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  Communication: Observation of local-bender eigenstates in acetylene.

Steeves, A. H., Park, B., Bechtel, H. A., Baraban, J. H., & Field, R. W. (2015). Communication: Observation of local-bender eigenstates in acetylene. Journal of Chemical Physics, 143(7): 071101. doi:10.1063/1.4928638.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0028-5B32-3 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0029-20FA-B
Genre: Journal Article

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2192698.pdf (Publisher version), 807KB
 
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 Creators:
Steeves, A. H., Author
Park, B.1, Author              
Bechtel, H. A., Author
Baraban, J. H., Author
Field, R. W., Author
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

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 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-1 state involving excitation in the non-totally symmetric bending modes. The N-b = 14 level, lying at 8971.69 cm(-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-b = 16 level, lying at 10218.9 cm(-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 reversible arrow vinylidene isomerization coordinate.

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Language(s): eng - English
 Dates: 2015-08-192015-08-21
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1063/1.4928638
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Title: Journal of Chemical Physics
Source Genre: Journal
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Pages: 4 Volume / Issue: 143 (7) Sequence Number: 071101 Start / End Page: - Identifier: -