Simulation of collision-induced absorption spectra based on classical trajectories andab initiopotential and induced dipole surfaces. II. CO2–Ar rototranslational band including true dimer contribution
| Autor: | Sergey V. Petrov, Daniil N. Chistikov, Yulia N. Kalugina, A.A. Vigasin, Artem A. Finenko, S.E. Lokshtanov |
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| Rok vydání: | 2021 |
| Předmět: |
Physics
спектральные моменты Absorption spectroscopy индуцированные дипольные моменты Ab initio General Physics and Astronomy Spectral line низкочастотное поглощение Dipole спектры поглощения Quantum mechanics Frequency domain Phase space потенциальная энергия межмолекулярного взаимодействия Trajectory Physical and Theoretical Chemistry Absorption (electromagnetic radiation) |
| Zdroj: | Journal of chemical physics. 2021. Vol. 155, № 6. P. 064301-1-064301-17 |
| ISSN: | 1089-7690 0021-9606 |
| Popis: | This paper presents further development of the new semi-classical trajectory-based formalism described in Paper I [Chistikov et al., J. Chem. Phys. 151, 194106 (2019)]. We report the results of simulation and analysis of the low-frequency collision-induced absorption (CIA) in CO2–Ar, including its true dimer component. Our consideration relies on the use of ab initio intermolecular potential energy and induced dipole surfaces for CO2–Ar calculated in an assumption of a rigid CO2 structure using the CCSD(T) method. The theory, the details of which are reported in Paper I [Chistikov et al., J. Chem. Phys. 151, 194106 (2019)], permits taking into account the effect of unbound and quasi-bound classical trajectories on the CIA in the range of a rototranslational band. This theory is largely extended by trajectory-based simulation of the true bound dimer absorption in the present paper. The spectra are obtained from a statistical average over a vast ensemble of classical trajectories restricted by properly chosen domains in the phase space. Rigorous classical theory is developed for two low-order spectral moments interpreted as the Boltzmann-weighted average of the respective dipole functions. These spectral moments were then used to check the accuracy of our trajectory-based spectra, for which both spectral moments can be evaluated independently in terms of specific integrals over the trajectory-based calculated spectral profiles. Good agreement between the spectral moments calculated as integrals over the frequency domain or the phase space largely supports the reliability of our simulated CIA spectra, which conform with the available microwave and far-infrared observations. |
| Databáze: | OpenAIRE |
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