Computational Study of the Rovibrational Spectrum of CO₂-N₂
The CO2-N2 complex is formed from two key components of Earth's atmosphere, and as such, has received some attention from both experimental and theoretical studies. On the theory side, a potential energy surface (PES) based on high level ab initio data was reported [Nasri et al., J. Chem. Phys., 2015, 142, 174301] and then used in more recently reported rovibrational calculations [Lara-Moreno et al., Phys. Chem. Chem. Phys., 2019, 21, 3550]. Accuracy of about 1 percent was achieved for calculated rotational transitions of the ground vibrational state of the complex, compared with previously reported microwave spectra. However, a very recent measurement of the geared bending mode frequency [Barclay et al., J. Chem. Phys., 2020, 153, 014303] recorded a value of 21.4 cm-1, which is wildly different from the corresponding calculated value of 45.9 cm-1. To provide some insight into this discrepancy, we have constructed a new more accurate PES, and used it to perform highly converged variational rovibrational calculations. Our new results yield a value of 21.1 cm-1 for that bending frequency, in close agreement with the experiment. We also obtain significantly improved predicted rotational transitions. Finally, we note that a very shallow well, previously reported as a distinct second isomer, is not found on our new PES, but rather a transition structure is seen in that location.
E. Quintas-Sánchez et al., "Computational Study of the Rovibrational Spectrum of CO₂-N₂," Physical Chemistry Chemical Physics, vol. 22, no. 39, pp. 22674 - 22683, Royal Society of Chemistry, Sep 2020.
The definitive version is available at https://doi.org/10.1039/d0cp04186f
Center for High Performance Computing Research
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17 Sep 2020