Communication: Observation of local-bender eigenstates in acetylene

Steeves, Adam H.; Park, G. Barratt; Bechtel, Hans A.; Baraban, Joshua H.; Field, Robert W.

doi:10.1063/1.4928638

Communication: Observation of local-bender eigenstates in acetylene

Journal Article · Wed Aug 19 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4928638· OSTI ID:1547026

^[1]; ^[2]; Bechtel, Hans A. ^[3]; ^[4]; ^[5]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ithaca College, Ithaca, NY (United States); Office of Scientific and Technical Information (OSTI)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Max Planck Inst. for Biophysical Chemistry, Göttingen (Germany)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Colorado, Boulder, CO (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Our work discusses 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_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 10 218.9 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 ⇌ vinylidene isomerization coordinate.

View Accepted Manuscript (DOE)

Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-87ER13671

OSTI ID:: 1547026

Alternate ID(s):: OSTI ID: 1229622

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 143; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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