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:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Colorado, Boulder, CO (United States)
- Univ. of Texas, Austin, TX (United States)
- Academia Sinica, Taipei (Taiwan); Univ. of British Columbia, Vancouver, BC (Canada)
- 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.
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
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.
@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}
}
Web of Science
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Works referencing / citing this record:
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