEP. 

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