Magnetic characterization, electronic structure and vibrational properties of (NH4)2 M(SO4)2·6H2O (M=Mn, Ni) crystals

Pacheco, Tiago S.; Ludwig, Zélia M.C.; Ullah, Saif; Mendonça, João Paulo Almeida de; Sato, F.; Souza, Rafael Limongi de; Paiva, Edinei Canuto; Martins, Maximiliano; Marques, Flávia C.; Andrade, Gustavo Fernandes Souza; Ghosh, Santunu

doi:10.1016/j.ssc.2021.114384

Cited by 4 publications

(3 citation statements)

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“…These above types of connections can be affected by agents such as dopants/impurities in the crystalline network of these materials. The presence of dopants can lead to changes in the normal vibrational modes of the molecular groups SO 4 , NH 4 , H 2 O, and M(H 2 O) 6 . − In recent years, several studies have been reporting on the attempt of doping Tutton salt family crystals, in addition to theoretical–computational studies (density functional theory (DFT)) where band structures and calculations of vibrational frequencies were studied. − Notably, our team synthesized K 2 M(SO 4 ) 2 (H 2 O) 6 mixed crystals, with M being a mixed composition of Ni/Co, to study the effects of a lithium dopant on the vibrational modes of the tetrahedral molecular groups SO 4 and octahedral Ni(H 2 O) 6 and Co(H 2 O) 6 , as reported by Pacheco et al…”

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confidence: 99%

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

et al. 2023

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In this work, we synthesized and studied the spectroscopic properties of (NH 4 ) 2 (SO 4 ) 2 Y(H 2 O) 6 (Y = Ni, Mg) crystals doped with AgNO 3 or H 3 BO 3 . These crystals constitute a series of hexahydrated salts known as Tutton salts. We investigated the influence of dopants on the vibrational modes of the tetrahedral ligands NH 4 and SO 4 , octahedral complexes Mg(H 2 O) 6 and Ni(H 2 O) 6 , and H 2 O molecules present in these crystals through Raman and infrared spectroscopies. We were able to identify bands that are attributed to the presence of Ag and B dopants, as well as band shifts caused by the presence of these dopants in the crystal lattice. A detailed study of the crystal degradation processes was performed by thermogravimetric measurements, where there was an increase in the initial temperature of crystal degradation due to the presence of dopants in the crystal lattice. Raman spectroscopy of the crystal residues after the thermogravimetric measurements helped us to elucidate the degradation processes occurring after the crystal pyrolysis process.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

et al. 2023

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“…] , a n d (NH 4 ) 2 Ni x Co 1-x (SO 4 ) 2 •6H 2 O [12]. However, few papers provide studies involving the occupation of Mn 2+ and Zn 2+ cations in the lattice structure of an individual or mixed Tutton salt [15,26,27]. Furthermore, few reports present computational investigations with information about bonding interactions in these systems [28].…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, few reports present computational investigations with information about bonding interactions in these systems [28]. It is known that computational chemistry tools, such as Hirshfeld surfaces, crystal voids, and density functional theory (DFT) calculations, can provide valuable features in support of experimental data for a better understanding of the interactions of constituent species in a Tutton salt, as well as their properties [24,26].…”

Section: Introductionmentioning

confidence: 99%

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

et al. 2022

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Tutton salts have been extensively explored in recent decades due to their attractive physical and chemical properties, which make them potential candidates for thermochemical heat storage systems and optical technologies. In this paper, a series of new mixed Tutton salts with the chemical formula (NH4)2Mn1–xZnx(SO4)2(H2O)6 is reported. Crystals are successfully grown by the solvent slow evaporation method and characterized by powder X-ray diffraction (PXRD) with Rietveld refinement. In particular, the crystal structure of the mixed (NH4)2Mn0.5Zn0.5(SO4)2(H2O)6 crystal is solved through PRXD data using the DICVOL06 algorithm for diffraction pattern indexing and the Le Bail method for lattice parameter and spatial group determination. The structure is refined using the Rietveld method implemented in TOPAS® and reported in the Cambridge Structural Database file number 2104098. Moreover, a computational study using Hirshfeld surface and crystal void analyses is conducted to identify and quantify the intermolecular interactions in the crystal structure as well as to determine the amount of free space in the unit cell. Furthermore, 2D-fingerprint plots are generated to evaluate the main intermolecular contacts that stabilize the crystal lattice. Density functional theory is employed to calculate the structural, thermodynamic, and electronic properties of the coordination [Zn(H2O)6]2+ and [Mn(H2O)6]2+ complexes present in the salts. Molecular orbitals, bond lengths, and the Jahn–Teller effect are also discussed. The findings suggest that in Mn-Zn salts several properties dependent on the electronic structure can be tuned up by modifying the chemical composition.

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Mixed tutton salts K2Mn0.15Co0.85(SO4)2(H2O)6 and K2Mn0.16Zn0.84(SO4)2(H2O)6 for applications in thermochemical devices: experimental physicochemical properties combined with first-principles calculations

de Oliveira Neto,

da Silva,

Alves

et al. 2024

J Mater Sci

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Magnetic characterization, electronic structure and vibrational properties of (NH4)2 M(SO4)2·6H2O (M=Mn, Ni) crystals

Cited by 4 publications

References 19 publications

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

Mixed tutton salts K2Mn0.15Co0.85(SO4)2(H2O)6 and K2Mn0.16Zn0.84(SO4)2(H2O)6 for applications in thermochemical devices: experimental physicochemical properties combined with first-principles calculations

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Magnetic characterization, electronic structure and vibrational properties of (NH4)2 M(SO4)2·6H2O (M=Mn, Ni) crystals

Cited by 4 publications

References 19 publications

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO3 or H3BO3

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO3 or H3BO3

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

Mixed tutton salts K2Mn0.15Co0.85(SO4)2(H2O)6 and K2Mn0.16Zn0.84(SO4)2(H2O)6 for applications in thermochemical devices: experimental physicochemical properties combined with first-principles calculations

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Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃