Energy relaxation of N2O in gaseous, supercritical, and liquid xenon and SF6.
| Autor: | Töpfer K; Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland., Erramilli S; Department of Physics and the Photonics Center, Boston University, 590 Commonwealth Ave., Boston Massachusetts 02215, USA., Ziegler LD; Department of Chemistry and the Photonics Center, Boston University, 8 St. Mary's St., Boston Massachusetts 02215, USA., Meuwly M; Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland.; Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of chemical physics [J Chem Phys] 2024 Nov 14; Vol. 161 (18). |
| DOI: | 10.1063/5.0235760 |
| Abstrakt: | Rotational and vibrational energy relaxation (RER and VER) of N2O embedded in xenon and SF6 environments ranging from the gas phase to the liquid, including the supercritical regime, is studied at a molecular level. Calibrated intermolecular interactions from high-level electronic structure calculations, validated against experiments for the pure solvents, were used to carry out classical molecular dynamics simulations corresponding to experimental state points for near-critical isotherms. The computed RER rates in low-density solvents of krotXe=(3.67±0.25)×1010 s-1 M-1 and krotSF6=(1.25±0.12)×1011 s-1 M-1 compare well with the rates determined by the analysis of two-dimensional infrared experiments. Simulations find that an isolated binary collision description is successful up to solvent concentrations of ∼4 M. For higher densities, including the supercritical regime, the simulations do not correctly describe RER, probably due to the neglect of solvent-solute coupling in the analysis of the rotational motion. For VER, the near-quantitative agreement between simulations and pump-probe experiments captures the solvent density-dependent trends. (© 2024 Author(s). Published under an exclusive license by AIP Publishing.) |
| Databáze: | MEDLINE |
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