Communication: Observation of local-bender eigenstates in acetylene

We report the observation of eigenstates that embody large-amplitude, local-bending vibrational motion in acetylene by stimulated emission pumping spectroscopy via vibrational levels of the S1 state involving excitation in the non-totally symmetric bending modes. The N[subscript b] = 14 level, lying at 8971.69 cm[superscript −1] (J = 0), is assigned on the basis of degeneracy due to dynamical symmetry breaking in the local-mode limit. The level pattern for the N[subscript b] = 16 level, lying at 10 218.9 cm[superscript−1], is consistent with expectations for increased separation of ℓ = 0 and 2 vibrational angular momentum components. Increasingly poor agreement between our observations and the predicted positions of these levels highlights the failure of currently available normal mode effective Hamiltonian models to extrapolate to regions of the potential energy surface involving large-amplitude displacement along the acetylene ⇌ vinylidene isomerization coordinateUnited States. Dept. of Energy. Office of Basic Energy Sciences. Chemical Sciences Geosciences and Biosciences Division (Award No. DE-FG0287ER13671