Topological analysis of chemical bonding in the layered FePSe₃ upon pressure‐induced phase transitions

Abstract

Two pressure-induced phase transitions have been theoretically studied in the layered iron phosphorus triselenide (FePSe 3). Topological analysis of chemical bonding in FePSe 3 has been performed based on the results of first-principles calculations within the periodic linear combination of atomic orbitals (LCAO) method with hybrid Hartree-Fock-DFT B3LYP functional. The first transition at about 6 GPa is accompanied by the symmetry change from R 3 to C2/m, whereas the semiconductor-to-metal transition (SMT) occurs at about 13 GPa leading to the symmetry change from C2/m to P 31m. We found that the collapse of the band gap at about 13 GPa occurs due to changes in the electronic structure of FePSe 3 induced by relative displacements of phosphorus or selenium atoms along the c-axis direction under pressure. The results of the topological analysis of the electron density and its Laplacian demonstrate that the pressure changes not only the interatomic distances but also the bond nature between the intralayer and interlayer phosphorus atoms. The interlayer P-P interactions are absent in two non-metallic FePSe 3 phases while after SMT the intralayer P-P interactions weaken and the interlayer P-P interactions appear.

Pressure-induced phase transitions in weak interlayer coupling CdPS3

“…[11][12][13][14][15][16][17] van der Waals MPX 3 exhibits an exceptional response to high pressure, since the distance between adjacent layers is effectively reduced, and the electronic properties are modified accordingly. [18][19][20][21][22][23][24][25] In MnPS 3 , three controllable piezochromic behaviors have been found for pressure values above 20 GPa. The symmetry of the structure switches from C2=m to P 31m at approximately 10 GPa and then into another C2=m phase above 30 GPa.…”

“…18,19,23,25 In addition to the phase transition, superconductivity emerges (below a critical temperature T c ) at approximately 2.5 K at 9.0 GPa and the maximum T c at approximately 5.5 K around 30 GPa. 20,23 All these structural transformations under high pressure are caused by the sliding of layers along different directions.…”

Elastic and piezoelectric properties of β-glycine – a quantum crystallography view on intermolecular interactions and a high-pressure phase transition

“…This approach is known as quantum crystallography (Grabowsky et al, 2017;Tsirelson, 2018;Genoni & Macchi, 2020;Grabowsky et al, 2020;Tsirelson & Stash, 2020;Macchi, 2022;Matta et al, 2023). One of the important aims of quantum crystallography is to elucidate the mechanical characteristics of crystals, relating microscopic properties (distortions of chemical bonds, changes in the intermolecular contacts under high pressure) and macroscopic properties, such as structural response to hydrostatic pressure, compressibility and piezoelectric properties (Zhurova et al, 2006;Coudert & Fuchs, 2016;Riffet et al, 2017;Tsirelson et al, 2019;Evarestov & Kuzmin, 2020;Bartashevich et al, 2020;Korabel'nikov & Zhuravlev, 2020;Mishra & Tewari, 2020;Bartashevich et al, 2021;Feng et al, 2021;Matveychuk et al, 2021;Bogdanov et al, 2022;Gajda et al, 2022;Zhuravlev & Korabel'nikov, 2022;Stachowicz et al, 2023). Revealing relations between structural changes and mechanical properties of crystals helps to understand the nature of the piezoelectric effect and to design new piezoelectric materials (Guerin et al, 2019;Vijayakanth et al, 2022;Ivanov et al, 2023), as well as to rationalize thermo-and photomechanical effects with applications for design of materials and devices (Naumov et al, 2013(Naumov et al, , 2015Koshima et al, 2021;Karothu et al, 2022;Awad et al, 2023).…”

“…Orbital-free quantum crystallography approaches provide new opportunities to characterize crystals under compression (Zhurova et al, 2006;Casati et al, 2016Casati et al, , 2017Coudert & Fuchs, 2016;Tsirelson et al, 2016;Riffet et al, 2017;Tsirelson et al, 2019;Tsirelson & Stash, 2020;Evarestov & Kuzmin, 2020;Bartashevich et al, 2020;Korabel'nikov & Zhuravlev, 2020;Mishra & Tewari, 2020;Bartashevich et al, 2021;Gajda et al, 2022;Zhuravlev & Korabel'nikov, 2022;Stachowicz et al, 2023). As in the classical theory of elasticity (Landau et al, 2009), the compression and stretching of the electronic continuum in molecules and crystals can be described by the density of the stress tensor, (r) (Rogers & Rappe, 2002;Tao et al, 2008;Tsirelson et al, 2016).…”