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Low-Frequency Anharmonic Couplings in Crystalline Bromoform: Theory


Sertcan, Beliz; Mousavi, Seyyed Jabbar; Iannuzzi, Marcella; Hamm, Peter (2023). Low-Frequency Anharmonic Couplings in Crystalline Bromoform: Theory. Journal of Chemical Physics, 158(1):014203.

Abstract

Theoretical calculations of the low-frequency anharmonic couplings of the beta-phase of crystalline bromoform are presented, based on DFT quantum chemistry calculations. Electrical and mechanical anharmonicities between intra- and intermolecular modes are calculated, revealing that electrical anharmonicity dominates the cross peaks intensities in the 2D Raman-THz response and crystalline, as well as liquid, bromoform. Furthermore, the experimentally observed difference in relative cross peak intensities between the two intramolecular modes of bromoform and intermolecular modes can be explained by orientational averaging, taking into account the double-degeneracy of the lower-frequency intramolecular mode. The good agreement with experimental results provides further evidence for our interpretation that the 2D Raman-THz response of bromoform is indeed related to the anharmonic coupling between intra- and intermolecular modes.

Abstract

Theoretical calculations of the low-frequency anharmonic couplings of the beta-phase of crystalline bromoform are presented, based on DFT quantum chemistry calculations. Electrical and mechanical anharmonicities between intra- and intermolecular modes are calculated, revealing that electrical anharmonicity dominates the cross peaks intensities in the 2D Raman-THz response and crystalline, as well as liquid, bromoform. Furthermore, the experimentally observed difference in relative cross peak intensities between the two intramolecular modes of bromoform and intermolecular modes can be explained by orientational averaging, taking into account the double-degeneracy of the lower-frequency intramolecular mode. The good agreement with experimental results provides further evidence for our interpretation that the 2D Raman-THz response of bromoform is indeed related to the anharmonic coupling between intra- and intermolecular modes.

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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
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:7 January 2023
Deposited On:04 Jan 2023 09:51
Last Modified:28 Jun 2024 01:37
Publisher:American Institute of Physics
ISSN:0021-9606
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1063/5.0134278
Project Information:
  • : FunderSwiss National Science Foundation
  • : Grant ID
  • : Project Title
  • : FunderMaxWater network of the Max Planck Society.
  • : Grant ID
  • : Project Title
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)
  • Content: Accepted Version