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Title: Laser-Induced Fluorescence Study of the S1 State of Doubly-Substituted 13 C Acetylene and Harmonic Force Field Determination

Abstract

In the first half of this study, rotational and vibrational constants of six Franck–Condon bright vibrational levels of S1 doubly-substituted 13C acetylene are determined from laser-induced fluorescence spectra and an updated geometry of the trans conformer of S1 acetylene is obtained. In the second half, we determine the quadratic force field of S1 acetylene on the basis of the harmonic frequencies of four isotopologues of acetylene. The effects of both diagonal and off-diagonal xij anharmonicities are removed from the input harmonic frequencies. Results from both experimental and theoretical studies of various isotopologues of acetylene (including those from the first half of this paper) are used to obtain a set of force constants that agrees well with ab initio calculations. Lastly, our set of force constants for S1 acetylene is an improvement over previous work by Tobiason et al., which did not include off-diagonal anharmonicities.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
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:
1557737
Grant/Contract Number:  
FG02-87ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 117; Journal Issue: 50; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jiang, Jun, Baraban, Joshua H., Park, G. Barratt, Clark, Michelle L., and Field, Robert W. Laser-Induced Fluorescence Study of the S1 State of Doubly-Substituted 13 C Acetylene and Harmonic Force Field Determination. United States: N. p., 2013. Web. doi:10.1021/jp407755m.
Jiang, Jun, Baraban, Joshua H., Park, G. Barratt, Clark, Michelle L., & Field, Robert W. Laser-Induced Fluorescence Study of the S1 State of Doubly-Substituted 13 C Acetylene and Harmonic Force Field Determination. United States. https://doi.org/10.1021/jp407755m
Jiang, Jun, Baraban, Joshua H., Park, G. Barratt, Clark, Michelle L., and Field, Robert W. Thu . "Laser-Induced Fluorescence Study of the S1 State of Doubly-Substituted 13 C Acetylene and Harmonic Force Field Determination". United States. https://doi.org/10.1021/jp407755m. https://www.osti.gov/servlets/purl/1557737.
@article{osti_1557737,
title = {Laser-Induced Fluorescence Study of the S1 State of Doubly-Substituted 13 C Acetylene and Harmonic Force Field Determination},
author = {Jiang, Jun and Baraban, Joshua H. and Park, G. Barratt and Clark, Michelle L. and Field, Robert W.},
abstractNote = {In the first half of this study, rotational and vibrational constants of six Franck–Condon bright vibrational levels of S1 doubly-substituted 13C acetylene are determined from laser-induced fluorescence spectra and an updated geometry of the trans conformer of S1 acetylene is obtained. In the second half, we determine the quadratic force field of S1 acetylene on the basis of the harmonic frequencies of four isotopologues of acetylene. The effects of both diagonal and off-diagonal xij anharmonicities are removed from the input harmonic frequencies. Results from both experimental and theoretical studies of various isotopologues of acetylene (including those from the first half of this paper) are used to obtain a set of force constants that agrees well with ab initio calculations. Lastly, our set of force constants for S1 acetylene is an improvement over previous work by Tobiason et al., which did not include off-diagonal anharmonicities.},
doi = {10.1021/jp407755m},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 50,
volume = 117,
place = {United States},
year = {Thu Sep 05 00:00:00 EDT 2013},
month = {Thu Sep 05 00:00:00 EDT 2013}
}

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Cited by: 9 works
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Works referenced in this record:

Analysis of the Near Ultraviolet Absorption Spectrum of Acetylene
journal, May 1954

  • Innes, K. Keith
  • The Journal of Chemical Physics, Vol. 22, Issue 5
  • DOI: 10.1063/1.1740204

The band system of acetylene
journal, September 1982


The direct observation, assignment, and partial deperturbation of the ν 4 and ν 6 vibrational fundamentals in A ̃  1 A u acetylene (C 2 H 2 )
journal, February 1993

  • Utz, A. L.; Tobiason, J. D.; Carrasquillo M., E.
  • The Journal of Chemical Physics, Vol. 98, Issue 4
  • DOI: 10.1063/1.464156

The direct observation, assignment, and partial deperturbation of ν 5 and ν 35 in A ̃  1 A u acetylene (C 2 H 2 )
journal, July 1993

  • Tobiason, J. D.; Utz, A. L.; Crim, F. F.
  • The Journal of Chemical Physics, Vol. 99, Issue 2
  • DOI: 10.1063/1.465357

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


IR−UV Double Resonance Spectroscopy of Acetylene in the à 1 A u n ν 3 ‘+ν 4 ‘ and n ν 3 ‘+ν 6 ‘ ( n = 2, 3) Ungerade Vibrational States
journal, November 2000

  • Mizoguchi, Miwako; Yamakita, Nami; Tsuchiya, Soji
  • The Journal of Physical Chemistry A, Vol. 104, Issue 45
  • DOI: 10.1021/jp001215y

New vibrational assignments in the Ā 1 A u -[Xtilde] 1 Σ + g electronic transition of acetylene, C 2 H 2 : the v′ 1 frequency
journal, February 2003


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

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

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


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


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

Reduced dimension discrete variable representation study of cis–trans isomerization in the S 1 state of C 2 H 2
journal, June 2011

  • Baraban, J. H.; Beck, A. R.; Steeves, A. H.
  • The Journal of Chemical Physics, Vol. 134, Issue 24
  • DOI: 10.1063/1.3570823

The band system of C2D2: Vibration-rotation constants for the state
journal, October 1989


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


Normal modes analysis of A ̃‐state acetylene based on directly observed fundamental vibrations
journal, October 1993

  • Tobiason, J. D.; Utz, A. L.; Sibert, E. L.
  • The Journal of Chemical Physics, Vol. 99, Issue 8
  • DOI: 10.1063/1.465927

The electronic state of monodeuterated acetylene
journal, October 1989


Vibration-Rotation Spectra of 13C Containing Acetylene
journal, October 1993

  • Dilonardo, G.; Ferracuti, P.; Fusina, L.
  • Journal of Molecular Spectroscopy, Vol. 161, Issue 2
  • DOI: 10.1006/jmsp.1993.1252

Anomalous Rotational line Intensities in Electronic Transitions of Polyatomic Molecules: Axis-Switching
journal, February 1965

  • Hougen, J. T.; Watson, J. K. G.
  • Canadian Journal of Physics, Vol. 43, Issue 2
  • DOI: 10.1139/p65-028

Vibration—Rotation Interaction in Polyatomic Molecules. II. The Determination of Coriolis Coupling Coefficients
journal, June 1956

  • Meal, Janet Hawkins; Polo, S. R.
  • The Journal of Chemical Physics, Vol. 24, Issue 6
  • DOI: 10.1063/1.1742729

Molecular Potential Functions Expressed in Cartesian Coordinates: Application to the Orbital Valency Force Field
journal, April 1971

  • Tyson, John; Claassen, Howard H.; Kim, Hyunyong
  • The Journal of Chemical Physics, Vol. 54, Issue 7
  • DOI: 10.1063/1.1675302

Works referencing / citing this record:

Probing the predissociated levels of the S 1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy
journal, November 2018

  • Jiang, Jun; Saladrigas, Catherine A.; Erickson, Trevor J.
  • The Journal of Chemical Physics, Vol. 149, Issue 17
  • DOI: 10.1063/1.5045046