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

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
DOI:https://doi.org/10.1021/jp407755m· OSTI ID:1557737
 [1];  [1];  [1];  [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
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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.

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-87ER13671
OSTI ID:
1557737
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 117, Issue 50; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

References (22)

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The direct observation, assignment, and partial deperturbation of ν 5 and ν 3 +ν 5 in A ̃  1 A u acetylene (C 2 H 2 ) journal July 1993
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
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
Perturbations in the 4 ν 3 level of the {\tf="PS7CD9"{\raise7pt\tilde \lower7ptA\clap}^\lower4pt{\hskip-.5pt1}\hskip-1ptA_u} state of acetylene, C 2 H 2 This article is part of a Special Issue on Spectroscopy at the University of New Brunswick in honour of Colan Linton and Ron Lees. journal May 2009
Darling–Dennison resonance and Coriolis coupling in the bending overtones of the ÃAu1 state of acetylene, C2H2 journal August 2008
Stretch-bend combination polyads in the Ã1Au state of acetylene, C2H2 journal August 2009
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
Reduced dimension discrete variable representation study of cis–trans isomerization in the S 1 state of C 2 H 2 journal June 2011
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
The electronic state of monodeuterated acetylene journal October 1989
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Anomalous Rotational line Intensities in Electronic Transitions of Polyatomic Molecules: Axis-Switching journal February 1965
Vibration—Rotation Interaction in Polyatomic Molecules. II. The Determination of Coriolis Coupling Coefficients journal June 1956
Molecular Potential Functions Expressed in Cartesian Coordinates: Application to the Orbital Valency Force Field journal April 1971

Cited By (2)

One-colour (∼220 nm) resonance-enhanced (S 1  − S 0 ) multi-photon dissociation of acetylene: probe of the C 2 A 1 Π u  −  X 1 Σ + g band by frequency-modulation spectroscopy journal February 2020
Probing the predissociated levels of the S 1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy journal November 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY