Low-frequency (gigahertz to terahertz) depolarized Raman scattering off n-alkanes, cycloalkanes, and six-membered rings: a physical interpretation

Farrell, A. J., González Jiménez, M. , Ramakrishnan, G. and Wynne, K. (2020) Low-frequency (gigahertz to terahertz) depolarized Raman scattering off n-alkanes, cycloalkanes, and six-membered rings: a physical interpretation. Journal of Physical Chemistry B, 124(35), pp. 7611-7624. (doi: 10.1021/acs.jpcb.0c03769) (PMID:32790389) (PMCID:PMC7476039)

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Abstract

Molecular liquids have long been known to undergo various distinct intermolecular motions, from fast li-brations and cage rattling oscillations to slow orientational and translational diffusion. However, their re-sultant gigahertz to terahertz spectra are far from simple, appearing as broad shapeless bands that span many orders of magnitude of frequency making meaningful interpretation troublesome. Ad hoc spectral lineshape fitting has become a notoriously fine art in the field; a unified approach to handling such spectra is long overdue. Here we apply ultrafast optical Kerr-effect (OKE) spectroscopy to study the intermolecular dynamics of room temperature n-alkanes, cycloalkanes, and six-carbon rings, as well as liquid methane and propane. This work provides stress-tests and converges upon an experimentally robust model across simple molecular series and range of temperatures, providing a blueprint for the interpretation of the dynamics of van der Waals liquids. This will enable the interpretation of low frequency spectra of more complex liquids.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Gonzalez Jimenez, Dr Mario and Ramakrishnan, Dr Gopakumar and Wynne, Professor Klaas and Farrell, Mr Andrew
Authors: Farrell, A. J., González Jiménez, M., Ramakrishnan, G., and Wynne, K.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Physical Chemistry B
Publisher:American Chemical Society
ISSN:1520-6106
ISSN (Online):1520-5207
Published Online:06 August 2020
Copyright Holders:Copyright © 2020 American Chemical Society
First Published:First published in Journal of Physical Chemistry B 124(35): 7611-7624
Publisher Policy:Reproduced under a Creative Commons License
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