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Title: Theoretical Treatment of the Coriolis Effect Using Hyperspherical Coordinates, with Application to the Ro-Vibrational Spectrum of Ozone

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Marquette Univ., Milwaukee, WI (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Here, several alternative methods for the description of the interaction between rotation and vibration are compared and contrasted using hyperspherical coordinates for a triatomic molecule. These methods differ by the choice of the z-axis and by the assumption of a prolate or oblate rotor shape of the molecule. For each case, a block-structure of the rotational–vibrational Hamiltonian matrix is derived and analyzed, and the advantages and disadvantages of each method are made explicit. This theory is then employed to compute ro-vibrational spectra of singly substituted ozone; roughly, 600 vibrational states of 16O18O16O and 16O16O18O isomers combined, with rotational excitations up to J = 5 and both inversion parities (21600 coupled ro-vibrational states in total). Splittings between the states of different parities, so-called K-doublings, are calculated and analyzed. The roles of the asymmetric-top rotor term and the Coriolis coupling term are determined individually, and it is found that they both affect these splittings, but in the opposite directions. Thus, the two effects partially cancel out, and the residual splittings are relatively small. Energies of the ro-vibrational states reported in this work for 16O18O16O and 16O16O18O are in excellent agreement with literature (available for low-vibrational excitation). New data obtained here for the highly excited vibrational states enable the first systematic study of the Coriolis effect in symmetric and asymmetric isotopomers of ozone.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001; AGS-1920523; AC02-05CH11231
OSTI ID:
1688753
Report Number(s):
LA-UR-19-31077
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 124, Issue 14; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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