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Signatures of Intra- and Intermolecular Vibrational Coupling in Halogenated Liquids Revealed by Two-Dimensional Raman-Terahertz Spectroscopy


Ciardi, Gustavo; Berger, Arian; Hamm, Peter; Shalit, Andrey (2019). Signatures of Intra- and Intermolecular Vibrational Coupling in Halogenated Liquids Revealed by Two-Dimensional Raman-Terahertz Spectroscopy. Journal of Physical Chemistry Letters, 10(15):4463-4468.

Abstract

Hybrid 2D Raman-THz spectroscopy with the Raman-THz-THz (RTT) pulse sequence is used to explore the ultrafast intra- and intermolecular degrees of freedom of liquid bromoform (CHBr3) in the frequency range of 1-8 THz. Cross peaks observed in these 2D spectra are assigned to the coupling between the narrow intramolecular modes of the molecules and the much broader intermolecular degrees of freedom of the liquid. This assignment is based on the frequency position of the crosspeaks, however, it is shown that these frequency positions can be deduced accurately only when properly taking into account the convolution of the molecular response with the instrument response function of the experimental setup, the latter of which distorts the 2D spectra considerably. The assignment is backed up with additional experiments on diiodomethane (CH2I2), which has only one intramolecular mode in the frequency range of the
experiment, and hence excludes the possibility of intramolecular couplings.

Abstract

Hybrid 2D Raman-THz spectroscopy with the Raman-THz-THz (RTT) pulse sequence is used to explore the ultrafast intra- and intermolecular degrees of freedom of liquid bromoform (CHBr3) in the frequency range of 1-8 THz. Cross peaks observed in these 2D spectra are assigned to the coupling between the narrow intramolecular modes of the molecules and the much broader intermolecular degrees of freedom of the liquid. This assignment is based on the frequency position of the crosspeaks, however, it is shown that these frequency positions can be deduced accurately only when properly taking into account the convolution of the molecular response with the instrument response function of the experimental setup, the latter of which distorts the 2D spectra considerably. The assignment is backed up with additional experiments on diiodomethane (CH2I2), which has only one intramolecular mode in the frequency range of the
experiment, and hence excludes the possibility of intramolecular couplings.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Materials Science
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:General Materials Science
Language:English
Date:1 August 2019
Deposited On:07 Feb 2020 10:54
Last Modified:29 Jul 2020 13:54
Publisher:American Chemical Society (ACS)
ISSN:1948-7185
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org10.1021/acs.jpclett.9b01528
OA Status:Green
Publisher DOI:https://doi.org/10.1021/acs.jpclett.9b01528
Project Information:
  • : FunderSwiss National Science Foundation (SNSF)
  • : Grant ID
  • : Project Title

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