Molecular-level understanding of the rovibrational spectra of N2O in gaseous, supercritical, and liquid SF6and Xe

Koner, Debasish (2023) Molecular-level understanding of the rovibrational spectra of N2O in gaseous, supercritical, and liquid SF6and Xe. The Journal of Chemical Physics, 158 (14). p. 144302. ISSN 0021-9606

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Abstract

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 N2O embedded in xenon and SF6 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 N2O 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.

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IITH Creators:

IITH Creators	ORCiD
Koner, Debasish	http://www.orcid.org/0000-0002-5116-4908

Item Type:

Article

Uncontrolled Keywords:

Infrared spectroscopy; Molecular dynamics; Vibrations (mechanical); Classical molecular dynamics; Dynamics simulation; Lines shapes; Liquid phase behavior; Molecular levels; Rovibrational spectrum; Solvent density; Supercritical; Supercritical phasis; Ultra-fast; Solvents

Subjects:

Chemistry
Chemistry > Inorganic chemistry

Divisions:

Department of Chemistry

Depositing User:

Mr Nigam Prasad Bisoyi

Date Deposited:

11 Sep 2023 04:29

Last Modified:

11 Sep 2023 04:29

URI:

http://raiithold.iith.ac.in/id/eprint/11664