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Artemov VG, Ryzhov A, Carlsen E, et al. Nonrotational Mechanism of Polarization in Alcohols. J Phys Chem B. 2020;124(48):11022-11029doi: 10.1021/acs.jpcb.0c09380.
Artemov, V. G., Ryzhov, A., Carlsen, E., Kapralov, P. O., & Ouerdane, H. (2020). Nonrotational Mechanism of Polarization in Alcohols. The journal of physical chemistry. B, 124(48), 11022-11029. https://doi.org/10.1021/acs.jpcb.0c09380
Artemov, Vasily G, et al. "Nonrotational Mechanism of Polarization in Alcohols." The journal of physical chemistry. B vol. 124,48 (2020): 11022-11029. doi: https://doi.org/10.1021/acs.jpcb.0c09380
Artemov VG, Ryzhov A, Carlsen E, Kapralov PO, Ouerdane H. Nonrotational Mechanism of Polarization in Alcohols. J Phys Chem B. 2020 Dec 03;124(48):11022-11029. doi: 10.1021/acs.jpcb.0c09380. Epub 2020 Nov 23. PMID: 33225700.
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J Phys Chem B. 2020 Dec 03;124(48):11022-11029. doi: 10.1021/acs.jpcb.0c09380. Epub 2020 Nov 23.

Nonrotational Mechanism of Polarization in Alcohols.

The journal of physical chemistry. B

Vasily G Artemov, Alexander Ryzhov, Emma Carlsen, Pavel O Kapralov, Henni Ouerdane

Affiliations

  1. Center for Energy Science and Technology, Skolkovo Institute of Science and Technology, 121205 Moscow, Russia.
  2. Department of Chemistry and Biochemistry, Brigham Young University, 84602 Provo, Utah, United States.
  3. Russian Quantum Center, 143025 Moscow, Russia.

PMID: 33225700 DOI: 10.1021/acs.jpcb.0c09380

Abstract

Chemical polarity governs various mechanical, chemical, and thermodynamic properties of dielectrics. Polar liquids have been amply studied, yet the basic mechanisms underpinning their dielectric properties remain not fully understood, as standard models following Debye's phenomenological approach do not account for quantum effects and cannot aptly reproduce the full dc-up-to-THz spectral range. Here, using the illustrative case of monohydric alcohols, we show that deep tunneling and the consequent intermolecular separation of excess protons and "proton-holes" in the polar liquids govern their static and dynamic dielectric properties on the same footing. We performed systematic ultrabroadband (0-10 THz) spectroscopy experiments with monohydric alcohols of different (0.4-1.6 nm) molecular lengths and show that the finite lifetime of molecular species and the proton-hole correlation length are the two principle parameters responsible for the dielectric response of all the studied alcohols across the entire frequency range. Our results demonstrate that a quantum nonrotational intermolecular mechanism drives the polarization in alcohols while the rotational mechanism of molecular polarization plays a secondary role, manifesting itself in the sub-terahertz region only.

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