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Title: Reduced dimension rovibrational variational calculations of the S1 state of C2H2. II. The S1 rovibrational manifold and the effects of isomerization

Abstract

Reduced dimension variational calculations have been performed for the rovibrational level structure of the S1 state of acetylene. The state reflects an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm–1 above the trans, and the barrier to cis-trans isomerization lies about 5000 cm–1 above the trans minimum. The trans vibrations ν4 (torsion) and ν6 (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x36 cross-anharmonicity since the pathway to isomerization is a combination of ν6 and ν3 (sym. bend). Near the isomerization barrier, the vibrational levels show an even-odd K-staggering of their rotational levels as a result of quantum mechanical tunneling through the barrier. The current calculations address all of these complications, and reproduce the observed K-structures of the bending and C–C stretching levels with good qualitative accuracy. It is anticipated that they will assist with the assignment of the irregular patterns near the isomerization barrier.

Authors:
 [1];  [1];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Colorado, Boulder, CO (United States)
  2. Univ. of Texas, Austin, TX (United States)
  3. Academia Sinica, Taipei (Taiwan); Univ. of British Columbia, Vancouver, BC (Canada)
  4. 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)
OSTI Identifier:
1557648
Grant/Contract Number:  
FG02-87ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Changala, P. Bryan, Baraban, Joshua H., Stanton, John F., Merer, Anthony J., and Field, Robert W. Reduced dimension rovibrational variational calculations of the S1 state of C2H2. II. The S1 rovibrational manifold and the effects of isomerization. United States: N. p., 2014. Web. doi:10.1063/1.4859876.
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Changala, P. Bryan, Baraban, Joshua H., Stanton, John F., Merer, Anthony J., & Field, Robert W. Reduced dimension rovibrational variational calculations of the S1 state of C2H2. II. The S1 rovibrational manifold and the effects of isomerization. United States. https://doi.org/10.1063/1.4859876
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Changala, P. Bryan, Baraban, Joshua H., Stanton, John F., Merer, Anthony J., and Field, Robert W. Mon . "Reduced dimension rovibrational variational calculations of the S1 state of C2H2. II. The S1 rovibrational manifold and the effects of isomerization". United States. https://doi.org/10.1063/1.4859876. https://www.osti.gov/servlets/purl/1557648.
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@article{osti_1557648,
title = {Reduced dimension rovibrational variational calculations of the S1 state of C2H2. II. The S1 rovibrational manifold and the effects of isomerization},
author = {Changala, P. Bryan and Baraban, Joshua H. and Stanton, John F. and Merer, Anthony J. and Field, Robert W.},
abstractNote = {Reduced dimension variational calculations have been performed for the rovibrational level structure of the S1 state of acetylene. The state reflects an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm–1 above the trans, and the barrier to cis-trans isomerization lies about 5000 cm–1 above the trans minimum. The trans vibrations ν4 (torsion) and ν6 (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x36 cross-anharmonicity since the pathway to isomerization is a combination of ν6 and ν3 (sym. bend). Near the isomerization barrier, the vibrational levels show an even-odd K-staggering of their rotational levels as a result of quantum mechanical tunneling through the barrier. The current calculations address all of these complications, and reproduce the observed K-structures of the bending and C–C stretching levels with good qualitative accuracy. It is anticipated that they will assist with the assignment of the irregular patterns near the isomerization barrier.},
doi = {10.1063/1.4859876},
journal = {Journal of Chemical Physics},
number = 2,
volume = 140,
place = {United States},
year = {Mon Jan 13 00:00:00 EST 2014},
month = {Mon Jan 13 00:00:00 EST 2014}
}
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https://doi.org/10.1063/1.4859876
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    Works referencing / citing this record:

    Full-dimensional quantum mechanics calculations for the spectroscopic characterization of the isomerization transition states of HOCO/DOCO systems
    journal, January 2018

    • Ma, Dandan; Ren, Haisheng; Ma, Jianyi
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 7
    • DOI: 10.1039/c7cp07673h
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