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Title: Communication: Observation of local-bender eigenstates in acetylene

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ithaca College, Ithaca, NY (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Max Planck Inst. for Biophysical Chemistry, Göttingen (Germany)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Colorado, Boulder, CO (United States)
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1547026
Alternate Identifier(s):
OSTI ID: 1229622
Grant/Contract Number:  
FG02-87ER13671; FG0287ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Steeves, Adam H., Park, G. Barratt, Bechtel, Hans A., Baraban, Joshua H., and Field, Robert W. Communication: Observation of local-bender eigenstates in acetylene. United States: N. p., 2015. Web. doi:10.1063/1.4928638.
Steeves, Adam H., Park, G. Barratt, Bechtel, Hans A., Baraban, Joshua H., & Field, Robert W. Communication: Observation of local-bender eigenstates in acetylene. United States. doi:10.1063/1.4928638.
Steeves, Adam H., Park, G. Barratt, Bechtel, Hans A., Baraban, Joshua H., and Field, Robert W. Wed . "Communication: Observation of local-bender eigenstates in acetylene". United States. doi:10.1063/1.4928638. https://www.osti.gov/servlets/purl/1547026.
@article{osti_1547026,
title = {Communication: Observation of local-bender eigenstates in acetylene},
author = {Steeves, Adam H. and Park, G. Barratt and Bechtel, Hans A. and Baraban, Joshua H. and Field, Robert W.},
abstractNote = {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 Nb = 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 Nb = 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.},
doi = {10.1063/1.4928638},
journal = {Journal of Chemical Physics},
number = 7,
volume = 143,
place = {United States},
year = {2015},
month = {8}
}

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