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Title: The rotation-vibration structure of the SO2 C1B2 state explained by a new internal coordinate force field

Abstract

A new quartic force field for the SO2 C~1B2 state has been derived, based on high resolution data from S16O2 and S18O2. Included are eight b2 symmetry vibrational levels of S16O2 reported in the first paper of this series [G. B. Park, et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C~ state vibrational levels, are well reproduced using our force field. Because the two stretching modes of the C~ state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and coworkers [M. E. Kellman and L. Xiao, J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularlymore » at vibrational energies of more than 2000 cm–1. Based on our force field, the structure of the Coriolis interactions in the C~ state of SO2 is also discussed. As a result, we identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, νβ (which correlates with the antisymmetric stretching mode in our assignment scheme).« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Institute of Technology, Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Massachusetts Institute of Technology
OSTI Identifier:
1248473
Alternate Identifier(s):
OSTI ID: 1247608
Grant/Contract Number:  
FG02-87ER13671; FG0287ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; SO2; sulfur dioxide; force field

Citation Formats

Jiang, Jun, Park, G. Barratt, and Field, Robert W. The rotation-vibration structure of the SO2 C1B2 state explained by a new internal coordinate force field. United States: N. p., 2016. Web. doi:10.1063/1.4945621.
Jiang, Jun, Park, G. Barratt, & Field, Robert W. The rotation-vibration structure of the SO2 C1B2 state explained by a new internal coordinate force field. United States. doi:10.1063/1.4945621.
Jiang, Jun, Park, G. Barratt, and Field, Robert W. Thu . "The rotation-vibration structure of the SO2 C1B2 state explained by a new internal coordinate force field". United States. doi:10.1063/1.4945621. https://www.osti.gov/servlets/purl/1248473.
@article{osti_1248473,
title = {The rotation-vibration structure of the SO2 C1B2 state explained by a new internal coordinate force field},
author = {Jiang, Jun and Park, G. Barratt and Field, Robert W.},
abstractNote = {A new quartic force field for the SO2 C~1B2 state has been derived, based on high resolution data from S16O2 and S18O2. Included are eight b2 symmetry vibrational levels of S16O2 reported in the first paper of this series [G. B. Park, et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C~ state vibrational levels, are well reproduced using our force field. Because the two stretching modes of the C~ state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and coworkers [M. E. Kellman and L. Xiao, J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm–1. Based on our force field, the structure of the Coriolis interactions in the C~ state of SO2 is also discussed. As a result, we identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, νβ (which correlates with the antisymmetric stretching mode in our assignment scheme).},
doi = {10.1063/1.4945621},
journal = {Journal of Chemical Physics},
number = 14,
volume = 144,
place = {United States},
year = {2016},
month = {4}
}

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Works referenced in this record:

Asymmetric structure and force field of the 1 B 2 ( 1 A′) state of sulphur dioxide
journal, November 1978


Sulfur dioxide: Rotational constants and asymmetric structure of the state
journal, March 1976


The investigation of double-minimum potentials in molecules
journal, June 1966


The ultraviolet spectrum of SO2 in matrix isolation and the vibrational structure of the 2348 Å system
journal, July 1973


Laser induced fluorescence spectroscopy of the C̃1B2X̃1A1 band of jet-cooled SO2: rotational and vibrational analyses in the 235-210 nm region
journal, June 1995


Vibrational propensity in the predissociation rate of SO2(C̃1B2) by two types of nodal patterns in vibrational wavefunctions
journal, September 1998


The calculation of the vibrational states of SO2 in the C̃1B2 electronic state up to the SO(3Σ−)+O(3P) dissociation limit
journal, March 2000


Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. III. Emission spectra from the C̃ 1B2 state
journal, November 1999

  • Xie, Daiqian; Ma, Guobin; Guo, Hua
  • The Journal of Chemical Physics, Vol. 111, Issue 17
  • DOI: 10.1063/1.480113

Investigation of the potential energy surfaces for the ground X̃1A1 and excited C̃1B2 electronic states of SO2
journal, April 1999


Theoretical studies of <mml:math altimg="si7.gif" display="inline" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:msup><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi>C</mml:mi></mml:mrow><mml:mrow><mml:mo stretchy="true">∼</mml:mo></mml:mrow></mml:mover></mml:mrow><mml:mrow><mml:mn>1</mml:mn></mml:mrow></mml:msup><mml:msub><mml:mrow><mml:mi>B</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math> absorption spectra of SO2 isotopomers
journal, May 2007


Experimental and theoretical exploration of photodissociation of SO2 via the C̃1B2 state: identification of the dissociation pathway
journal, September 1997


Rovibrational dependences of the predissociation in the C̃ 1B2 state of SO2
journal, January 1988


Fermi resonance phase space structure from experimental spectra
journal, December 1986

  • Kellman, Michael E.; Lynch, Eric D.
  • The Journal of Chemical Physics, Vol. 85, Issue 12
  • DOI: 10.1063/1.451358

Semiclassical phase space evolution of Fermi resonance spectra
journal, February 1988

  • Kellman, Michael E.; Lynch, Eric D.
  • The Journal of Chemical Physics, Vol. 88, Issue 4
  • DOI: 10.1063/1.454053

Catastrophe map classification of the generalized normal–local transition in Fermi resonance spectra
journal, October 1990

  • Xiao, Lin; Kellman, Michael E.
  • The Journal of Chemical Physics, Vol. 93, Issue 8
  • DOI: 10.1063/1.459576

New assignment of Fermi resonance spectra
journal, October 1990

  • Kellman, Michael E.; Xiao, Lin
  • The Journal of Chemical Physics, Vol. 93, Issue 8
  • DOI: 10.1063/1.459577

Phase space bifurcation structure and the generalized local‐to‐normal transition in resonantly coupled vibrations
journal, February 1990

  • Li, Zhiming; Xiao, Lin; Kellman, Michael E.
  • The Journal of Chemical Physics, Vol. 92, Issue 4
  • DOI: 10.1063/1.458018

Observation of b2 symmetry vibrational levels of the SO2 C̃ 1B2 state: Vibrational level staggering, Coriolis interactions, and rotation-vibration constants
journal, April 2016

  • Park, G. Barratt; Jiang, Jun; Saladrigas, Catherine A.
  • The Journal of Chemical Physics, Vol. 144, Issue 14
  • DOI: 10.1063/1.4944924

Millimeter-wave optical double resonance schemes for rapid assignment of perturbed spectra, with applications to the C̃1B2 state of SO 2
journal, April 2015

  • Park, G. Barratt; Womack, Caroline C.; Whitehill, Andrew R.
  • The Journal of Chemical Physics, Vol. 142, Issue 14
  • DOI: 10.1063/1.4916908

Anharmonic force constant calculations
journal, December 1972


Equilibrium structure and potential function of sulfur dioxide from the microwave spectrum in the excited vibrational state
journal, January 1964


Franck—Condon Factors for Polyatomic Molecules
journal, December 1964

  • Sharp, T. E.; Rosenstock, H. M.
  • The Journal of Chemical Physics, Vol. 41, Issue 11
  • DOI: 10.1063/1.1725748

The origin of unequal bond lengths in the C̃1B2 state of SO2: Signatures of high-lying potential energy surface crossings in the low-lying vibrational structure
journal, April 2016

  • Park, G. Barratt; Jiang, Jun; Field, Robert W.
  • The Journal of Chemical Physics, Vol. 144, Issue 14
  • DOI: 10.1063/1.4945622

High resolution absorption cross section measurements of SO2 at 213 K in the wavelength region 172–240 nm
journal, September 1984


The HITRAN2012 molecular spectroscopic database
journal, November 2013

  • Rothman, L. S.; Gordon, I. E.; Babikov, Y.
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 130, p. 4-50
  • DOI: 10.1016/j.jqsrt.2013.07.002

Vibrational Coupling Pathways in Methanol As Revealed by Coherence-Converted Population Transfer Fourier Transform Microwave Infrared Double-Resonance Spectroscopy
journal, July 2010

  • Twagirayezu, Sylvestre; Clasp, Trocia N.; Perry, David S.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 25
  • DOI: 10.1021/jp1019735

Trimethylene Oxide. I. Microwave Spectrum, Dipole Moment, and Double Minimum Vibration
journal, December 1960

  • Chan, Sunney I.; Zinn, John; Fernandez, Jose
  • The Journal of Chemical Physics, Vol. 33, Issue 6
  • DOI: 10.1063/1.1731477

The two-dimensional anharmonic oscillator
journal, July 1976


The two-dimensional anharmonic oscillator
journal, July 1976