Low-frequency anharmonic couplings in bromoform revealed from 2D Raman-THz spectroscopy: From the liquid to the crystalline phase

Mousavi, Setareh; Berger, Arian; Hamm, Peter; Shalit, Andrey

doi:10.1063/5.0090520

Cited by 4 publications

(2 citation statements)

References 52 publications

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“…Similarly, THz-THz-Raman spectroscopy recently revealed signatures of anharmonic coupling between phonons of ionic solid LiNbO 3 56 . Finally, Raman-THz-THz and THz-Raman-THz spectroscopies have been used to study the inhomogeneity of liquid water and aqueous solutions 57 , 58 , as well as the coupling among intermolecular and intramolecular modes in liquid and solid bromoform 59 , 60 . Even so, due to limited availability of efficient THz emitter materials, not all frequencies have been covered by the reported techniques.…”

Section: Introductionmentioning

confidence: 99%

Two-dimensional infrared-Raman spectroscopy as a probe of water’s tetrahedrality

Begušić

Blake

2023

Nat Commun

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Two-dimensional spectroscopic techniques combining terahertz (THz), infrared (IR), and visible pulses offer a wealth of information about coupling among vibrational modes in molecular liquids, thus providing a promising probe of their local structure. However, the capabilities of these spectroscopies are still largely unexplored due to experimental limitations and inherently weak nonlinear signals. Here, through a combination of equilibrium-nonequilibrium molecular dynamics (MD) and a tailored spectrum decomposition scheme, we identify a relationship between the tetrahedral order of liquid water and its two-dimensional IR-IR-Raman (IIR) spectrum. The structure-spectrum relationship can explain the temperature dependence of the spectral features corresponding to the anharmonic coupling between low-frequency intermolecular and high-frequency intramolecular vibrational modes of water. In light of these results, we propose new experiments and discuss the implications for the study of tetrahedrality of liquid water.

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Section: Introductionmentioning

confidence: 99%

Two-dimensional infrared-Raman spectroscopy as a probe of water’s tetrahedrality

Begušić

Blake

2023

Nat Commun

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“…45 Finally, Raman-THz-THz and THz-Raman-THz spectroscopies have been used to study the inhomogeneity of liquid water and aqueous solutions, 46,47 as well as the coupling among intermolecular and intramolecular modes in liquid and solid bromoform. 48,49 Even so, due to a limited availability of efficient THz emitter materials, not all frequencies have been covered by the reported techniques. Specifically, most two-dimensional hybrid THz-Raman spectroscopies of liquid water targeted hydrogen-bond bending and stretching modes, i.e., frequencies up to 400 cm −1 , leaving the water librational dynamics largely unexplored.…”

mentioning

confidence: 99%

Two-dimensional infrared-Raman spectroscopy as a probe of water's tetrahedrality

Begušić¹,

Blake²

2022

Preprint

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Two-dimensional spectroscopic techniques combining terahertz (THz), infrared (IR), and visible pulses offer a wealth of information about coupling among vibrational modes in molecular liquids, thus providing a promising probe of their local structure.However, the capabilities of these spectroscopies are still largely unexplored due to experimental limitations and inherently weak nonlinear signals. Here, through a combination of equilibrium-nonequilibrium molecular dynamics (MD) and a tailored spectrum decomposition scheme, we identify a relationship between the tetrahedral order of liquid water and its two-dimensional IR-IR-Raman (IIR) spectrum. The structure-spectrum relationship can explain the temperature dependence of the spectral features corresponding to the anharmonic coupling between low-frequency intermolecular and high-frequency intramolecular vibrational modes of water. In light of these results, we propose new experiments and discuss the implications for the study of tetrahedrality of liquid water.

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Low-frequency anharmonic couplings in crystalline bromoform: Theory

Sertcan

Mousavi

Iannuzzi

et al. 2023

The Journal of Chemical Physics

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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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Low-frequency anharmonic couplings in bromoform revealed from 2D Raman-THz spectroscopy: From the liquid to the crystalline phase

Cited by 4 publications

References 52 publications

Two-dimensional infrared-Raman spectroscopy as a probe of water’s tetrahedrality

Two-dimensional infrared-Raman spectroscopy as a probe of water’s tetrahedrality

Two-dimensional infrared-Raman spectroscopy as a probe of water's tetrahedrality

Low-frequency anharmonic couplings in crystalline bromoform: Theory

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