Molecular-level understanding of the rovibrational spectra of N 2 O in gaseous, supercritical, and liquid SF 6 and Xe.

Autor: Töpfer K; Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland., Koner D; Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland., Erramilli S; Department of Chemistry and the Photonics Center, Boston University, 8 St. Mary's St., 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.
Jazyk: angličtina
Zdroj: The Journal of chemical physics [J Chem Phys] 2023 Apr 14; Vol. 158 (14), pp. 144302.
DOI: 10.1063/5.0143395
Abstrakt: The transition between the gas-, supercritical-, and liquid-phase behavior is a fascinating topic, which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the vibrational spectroscopy of N 2 O embedded in xenon and SF 6 as solvents provides an avenue to characterize the transitions between different phases as the concentration (or density) of the solvent increases. The present work demonstrates that classical molecular dynamics (MD) simulations together with accurate interaction potentials allows us to (semi-)quantitatively describe the transition in rotational vibrational infrared spectra from the P-/R-branch line shape for the stretch vibrations of N 2 O at low solvent densities to the Q-branch-like line shapes at high densities. The results are interpreted within the classical theory of rigid-body rotation in more/less constraining environments at high/low solvent densities or based on phenomenological models for the orientational relaxation of rotational motion. It is concluded that classical MD simulations provide a powerful approach to characterize and interpret the ultrafast motion of solutes in low to high density solvents at a molecular level.
Databáze: MEDLINE
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