Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Single-particle and collective excitations of polar water molecules confined in nano-pores within a cordierite crystal lattice. / Belyanchikov, M. A.; Bedran, Z. V.; Savinov, M. и др.
в: Physical Chemistry Chemical Physics, Том 24, № 11, 21.02.2022, стр. 6890-6904.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Single-particle and collective excitations of polar water molecules confined in nano-pores within a cordierite crystal lattice
AU - Belyanchikov, M. A.
AU - Bedran, Z. V.
AU - Savinov, M.
AU - Bednyakov, P.
AU - Proschek, P.
AU - Prokleska, J.
AU - Abalmasov, V. A.
AU - Zhukova, E. S.
AU - Thomas, V. G.
AU - Dudka, A.
AU - Zhugayevych, A.
AU - Petzelt, J.
AU - Prokhorov, A. S.
AU - Anzin, V. B.
AU - Kremer, R. K.
AU - Fischer, J. K.H.
AU - Lunkenheimer, P.
AU - Loidl, A.
AU - Uykur, E.
AU - Dressel, M.
AU - Gorshunov, B.
N1 - Funding Information: We are grateful to A. Bokov, H. P.Büchler, A. Bush, M. Fyta, V. S. Gorelik, J. Hlinka, S. Kamba, and V. I. Torgashev for fruitful discussions. We acknowledge financial support from the Russian Science Foundation (21-72-00026, 22-22-00091), the Ministry of Science and Higher Education of the Russian Federation (No. FSMG-2021-0005), RFBR, project number 20-02-00314, Czech Science Foundation (20-01527S), Deutsche Forschungsgemeinschaft (DR228/61-1) and of the Stuttgart/Ulm Research Center for Integrated Quantum Science and Technology (IQST). E. U. acknowledges the support from the European Social Fund and by the Ministry of Science Research and the Arts of Baden-Württemberg. A. D. acknowledges support from the Ministry of Science and Higher Education of the Russian Federation (project RFMEFI62119X0035 and the State assignment of the FSRC “Crystallography and Photonics” RAS) and the Shared Research Center FSRC “Crystallography and Photonics”, RAS, in part of the X-ray diffraction study. Publisher Copyright: © 2022 The Royal Society of Chemistry.
PY - 2022/2/21
Y1 - 2022/2/21
N2 - Recently, the low-temperature phase of water molecules confined within nanocages formed by the crystalline lattice of water-containing cordierite crystals has been reported to comprise domains with ferroelectrically ordered dipoles within the a, b-planes which are antiferroelectrically alternating along the c-axis. In the present work, comprehensive broad-band dielectric spectroscopy is combined with specific heat studies and molecular dynamics and Monte Carlo simulations in order to investigate in more detail the collective modes and single-particle excitations of nanoconfined water molecules. From DFT-MD simulations we reconstruct the potential-energy landscape experienced by the H2O molecules. A rich set of anisotropic temperature-dependent excitations is observed in the terahertz frequency range. Their origin is associated with the complex rotational/translational vibrations of confined H2O molecules. A strongly temperature dependent relaxational excitation, observed at radio-microwave frequencies for the electric field parallel to the crystallographic a-axis, E||a is analyzed in detail. The temperature dependences of loss-peak frequency and dielectric strength of the excitation together with specific heat data confirm a ferroelectric order-disorder phase transition at T0 ≈ 3 K in the network of H2O dipoles. Additional dielectric data are also provided for polarization E||b, too. Overall, these combined experimental investigations enable detailed conclusions concerning the dynamics of the confined water molecules that develop within their microscopic energy landscapes.
AB - Recently, the low-temperature phase of water molecules confined within nanocages formed by the crystalline lattice of water-containing cordierite crystals has been reported to comprise domains with ferroelectrically ordered dipoles within the a, b-planes which are antiferroelectrically alternating along the c-axis. In the present work, comprehensive broad-band dielectric spectroscopy is combined with specific heat studies and molecular dynamics and Monte Carlo simulations in order to investigate in more detail the collective modes and single-particle excitations of nanoconfined water molecules. From DFT-MD simulations we reconstruct the potential-energy landscape experienced by the H2O molecules. A rich set of anisotropic temperature-dependent excitations is observed in the terahertz frequency range. Their origin is associated with the complex rotational/translational vibrations of confined H2O molecules. A strongly temperature dependent relaxational excitation, observed at radio-microwave frequencies for the electric field parallel to the crystallographic a-axis, E||a is analyzed in detail. The temperature dependences of loss-peak frequency and dielectric strength of the excitation together with specific heat data confirm a ferroelectric order-disorder phase transition at T0 ≈ 3 K in the network of H2O dipoles. Additional dielectric data are also provided for polarization E||b, too. Overall, these combined experimental investigations enable detailed conclusions concerning the dynamics of the confined water molecules that develop within their microscopic energy landscapes.
UR - http://www.scopus.com/inward/record.url?scp=85127200454&partnerID=8YFLogxK
U2 - 10.1039/d1cp05338h
DO - 10.1039/d1cp05338h
M3 - Article
C2 - 35253024
AN - SCOPUS:85127200454
VL - 24
SP - 6890
EP - 6904
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 11
ER -
ID: 35811760