Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics
The structure of an aqueous solution of potassium dihydrogen phosphate (KH<sub>2</sub>PO<sub>4</sub>, KDP) was studied by small-angle X-ray scattering (SAXS) and molecular dynamics (MD). According to SAXS data, the octameric species (KH<sub>2</sub>PO<sub>4&l...
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MDPI AG
2023-11-01
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| author | Andrey E. Sukhanov Petr V. Konarev Vladimir I. Timofeev Ildar F. Garipov Ekaterina S. Smirnova Georgy S. Peters Kseniia B. Ilina Yury V. Pisarevsky Olga A. Alekseeva Mikhail V. Kovalchuk |
| author_facet | Andrey E. Sukhanov Petr V. Konarev Vladimir I. Timofeev Ildar F. Garipov Ekaterina S. Smirnova Georgy S. Peters Kseniia B. Ilina Yury V. Pisarevsky Olga A. Alekseeva Mikhail V. Kovalchuk |
| author_sort | Andrey E. Sukhanov |
| collection | DOAJ |
| description | The structure of an aqueous solution of potassium dihydrogen phosphate (KH<sub>2</sub>PO<sub>4</sub>, KDP) was studied by small-angle X-ray scattering (SAXS) and molecular dynamics (MD). According to SAXS data, the octameric species (KH<sub>2</sub>PO<sub>4</sub>)<sub>8</sub> are formed in solution in addition to K<sup>+</sup>, (H<sub>2</sub>PO<sub>4</sub>)<sup>−</sup>, and KH<sub>2</sub>PO<sub>4</sub>, while the presence of other types of oligomers is not observed. When the temperature drops below the saturation temperature (~60 °C), the volume fraction of octamers increases sharply, reaching 50% at 4 °C. The results of MD calculations of the temporal stability relationships of dimers (KH<sub>2</sub>PO<sub>4</sub>)<sub>2</sub>, tetramers (KH<sub>2</sub>PO<sub>4</sub>)<sub>4</sub>, and octamers (KH<sub>2</sub>PO<sub>4</sub>)<sub>8</sub> show that the dimers and tetramers disintegrate rapidly (50–100 ps), while the octamers remain stable. A comparative analysis of the bonds between the octamers and the KDP crystal lattice was carried out when the octamer was inserted during crystal growth in the directions [001] and [100]. The possible relationship of the obtained results with the changes in the anisotropy of growth rates (habitus) of KDP crystals at different degrees of supersaturation is discussed. |
| first_indexed | 2024-03-09T16:54:42Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-09T16:54:42Z |
| publishDate | 2023-11-01 |
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| series | Crystals |
| spelling | doaj.art-5ddcb7a559d2446abf822b70dda80ed42023-11-24T14:36:48ZengMDPI AGCrystals2073-43522023-11-011311157710.3390/cryst13111577Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular DynamicsAndrey E. Sukhanov0Petr V. Konarev1Vladimir I. Timofeev2Ildar F. Garipov3Ekaterina S. Smirnova4Georgy S. Peters5Kseniia B. Ilina6Yury V. Pisarevsky7Olga A. Alekseeva8Mikhail V. Kovalchuk9A.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaNational Research Centre “Kurchatov Institute”, 1, Akademika Kurchatova Pl., 123182 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaA.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 59, Leninskii Prospect, 119333 Moscow, RussiaThe structure of an aqueous solution of potassium dihydrogen phosphate (KH<sub>2</sub>PO<sub>4</sub>, KDP) was studied by small-angle X-ray scattering (SAXS) and molecular dynamics (MD). According to SAXS data, the octameric species (KH<sub>2</sub>PO<sub>4</sub>)<sub>8</sub> are formed in solution in addition to K<sup>+</sup>, (H<sub>2</sub>PO<sub>4</sub>)<sup>−</sup>, and KH<sub>2</sub>PO<sub>4</sub>, while the presence of other types of oligomers is not observed. When the temperature drops below the saturation temperature (~60 °C), the volume fraction of octamers increases sharply, reaching 50% at 4 °C. The results of MD calculations of the temporal stability relationships of dimers (KH<sub>2</sub>PO<sub>4</sub>)<sub>2</sub>, tetramers (KH<sub>2</sub>PO<sub>4</sub>)<sub>4</sub>, and octamers (KH<sub>2</sub>PO<sub>4</sub>)<sub>8</sub> show that the dimers and tetramers disintegrate rapidly (50–100 ps), while the octamers remain stable. A comparative analysis of the bonds between the octamers and the KDP crystal lattice was carried out when the octamer was inserted during crystal growth in the directions [001] and [100]. The possible relationship of the obtained results with the changes in the anisotropy of growth rates (habitus) of KDP crystals at different degrees of supersaturation is discussed.https://www.mdpi.com/2073-4352/13/11/1577three-stage crystallization modelnonclassical crystallizationprecursor clusterswater solutionsmall-angle X-ray scatteringKDP |
| spellingShingle | Andrey E. Sukhanov Petr V. Konarev Vladimir I. Timofeev Ildar F. Garipov Ekaterina S. Smirnova Georgy S. Peters Kseniia B. Ilina Yury V. Pisarevsky Olga A. Alekseeva Mikhail V. Kovalchuk Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics Crystals three-stage crystallization model nonclassical crystallization precursor clusters water solution small-angle X-ray scattering KDP |
| title | Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics |
| title_full | Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics |
| title_fullStr | Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics |
| title_full_unstemmed | Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics |
| title_short | Study of the Formation of Precursor Clusters in an Aqueous Solution of KH<sub>2</sub>PO<sub>4</sub> by Small-Angle X-ray Scattering and Molecular Dynamics |
| title_sort | study of the formation of precursor clusters in an aqueous solution of kh sub 2 sub po sub 4 sub by small angle x ray scattering and molecular dynamics |
| topic | three-stage crystallization model nonclassical crystallization precursor clusters water solution small-angle X-ray scattering KDP |
| url | https://www.mdpi.com/2073-4352/13/11/1577 |
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