Rotationally Inelastic Scattering of O₃-Ar: State-To-State Rates with the Multiconfigurational Time Dependent Hartree Method
The Chapman cycle, proposed in 1930, describes the various steps in the ongoing formation and destruction of stratospheric ozone. A key step in the formation process is the stabilization of metastable ozone molecules through collisions with a third body, usually an inert collider such as N2. The "ozone isotopic anomaly" refers to the observation of larger-than-expected atmospheric concentrations for certain ozone isotopologues. Previous studies point to the formation steps as the origin of this effect. A possibly key aspect of the ozone formation dynamics is that of the relative efficiencies of the collisional cooling of different isotopologues. Although the substitution of low-abundance 18O for 16O in O3 molecules corresponds to a relatively small net change in mass, related to this are some subtleties due to symmetry-breaking and a resulting more than doubling of the density of allowed states governed by nuclear-spin statistics for bosons. Recently, a highly accurate 3D potential energy surface (PES) describing O3-Ar interactions has been constructed and used to benchmark the low-lying rovibrational states of the complex. Here, using this new PES, we have studied the collisional energy-transfer dynamics using the MultiConfiguration Time Dependent Hartree method. A study of the rotationally inelastic scattering was performed for the parent 16O16O16O-Ar system and compared with that of the 16O16O18O-Ar isotopologue. The state-to-state cross-sections and rates from the 00,0 initial state to low lying excited states are reported. Analysis of these results yields insight into the interplay between small changes in the rotational constants of O3 and the reduced mass of the O3-Ar collision system, combined with that of the symmetry-breaking and introduction of a new denser manifold of allowed states.
S. Sur et al., "Rotationally Inelastic Scattering of O₃-Ar: State-To-State Rates with the Multiconfigurational Time Dependent Hartree Method," Physical Chemistry Chemical Physics, vol. 22, no. 4, pp. 1869-1880, Royal Society of Chemistry, Apr 2020.
The definitive version is available at https://doi.org/10.1039/c9cp06501f
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01 Apr 2020