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Density functional theory study of single-molecule ferroelectricity in Preyssler-type polyoxometalates

  • Dades identificatives

    Identificador: imarina:9182622
    Autors:
    Wang, FeiLang, ZhonglingYan, LikaiStroppa, AlessandroPoblet, Josep M.de Graaf, Coen
    Resum:
    A detailed study on the single-molecule ferroelectric property of Preyssler-type polyoxometalates (POMs), [M3+P5W30O110](12-) (M = La, Gd, and Lu), is performed by density functional theory calculations. Linked to one H2O molecule, the cation (M3+) encapsulated in the cavity of the Preyssler framework is off-centered, and it generates a permanent dipole, which is essential for a ferroelectric ground state. Accompanied with a 180 degrees rotation of H2O, the switching of M3+ between two isoenergetic sites on both sides of the cavity results in a calculated barrier of 1.15 eV for Gd3+, leading to the inversion of electric polarization. The height of the barrier is in good agreement with the experimentally measured barrier for the Tb3+ ion, whose ionic radius is similar to Gd3+. The total polarization value of the crystal is estimated to be 4.7 mu C/cm(2) as calculated by the modern theory of polarization, which is quite close to the experimental value. Considering that the order of contributions to the polarization is M3+-H2O > counter-cations (K+) > [P5W30O110](15-), the interconversion of M3+-H2O between the two isoenergetic sites is predicted to be the main origin of ferroelectricity with a polarization contribution of 3.4 mu C/cm(2); the K+ counter-cations contribute by 1.2 mu C/cm(2) and it cannot be disregarded, while the framework appears to contribute negligibly to the total polarization. Our study suggests that a suitable choice of M3+-H2O could be used to tune the single-molecule ferroelectricity in Preyssler-type polyoxometalates.
  • Altres:

    Autor segons l'article: Wang, Fei; Lang, Zhongling; Yan, Likai; Stroppa, Alessandro; Poblet, Josep M.; de Graaf, Coen;
    Departament: Química Física i Inorgànica
    Autor/s de la URV: De Graaf, Cornelis / Poblet Rius, Josep Maria / Wang, Fei
    Paraules clau: Single molecule Positive ions Polyoxometalates Polarization Permanent dipoles Molecules Modern theory of polarization Interconversions Ground state Ferroelectricity Ferroelectric property Experimental values Electric polarization Density functional theory studies Density functional theory
    Resum: A detailed study on the single-molecule ferroelectric property of Preyssler-type polyoxometalates (POMs), [M3+P5W30O110](12-) (M = La, Gd, and Lu), is performed by density functional theory calculations. Linked to one H2O molecule, the cation (M3+) encapsulated in the cavity of the Preyssler framework is off-centered, and it generates a permanent dipole, which is essential for a ferroelectric ground state. Accompanied with a 180 degrees rotation of H2O, the switching of M3+ between two isoenergetic sites on both sides of the cavity results in a calculated barrier of 1.15 eV for Gd3+, leading to the inversion of electric polarization. The height of the barrier is in good agreement with the experimentally measured barrier for the Tb3+ ion, whose ionic radius is similar to Gd3+. The total polarization value of the crystal is estimated to be 4.7 mu C/cm(2) as calculated by the modern theory of polarization, which is quite close to the experimental value. Considering that the order of contributions to the polarization is M3+-H2O > counter-cations (K+) > [P5W30O110](15-), the interconversion of M3+-H2O between the two isoenergetic sites is predicted to be the main origin of ferroelectricity with a polarization contribution of 3.4 mu C/cm(2); the K+ counter-cations contribute by 1.2 mu C/cm(2) and it cannot be disregarded, while the framework appears to contribute negligibly to the total polarization. Our study suggests that a suitable choice of M3+-H2O could be used to tune the single-molecule ferroelectricity in Preyssler-type polyoxometalates.
    Àrees temàtiques: Química Physics, applied Nanoscience & nanotechnology Materials science, multidisciplinary Materials science (miscellaneous) Materials science (all) Materiais General materials science General engineering Engineering (miscellaneous) Engineering (all) Engenharias iii Engenharias ii Ciências agrárias i Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: coen.degraaf@urv.cat fei.wang@urv.cat josepmaria.poblet@urv.cat
    Identificador de l'autor: 0000-0001-8114-6658 0000-0001-5106-5793 0000-0002-4533-0623
    Data d'alta del registre: 2024-07-27
    Volum de revista: 9
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Enllaç font original: https://aip.scitation.org/doi/10.1063/5.0035778
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Apl Materials. 9 (2):
    Referència de l'ítem segons les normes APA: Wang, Fei; Lang, Zhongling; Yan, Likai; Stroppa, Alessandro; Poblet, Josep M.; de Graaf, Coen; (2021). Density functional theory study of single-molecule ferroelectricity in Preyssler-type polyoxometalates. Apl Materials, 9(2), -. DOI: 10.1063/5.0035778
    DOI de l'article: 10.1063/5.0035778
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2021
    Tipus de publicació: Journal Publications
  • Paraules clau:

    Engineering (Miscellaneous),Materials Science (Miscellaneous),Materials Science, Multidisciplinary,Nanoscience & Nanotechnology,Physics, Applied
    Single molecule
    Positive ions
    Polyoxometalates
    Polarization
    Permanent dipoles
    Molecules
    Modern theory of polarization
    Interconversions
    Ground state
    Ferroelectricity
    Ferroelectric property
    Experimental values
    Electric polarization
    Density functional theory studies
    Density functional theory
    Química
    Physics, applied
    Nanoscience & nanotechnology
    Materials science, multidisciplinary
    Materials science (miscellaneous)
    Materials science (all)
    Materiais
    General materials science
    General engineering
    Engineering (miscellaneous)
    Engineering (all)
    Engenharias iii
    Engenharias ii
    Ciências agrárias i
    Astronomia / física
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