Title

Communication: Observation of local-bender eigenstates in acetylene

Document Type

Article

Publication Date

8-21-2015

Abstract

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 S state involving excitation in the non-totally symmetric bending modes. The N = 14 level, lying at 8971.69 cm (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 = 16 level, lying at 10 218.9 cm , is consistent with expectations for increased separation of = 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 coordinate. 1 b b -1 -1

Publication Name

Journal of Chemical Physics

Volume Number

143

Issue Number

7

DOI

10.1063/1.4928638

Article

071101

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