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Computational Study of the Rovibrational Spectrum of CO₂-N₂
Physical Chemistry Chemical Physics
  • Ernesto Quintas-Sánchez, Missouri University of Science and Technology
  • Richard Dawes, Missouri University of Science and Technology
  • Xiao Gang Wang
  • Tucker Carrington
Abstract

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.

Department(s)
Chemistry
Research Center/Lab(s)
Center for High Performance Computing Research
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2020 Royal Society of Chemistry, All rights reserved.
Publication Date
9-17-2020
Publication Date
17 Sep 2020
PubMed ID
33016299
Disciplines
Citation Information
Ernesto Quintas-Sánchez, Richard Dawes, Xiao Gang Wang and Tucker Carrington. "Computational Study of the Rovibrational Spectrum of CO₂-N₂" Physical Chemistry Chemical Physics Vol. 22 Iss. 39 (2020) p. 22674 - 22683 ISSN: 1463-9076
Available at: http://works.bepress.com/richard_dawes/142/