Communication: Observation of local-bender eigenstates in acetylene
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JCP_143_071101.pdf
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Author(s)
Steeves, Adam H.
Park III, George Barratt
Bechtel, Hans Anthony
Baraban, Joshua Herschel
Field, Robert W
Date Issued
August 2015
Journal
Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Steeves, Adam H., G. Barratt Park, Hans A. Bechtel, Joshua H. Baraban, and Robert W. Field. “Communication: Observation of Local-Bender Eigenstates in Acetylene.” J. Chem. Phys. 143, no. 7 (August 21, 2015): 071101. © 2015 AIP Publishing LLC.
Version
Final published version
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 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 coordinate
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1063/1.4928638
