Pressure gradient effect on spin-crossover materials: Experiment vs theory

Rusu, Ionela; Manolache-Rusu, Ioan Cozmin; Diaconu, Andrei; Palamarciuc, Oleg; Gural'skiy, Il’ya A.; Molnár, Gábor; Rotaru, Aurelian

doi:10.1063/5.0042582

Cited by 7 publications

(9 citation statements)

References 45 publications

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“…Therefore, the transition becomes gradual with hysteresis. The influence of pressure on the shape of the transition loop recently has been studied in ref , and it has been shown that the gradient of the pressure results in inclined the ST loop . Here, we show that not only the pressure gradient but also the internal pressure caused by different compressibilities of HS and LS molecules are changed when the pressure variation inclines the hysteresis loop and induces the mixing intermediate state.…”

Section: Discussionmentioning

confidence: 99%

“…The influence of pressure on the shape of the transition loop recently has been studied in ref 50, and it has been shown that the gradient of the pressure results in inclined the ST loop. 50 Here, we show that not only the pressure gradient but also the internal pressure caused by different compressibilities of HS and LS molecules are changed when the pressure variation inclines the hysteresis loop and induces the mixing intermediate state. The difference between internal and external pressure is comparable to the difference between magnetic induction inside a magnet and an external magnetic field.…”

Section: Hs Lsmentioning

confidence: 99%

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Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds

Li¹,

Каліта²,

Fylymonov³

et al. 2022

Inorg. Chem.

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Recently, the possibility of exploiting the phenomenon of spin transition (ST) has been intensively investigated; therefore, it is particularly important to study the behavior of ST under various stimuli. Here, the shape and content of the intermediate phase of ST in Hoffmann-like compounds [Fe(Fpz) 2 M(CN) 4 ] (M = Pt, Pd) under external stimuli are studied. For this purpose, magnetic and Raman spectroscopy studies were carried out. In pressure-induced spin transition (PIST), a mixture of high-spin and low-spin states appears, while in temperature-induced spin transition (TIST), a homogeneous state occurs. The first-order ST induced by pressure has a hysteresis but is not abrupt. However, the temperature-induced spin transition at ambient pressure is hysteretic and abrupt. To investigate this difference, we discuss using a thermodynamic model that considers elastic interactions, showing that the slope of the hysteresis loop is related to the appearance of internal pressure, which is related to the difference in sample compressibility under high-spin and low-spin states.

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Section: Discussionmentioning

confidence: 99%

Section: Hs Lsmentioning

confidence: 99%

Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds

Li¹,

Каліта²,

Fylymonov³

et al. 2022

Inorg. Chem.

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show abstract

“…The FORC diagram method has been proved a very sensitive tool for the characterization of the hysteretic properties of spin transition materials as it gives more information about the spin-domain structure which influences the material's behavior inside the hysteresis loop [24,25]. Figure 7 shows the FORC diagrams obtained within the framework of the CPM where the contour plot has a circular shape and for four other values of the sample contrast parameter C, expressed in reversal-measurement temperature coordinates.…”

Section: Km Correction On the Forc Diagrammentioning

confidence: 99%

Monitoring Spin-Crossover Properties by Diffused Reflectivity

et al. 2021

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In this work we present a detailed study showing the importance of the Kubelka-Munk (KM) correction in the analysis of diffuse reflectivity measurements to characterize spin crossover compounds. Combined reflectance and magnetic susceptibility measurements are carried out as a function of temperature or time to highlight the conditions under which this correction becomes critical. In particular, we investigate the influence of the color contrast between the two spin states on the reflectance measurements. Interestingly, the samples’ contrast seems to play an important role on the spin-like domain structure as suggested by the symmetry of the FORC diagrams. These latest results are discussed within the framework of Classical Preisach model (CPM).

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“…This aspect was recently pointed out in spin-crossover (SCO) solids, as such gradients could be a major ingredient to describe the hysteretic properties of these materials. 58 In the case of PBAs, these distortions may involve correlated tilts of the metallocyanide units, presumably at medium distances due to the inherent structural disorder, and have a large counteraction on the charge transfer processes because of a decrease of the transfer integral.…”

Section: Impact Of Inhomogeneous Stress Fieldsmentioning

confidence: 99%

High-pressure behavior of heteroepitaxial core–shell particles made of Prussian blue analogs

Maurin

Itoi

Cain

et al. 2021

Journal of Applied Physics

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We report the compressibility of two Prussian blue analogues (PBA) under hydrostatic pressure, one with small and one with relatively large cubic unit cell among PBAs, and investigate the modification of their elastic properties when the two lattices are coupled within a heteroepitaxial core-shell structure. Bulk modulus (K0) values are derived from x-ray powder diffraction experiments using a diamond anvil cell with silicone oil as pressure-transmitting medium. The pressure-volume curves fitted to Murnaghan equations of states show that K0 inversely scales with the crystal packing for the rubidium cobalt hexacyanoferrate and rubidium nickel hexacyanochromate samples (K0  29 GPa for Co-Fe PBA, a0 = 9.95 Å and  20 GPa for Ni-Cr PBA, a0 = 10.48 Å with a0 the lattice constant at ambient pressure). The two single-phase samples undergo a cubic-to-rhombohedral phase transition above ~ 0.8 GPa, which correlates fairly well with the build-up of nonhydrostatic pressure contributions in the cell. Within the core-shell structure, the volume change observed for the core scales with that of the shell because of the configuration close to the case of a solid pressure-transmitting medium. The Ni-Cr PBA shell layer exhibits an increased rhombohedral distortion with respect to the single-phase reference possibly associated with shearing at the core-shell interface. Its bulk modulus is not significantly modified with respect to that of the single-phase sample despite the presence of defects associated with the growth mode, whereas the P-V curve of the core suggests a stiffening of the Co-Fe PBA lattice.

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Pressure gradient effect on spin-crossover materials: Experiment vs theory

Cited by 7 publications

References 45 publications

Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds

Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds

Monitoring Spin-Crossover Properties by Diffused Reflectivity

High-pressure behavior of heteroepitaxial core–shell particles made of Prussian blue analogs

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