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Title: The rotation-vibration structure of the SO 2 C 1B 2 state explained by a new internal coordinate force field

A new quartic force field for the SO 2 C ~ 1B 2 state has been derived, based on high resolution data from S 16O 2 and S 18O 2. Included are eight b 2 symmetry vibrational levels of S 16O 2 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 thatmore » 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 SO 2 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, ν β (which correlates with the antisymmetric stretching mode in our assignment scheme).« less
 [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States)
Publication Date:
Grant/Contract Number:
FG02-87ER13671; FG0287ER13671
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 14; Journal ID: ISSN 0021-9606
American Institute of Physics (AIP)
Research Org:
Massachusetts Institute of Technology, Cambridge, MA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Orgs:
Massachusetts Institute of Technology
Country of Publication:
United States
74 ATOMIC AND MOLECULAR PHYSICS; SO2; sulfur dioxide; force field
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1247608