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Title: Full dimensional Franck-Condon factors for the acetylene $$\tilde{A}$$ 1 A u —$$\tilde{X}$$ 1Σ$$^{+}_{g}$$ transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4896532· OSTI ID:1546603
 [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
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Franck-Condon vibrational overlap integrals for the $$\tilde{A}$$ 1$$A$$u-$$\tilde{X}$$ 1$$Σ$$$^{+}_{g}$$ transition in acetylene have been calculated in full dimension in the harmonic normal mode basis. The calculation uses the method of generating functions first developed for polyatomic Franck-Condon factors by Sharp and Rosenstock [J. Chem. Phys. 41(11), 3453–3463 (1964)], and previously applied to acetylene by Watson [J. Mol. Spectrosc. 207(2), 276–284 (2001)] in a reduced-dimension calculation. Because the transition involves a large change in the equilibrium geometry of the electronic states, two different types of corrections to the coordinate transformation are considered to first order: corrections for axis-switching between the Cartesian molecular frames and corrections for the curvilinear nature of the normal modes at large amplitude. The angular factor in the wavefunction for the out-of-plane component of the trans bending mode, ν 4 " , is treated as a rotation, which results in an Eckart constraint on the polar coordinates of the bending modes. To simplify the calculation, the other degenerate bending mode, ν 5 " , is integrated in the Cartesian basis and later transformed to the constrained polar coordinate basis, restoring the conventional v and l quantum numbers. An updated $$\tilde{A}$$-state harmonic force field obtained recently in the R. W. Field research group is evaluated. The results for transitions involving the gerade vibrational modes are in qualitative agreement with experiment. Calculated results for transitions involving ungerade modes are presented in Paper II of this series [G. B. Park, J. H. Baraban, and R. W. Field, “Full dimensional Franck–Condon factors for the acetylene $$\tilde{A}$$ 1$$A$$u-$$\tilde{X}$$ 1$$Σ$$$^{+}_{g}$$transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes,” J. Chem. Phys. 141, 134305 (2014)].

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
FG02-87ER13671; FG0287ER13671
OSTI ID:
1546603
Alternate ID(s):
OSTI ID: 1420697
Journal Information:
Journal of Chemical Physics, Vol. 141, Issue 13; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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Cited By (5)

Photoelectron spectroscopy of boron-containing reactive intermediates using synchrotron radiation: BH 2 , BH, and BF journal January 2020
Probing the predissociated levels of the S 1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy journal November 2018
Generalized oscillator strengths of the low-lying valence-shell excitations of N 2 , O 2, and C 2 H 2 studied by fast electron and inelastic x-ray scattering journal March 2019
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
Fundamental mechanisms for molecular energy conversion and chemical reactions at surfaces journal August 2019

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