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 Wynne, Professor Klaas and Farrell, Mr Andrew and Ramakrishnan, Dr Gopakumar |
| 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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