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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 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.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5]
+ Show Author Affiliations
  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). Chemical Sciences, Geosciences, and Biosciences Division
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.
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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. https://doi.org/10.1063/1.4928638
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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. https://doi.org/10.1063/1.4928638. https://www.osti.gov/servlets/purl/1547026.
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@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 = {Wed Aug 19 00:00:00 EDT 2015},
month = {Wed Aug 19 00:00:00 EDT 2015}
}
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https://doi.org/10.1063/1.4928638
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Works referenced in this record:

Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization
journal, December 2014

  • Han, Huixian; Li, Anyang; Guo, Hua
  • The Journal of Chemical Physics, Vol. 141, Issue 24
  • DOI: 10.1063/1.4904859

Anharmonic force fields of cis - and trans -S 1 C 2 H 2
journal, July 2012

The à 1 A u state of acetylene: ungerade vibrational levels in the region 45,800–46,550 cm −1
journal, July 2012

The electronic state of acetylene: Geometry and axis-switching effects
journal, November 1990

New vibrational force-field expansion of coupled linear benders: application to the X state of acetylene
journal, July 2003

Simplified Cartesian Basis Model for Intrapolyad Emission Intensities in the Bent-to-Linear Electronic Transition of Acetylene
journal, January 2015

  • Park, G. Barratt; Steeves, Adam H.; Baraban, Joshua H.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 5
  • DOI: 10.1021/jp5113608

Harmonically coupled, anharmonic oscillator model for the bending modes of acetylene
journal, June 1992

  • Lehmann, Kevin K.
  • The Journal of Chemical Physics, Vol. 96, Issue 11
  • DOI: 10.1063/1.462313

Vibrational Spectroscopic Database on Acetylene, X̃ 1Σg+ (12C2H2, 12C2D2, and 13C2H2)
journal, September 2003

  • Herman, M.; Campargue, A.; El Idrissi, M. I.
  • Journal of Physical and Chemical Reference Data, Vol. 32, Issue 3
  • DOI: 10.1063/1.1531651

Electronic Signatures of Large Amplitude Motions:  Dipole Moments of Vibrationally Excited Local-Bend and Local-Stretch States of S 0 Acetylene †
journal, September 2006

  • Wong, Bryan M.; Steeves, Adam H.; Field, Robert W.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 38
  • DOI: 10.1021/jp061924x

Direct observation of the symmetric stretching modes of à 1 A u acetylene by pulsed supersonic jet laser induced fluorescence
journal, August 2008

The bending dynamics of acetylene
journal, July 1996

  • McCoy, Anne B.; Sibert, Edwin L.
  • The Journal of Chemical Physics, Vol. 105, Issue 2
  • DOI: 10.1063/1.471899

Spectroscopic signatures of bond-breaking internal rotation. II. Rotation-vibration level structure and quantum monodromy in HCP
journal, January 2001

  • Jacobson, Matthew P.; Child, Mark S.
  • The Journal of Chemical Physics, Vol. 114, Issue 1
  • DOI: 10.1063/1.1330746

T HE D YNAMICS OF “S TRETCHED M OLECULES ”: Experimental Studies of Highly Vibrationally Excited Molecules With Stimulated Emission Pumping
journal, October 2001

Cis-trans isomerization in the S 1 state of acetylene: Identification of cis-well vibrational levels
journal, June 2011

  • Merer, Anthony J.; Steeves, Adam H.; Baraban, Joshua H.
  • The Journal of Chemical Physics, Vol. 134, Issue 24
  • DOI: 10.1063/1.3599091

Numerical pattern recognition analysis of acetylene dispersed fluorescence spectra
journal, May 1998

  • O’Brien, Jonathan P.; Jacobson, Matthew P.; Sokol, Jennifer J.
  • The Journal of Chemical Physics, Vol. 108, Issue 17
  • DOI: 10.1063/1.476127

Bending dynamics from acetylene spectra: Normal, local, and precessional modes
journal, December 1996

  • Rose, John P.; Kellman, Michael E.
  • The Journal of Chemical Physics, Vol. 105, Issue 24
  • DOI: 10.1063/1.472882

Darling–Dennison resonance and Coriolis coupling in the bending overtones of the ÃAu1 state of acetylene, C2H2
journal, August 2008

  • Merer, Anthony J.; Yamakita, Nami; Tsuchiya, Soji
  • The Journal of Chemical Physics, Vol. 129, Issue 5
  • DOI: 10.1063/1.2939246

Overtone Frequencies and Intensities in the Local Mode Picture
book, January 1984

Local mode behavior in the acetylene bending system
journal, January 1999

  • Jacobson, Matthew P.; Silbey, Robert J.; Field, Robert W.
  • The Journal of Chemical Physics, Vol. 110, Issue 2
  • DOI: 10.1063/1.478052

Higher vibrational levels of a bent triatomic molecule
journal, January 1964

Complete experimental rovibrational eigenenergies of HCN up to 6880 cm −1 above the ground state
journal, June 2011

  • Mellau, Georg Ch.
  • The Journal of Chemical Physics, Vol. 134, Issue 23
  • DOI: 10.1063/1.3598942

OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide
journal, June 2006

  • Fry, Juliane L.; Matthews, Jamie; Lane, Joseph R.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 22
  • DOI: 10.1021/jp0612127

Molecular constants for the bending modes of acetylene 12C2H2
journal, October 1972

Quantum, semiclassical and classical dynamics of the bending modes of acetylene
journal, July 1996

  • Sibert, Edwin L.; McCoy, Anne B.
  • The Journal of Chemical Physics, Vol. 105, Issue 2
  • DOI: 10.1063/1.471900

Periodic orbits and bifurcation diagrams of acetylene/vinylidene revisited
journal, May 2003

  • Prosmiti, Rita; Farantos, Stavros C.
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1565991

Laser-Induced Fluorescence Study of the S 1 State of Doubly-Substituted 13 C Acetylene and Harmonic Force Field Determination
journal, September 2013

  • Jiang, Jun; Baraban, Joshua H.; Park, G. Barratt
  • The Journal of Physical Chemistry A, Vol. 117, Issue 50
  • DOI: 10.1021/jp407755m

Full dimensional Franck-Condon factors for the acetylene à 1 A u —X̃ Σg+1 transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes
journal, October 2014

  • Park, G. Barratt; Baraban, Joshua H.; Field, Robert W.
  • The Journal of Chemical Physics, Vol. 141, Issue 13
  • DOI: 10.1063/1.4896533

The infrared-ultraviolet dispersed fluorescence spectrum of acetylene: New classes of bright states
journal, May 2001

  • Hoshina, Kennosuke; Iwasaki, Atsushi; Yamanouchi, Kaoru
  • The Journal of Chemical Physics, Vol. 114, Issue 17
  • DOI: 10.1063/1.1333006

Bending Dynamics of Acetylene:  New Modes Born in Bifurcations of Normal Modes †
journal, September 2006

  • Tyng, Vivian; Kellman, Michael E.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 38
  • DOI: 10.1021/jp057357f

Probing highly excited vibrational eigenfunctions using a modified single Lanczos propagation method: Application to acetylene (HCCH)
journal, January 2003

  • Xu, Dingguo; Chen, Rongqing; Guo, Hua
  • The Journal of Chemical Physics, Vol. 118, Issue 16
  • DOI: 10.1063/1.1562626

Stretch-bend combination polyads in the Ã1Au state of acetylene, C2H2
journal, August 2009

  • Steeves, Adam H.; Bechtel, Hans A.; Merer, Anthony J.
  • Journal of Molecular Spectroscopy, Vol. 256, Issue 2
  • DOI: 10.1016/j.jms.2009.05.005
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