Role of zero-point effects in stabilizing the ground state structure of bulk Fe<sub>2</sub>P

Bhat, Soumya S.; Gupta, Kapil; Bhattacharjee, Satadeep; Lee, Seung Cheol

doi:10.1088/1361-648x/aabe52

Cited by 7 publications

(24 citation statements)

References 43 publications

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“…However, the authors did not provide the details of their calculations. DFT calculations carried out by Bhat et al 29 showed that C22/C23 phase www.nature.com/scientificreports www.nature.com/scientificreports/ transition occurred at about 300 K indicating that C23-allabogdanite can be stable at ambient conditions. The use of DFT + U approach also led to the stability of allabogdanite 29 .…”

Section: Discussionmentioning

confidence: 99%

“…DFT calculations carried out by Bhat et al 29 showed that C22/C23 phase www.nature.com/scientificreports www.nature.com/scientificreports/ transition occurred at about 300 K indicating that C23-allabogdanite can be stable at ambient conditions. The use of DFT + U approach also led to the stability of allabogdanite 29 . Finally, considering the energy contribution of zero-point spin fluctuations (ZPSF) Fe 2 P-barringerite phase became energetically favorable, which, according to the authors, represents the exceptionally rare case of bulk material stabilization 29 .…”

Section: Discussionmentioning

confidence: 99%

“…The use of DFT + U approach also led to the stability of allabogdanite 29 . Finally, considering the energy contribution of zero-point spin fluctuations (ZPSF) Fe 2 P-barringerite phase became energetically favorable, which, according to the authors, represents the exceptionally rare case of bulk material stabilization 29 . Our DFT calculations have shown that the allabogdanite phase is stable at ambient conditions without ZPSF energy contribution.…”

Section: Discussionmentioning

confidence: 99%

“…Firstly, ab initio calculations showed that Fe 2 P-allabogdanite is energetically favorable compared to Fe 2 P-barringerite at ambient conditions 28 , which contradicts the experimental evidence for barringerite as an ambient pressure phase 19 . Bhat et al 29 took into account the spin fluctuations to obtain preferable energetic stability of barringerite at ambient conditions, which, according to the authors, is an "exceptional case" in ab initio calculations. Secondly, C23 Co 2 P-allabogdanite modification is thermodynamically stable at ambient conditions 25 .…”

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(Fe,Ni)2P allabogdanite can be an ambient pressure phase in iron meteorites

Litasov

Bekker

Sagatov

et al. 2020

Sci Rep

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An orthorhombic modification of (Fe,Ni) 2 P, allabogdanite, found in iron meteorites was considered to be thermodynamically stable at pressures above 8 GPa and temperatures of 1673 K according to the results of recent static high-pressure and high-temperature experiments. A hexagonal polymorphic modification of (Fe,Ni) 2 P, barringerite, was considered to be stable at ambient conditions. Experimental investigation through the solid-state synthesis supported by ab initio calculations was carried out to clarify the stability fields of (Fe,Ni) 2 P polymorphs. Both experimental and theoretical studies show that fe 2 P-allabogdanite is a low-temperature phase stable at ambient conditions up to a temperature of at least 773 K and, therefore, is not necessarily associated with high pressures. This is consistent with the textural relationships of allabogdanite in iron meteorites. Fe 2 P plays a substantial role in the mineralogy of iron meteorites. Two polymorphic modifications of Fe 2 P−Ni 2 P solid-solution currently known are hexagonal barringerite (C22) 1,2 and orthorhombic allabogdanite (C23) 3,4. Barringerite was discovered in the Ollague pallasite found in Bolivia 1. The composition determined by electron probe microanalysis was (Fe 0.58 Ni 0.42 Co 0.003) 1.95 P. It is isostructural with the hexagonal modification of Fe 2 P with lattice parameters a = 5.87(7) Å and c = 3.44(4) Å. In a short time after its discovery, it was shown that the Ollague meteorite is a fragment of a very large, up to several hundred kilograms, Imilac pallasite, the numerous fragments of which were found in the province of Antofagasta, Chile. It turned out that the Ollague meteorite was artificially reheated, which could cause high-temperature changes in the chemical and mineral compositions 5. It is noteworthy that barringerite has never been observed in other fragments of the Imilac meteorite or other investigated pallasites. Some barringerite findings are associated with placers 6 , but their sources are probably cosmogenic 2. Detailed mineralogical and crystal-chemical characterization of terrestrial barringerite from pyrometamorphic rocks of the Hatrurim formation, Israel is reported by Britvin et al. 2. The mineral occurs in associations of the so-called «paralavas» − initially silicate-carbonate sedimentary rocks that remelted during pyrometamorphic processes at about 1300 K, but under low pressure. Barringerite from the Hatrurim formation is almost pure Fe 2 P, the exact composition is (Fe 1.95 Ni 0.03 Cr 0.02) 2.00 P. The unit cell parameters determined by single crystal X-ray diffraction are a = 5.867(1) Å and c = 3.464(1) Å with Z = 3. The orthorhombic modification of Fe 2 P−Ni 2 P solid-solution, allabogdanite was first detected in anomalous Onello high-Ni ataxite found in 1997 in the alluvium of the Onello River, Yakutia, Russia 3. Earlier this mineral in the Onello ataxite was considered barringerite 7-9. The unit cell parameters of allabogdanite refined from single-crystal data are a = 5.792(7) Å, b = 3.564(4) Å, and c = 6.69...

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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(Fe,Ni)2P allabogdanite can be an ambient pressure phase in iron meteorites

Litasov

Bekker

Sagatov

et al. 2020

Sci Rep

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“…In zero applied field (ZF), 31 P and 57 Fe nuclei resonate in their hyperfine fields, giving rise to distinct resonance lines for each crystallographic site. We detected the 57 Fe resonance stemming from Fe2 and the 31 P resonances of P1 and P2 and unambiguously assigned them to their respective nuclei, thus correcting the peak attribution by an early NMR work [23], which is proven here to be erroneous.…”

Section: Introductionmentioning

confidence: 99%

Ab initio modeling and experimental investigation of Fe2P by DFT and spin spectroscopies

Bonfà

Isah

Frandsen

et al. 2021

Phys. Rev. Materials

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Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe₂P Polymorphs

Kong,

Singh,

Sarkar

et al. 2024

Chem. Mater.

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Iron phosphide (Fe 2 P) crystallizes in its own hexagonal crystal structure type (h-Fe 2 P). As found in meteorites, orthorhombic polymorph (o-Fe 2 P) was originally reported as a high-temperature and high-pressure phase. Recently, o-Fe 2 P was described as being stable at ambient pressure, yet no synthetic methods were developed for singlecrystal growth or single-phase bulk powder synthesis. Here, we report a successful method for growing o-Fe 2 P single crystals and synthesizing phase-pure polycrystalline samples using tin-flux. In situ powder X-ray diffraction studies showed that the phase transition from o-Fe 2 P to h-Fe 2 P occurs at about 873 K, and below that temperature, the formation of the o-Fe 2 P phase is favored thermodynamically rather than kinetically. Systematic comparison of transport, magnetic, and electrocatalytic properties of both h-Fe 2 P and o-Fe 2 P phases showed a substantial impact of the crystal structure on properties. The orthorhombic structural distortion resulted in considerable changes in magnetic properties, with the o-Fe 2 P phase exhibiting a 60% lower Fe magnetic moment and a substantially higher ferromagnetic Curie temperature than h-Fe 2 P. Electrochemical measurements toward the hydrogen evolution reaction in acidic media showed that the o-Fe 2 P phase requires an 80 mV lower overpotential than the h-Fe 2 P phase to generate a current density of −10 mA/cm 2 , and their electronic structures suggest that the higher density of states at the Fermi energy is the origin of superior catalytic activity in o-Fe 2 P.

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Role of zero-point effects in stabilizing the ground state structure of bulk Fe₂P

Cited by 7 publications

References 43 publications

(Fe,Ni)2P allabogdanite can be an ambient pressure phase in iron meteorites

(Fe,Ni)2P allabogdanite can be an ambient pressure phase in iron meteorites

Ab initio modeling and experimental investigation of Fe2P by DFT and spin spectroscopies

Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe₂P Polymorphs

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Role of zero-point effects in stabilizing the ground state structure of bulk Fe2P

Cited by 7 publications

References 43 publications

(Fe,Ni)2P allabogdanite can be an ambient pressure phase in iron meteorites

(Fe,Ni)2P allabogdanite can be an ambient pressure phase in iron meteorites

Ab initio modeling and experimental investigation of Fe2P by DFT and spin spectroscopies

Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe2P Polymorphs

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Product

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Role of zero-point effects in stabilizing the ground state structure of bulk Fe₂P

Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe₂P Polymorphs