Collective dynamics and self-motions in the van der Waals liquid tetrahydrofuran from meso- to inter-molecular scales disentangled by neutron spectroscopy with polarization analysis

By using time-of-flight neutron spectroscopy with polarization analysis, we have separated coherent and incoherent contributions to the scattering of deuterated tetrahydrofuran in a wide scattering vector (Q)-range from meso- to inter-molecular length scales. The results are compared with those rece...

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Bibliographic Details
Published in:The Journal of chemical physics 2023-05, Vol.158 (18)
Main Authors: Arbe, Arantxa, Nilsen, Gøran J., Devonport, Mark, Farago, Bela, Alvarez, Fernando, Martínez González, José A., Colmenero, Juan
Format: Article
Language:English
Subjects:
Coherent scattering
Deuteration
Diffusion
Hydrogen bonds
Molecular interactions
Phenomenology
Physics
Polarization
Relaxation time
Scattering functions
Spectroscopic analysis
Spectrum analysis
Tetrahydrofuran
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Summary:By using time-of-flight neutron spectroscopy with polarization analysis, we have separated coherent and incoherent contributions to the scattering of deuterated tetrahydrofuran in a wide scattering vector (Q)-range from meso- to inter-molecular length scales. The results are compared with those recently reported for water to address the influence of the nature of inter-molecular interactions (van der Waals vs hydrogen bond) on the dynamics. The phenomenology found is qualitatively similar in both systems. Both collective and self-scattering functions are satisfactorily described in terms of a convolution model that considers vibrations, diffusion, and a Q-independent mode. We observe a crossover in the structural relaxation from being dominated by the Q-independent mode at the mesoscale to being dominated by diffusion at inter-molecular length scales. The characteristic time of the Q-independent mode is the same for collective and self-motions and, contrary to water, faster and with a lower activation energy (≈1.4 Kcal/mol) than the structural relaxation time at inter-molecular length scales. This follows the macroscopic viscosity behavior. The collective diffusive time is well described by the de Gennes narrowing relation proposed for simple monoatomic liquids in a wide Q-range entering the intermediate length scales, in contraposition to the case of water.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0147427