| Autor: |
Selim, Taha, van der Avoird, Ad, Groenenboom, Gerrit C. |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 10/28/2023, Vol. 159 Issue 16, p1-15, 15p |
| Abstrakt: |
Modeling environments that are not in local thermal equilibrium, such as protoplanetary disks or planetary atmospheres, with molecular spectroscopic data from space telescopes requires knowledge of the rate coefficients of rovibrationally inelastic molecular collisions. Here, we present such rate coefficients in a temperature range from 10 to 500 K for collisions of CO2 with He atoms in which CO2 is (de)excited in the bend mode. They are obtained from numerically exact coupled-channel (CC) calculations as well as from calculations with the less demanding coupled-states approximation (CSA) and the vibrational close-coupling rotational infinite-order sudden (VCC-IOS) method. All of the calculations are based on a newly calculated accurate ab initio four-dimensional CO2–He potential surface including the CO2 bend (ν2) mode. We find that the rovibrationally inelastic collision cross sections and rate coefficients from the CSA and VCC-IOS calculations agree to within 50% with the CC results at the rotational state-to-state level, except for the smaller ones and in the low energy resonance region, and to within 20% for the overall vibrational quenching rates except for temperatures below 50 K where resonances provide a substantial contribution. Our CC quenching rates agree with the most recent experimental data within the error bars. We also compared our results with data from Clary et al. calculated in the 1980s with the CSA [A. J. Banks and D. C. Clary, J. Chem. Phys. 86, 802 (1987)] and VCC-IOS [D. C. Clary, J. Chem. Phys. 78, 4915 (1983)] methods and a simple atom-atom model potential based on ab initio Hartree–Fock calculations and found that their cross sections agree fairly well with ours for collision energies above 500 cm−1, but that the inclusion of long range attractive dispersion interactions is crucial to obtain reliable cross sections at lower energies and rate coefficients at lower temperatures. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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