A Spectroscopic Description of Asymmetric Isotopologues of CO2

Bermúdez-Montana M. Rodriguez-Arcos M. Carvajal M. Ostertag-Henning C. Lemus R.
Journal of Physical Chemistry A
Doi 10.1021/acs.jpca.3c00890
Volumen 127 páginas 6357 - 6376
Citas: 0
© 2023 American Chemical SocietyA polyad-conserving algebraic model applied to vibrational excitations of asymmetric isotopologues of CO2 is presented. First, the problem of vibrational excitations is studied by taking into account only the minimum subspace of states to characterize the Fermi interaction. This analysis allows an estimation of the force constants as well as the feasibility of describing the system in a local mode scheme, in terms of SU(2) operators associated with Morse ladder operators for the stretches. This description together with the algebraic U(3) for the bends establishes the dynamical group SU1(2) × U(3) × SU2(2) for a series of isotopologues. Six isotopologues are considered, namely, 16O12C18O, 16O12C17O, 16O13C18O, 16O13C17O, 17O13C18O, and 17O12C18O in their electronic ground states. For isotopologues 16O12C18O, 16O12C17O, 17O12C18O, and 16O13C18O, the vibrational description was carried out using a Hamiltonian involving 14 parameters. For this series of isotopologues with a number of energy terms 90, 57, 42, and 40, the deviations obtained were rms = 0.15, 0.10, 0.06, and 0.07 cm-1, respectively. For 16O13C17O, with 28 experimental energies and involving 13 parameters, the deviation was rms = 0.05 cm-1, while for 17O13C18O, a different strategy was proposed since only 12 experimental energy levels. In all cases, the polyad scheme P212 = 2(?1 + ?3) + ?2 was considered. In addition, a new criterion of locality/normality degree is proposed, embracing the case of molecules with normal mode behavior, in particular, the isotopologues of CO2
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