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Rotranslational dynamics of confined water. II. Spectroscopic evidence of confinement effects on the far-infrared spectra of water isotopologues in argon and krypton matrices

Abstract : Water molecules trapped in rare gas matrices exhibit conspicuous shifts in their far-infrared (FIR), rotranslational spectral features compared with the corresponding transitions observed in the gas phase. These confinement-induced perturbations have been related not only to the quantization of translational motion but also to the coupling between the orientational and positional degrees of freedom: the rotation-translation coupling (RTC). As the propensity displayed by the nuclear spin isomers (NSI) of water to undergo interconversion in confinement is intimately related to how its nuclear spin degrees of freedom are coupled with those for intra- and intermolecular motions, confinement-induced RTC should also strongly impact the NSI interconversion mechanisms and rates. Insight into the rotranslational dynamics for H216O, H217O, and H218O, confined in argon and krypton matrices, is provided here based on the evolution of rotranslational spectra induced by NSI interconversion while a definitive assignment is provided from the transition energies and intensities calculated using the confined rotor model [Paper I, Wespiser et al., J. Chem. Phys. 156, 074304 (2021)]. In order to build a complete rotranslational energy diagram of confined water, which is fundamental to understand the NSI interconversion rates, the energy difference between the ground ortho and para rotranslational states is derived from the temperature dependence of the intensity ratio of mid-infrared lines emerging from these states. These investigations should provide deeper insight of the factors that control NSI interconversion of water isotopologues under extreme confinement.
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https://hal-insu.archives-ouvertes.fr/insu-03717129
Contributor : Nathalie POTHIER Connect in order to contact the contributor
Submitted on : Friday, July 8, 2022 - 8:54:20 AM
Last modification on : Wednesday, August 3, 2022 - 3:59:35 AM

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T. Putaud, C. Wespiser, M. Bertin, J. -H. Fillion, Y. Kalugina, et al.. Rotranslational dynamics of confined water. II. Spectroscopic evidence of confinement effects on the far-infrared spectra of water isotopologues in argon and krypton matrices. The Journal of Chemical Physics, 2022, 156, ⟨10.1063/5.0079566⟩. ⟨insu-03717129⟩

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