The role of P 3s2 lone pair (E) in structure, properties and phase transitions of black phosphorus. Stereochemistry and ab initio topology analyses
| dc.rights.license | open | en_US |
| dc.relation.isnodouble | e123e694-69c1-41d4-a955-84b9c87d4d44 | * |
| hal.structure.identifier | Laboratoire des Composites Thermostructuraux [LCTS] | |
| dc.contributor.author | GALY, Jean | |
| hal.structure.identifier | Laboratoire des Composites Thermostructuraux [LCTS] | |
| dc.contributor.author | VIGNOLES, Gérard L. | |
| dc.date.accessioned | 2021-07-21T13:07:20Z | |
| dc.date.available | 2021-07-21T13:07:20Z | |
| dc.date.issued | 2020-02-01 | |
| dc.identifier.issn | 1293-2558 | en_US |
| dc.identifier.uri | oai:crossref.org:10.1016/j.solidstatesciences.2019.106068 | |
| dc.identifier.uri | https://oskar-bordeaux.fr/handle/20.500.12278/110156 | |
| dc.description.abstractEn | An approach merging crystal chemistry and density functional theory (DFT) electron localization function (ELF) taking P 3s2 lone pair (E) into account induces a full renewal of stereochemistry of black phosphorus, its crystal network evolutions and phase transitions under increasing pressures from atmospheric up to 32 GPa. Orthorhombic (Cmce) black P at ambient pressure, shows a packing of puckered [P]n layers - orthogonal to [010] - separated by a large free interspace (3.071 Å), which actually is partially filled by lone pairs (E) (P-E ~ 0.8 Å). Each P exhibits its lone pair pointing outside the [P]n layer, sandwiching it between two [E]n layers into a new stacking sequence … [EP2E]n … denoted O-[PE]n. The free interspace between [EP2E]n layers is much smaller 1.858 Å but allows sliding along [001]. The pressure evolving up to 2.66 GPa, all structural details have been followed and reported, including the layer thickness reduction along [010] and the sliding along [001] of consecutive layers. A mechanism for the phase transition occurring around 5.5 GPa is proposed. Depicted in the trigonal system the new layered phase R-[PE]n involves a bond rearrangement through E-E layer in zigzag phosphorus layers and P-E rotation and alignment with the A axis. Now, the phosphorene layers have P-E patterns oriented towards each other in their interspace. A very particular phenomenon occurs around ~11 GPa the lone pair centroid Ec (P-Ec = 0.73 Å) splits into three partially occupied sites Ed around the A axis which explains observed variations in properties at this critical pressure. So, we claim that there are two trigonal phases, R1-[PE] up to 11 GPa followed by a second form R2-[PE] directly caused by lone pair displacement from Ec to Ed and its influence on layer stacking. A further layer sliding brings the phosphorus atomic layers close enough to each other to establish new P-P bonds and then to cause an ultimate transition to cubic system, with a new structure, isostructural to Po. The mechanisms of the transitions are detailed. | |
| dc.language.iso | EN | en_US |
| dc.rights | Attribution-NonCommercial-NoDerivs 3.0 United States | * |
| dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/3.0/us/ | * |
| dc.source | crossref | |
| dc.subject.en | P3s2 lone pair | |
| dc.subject.en | Black phosphorus | |
| dc.subject.en | Solid state stereochemistry | |
| dc.subject.en | Phase transitions & high pressures | |
| dc.subject.en | DFT | |
| dc.subject.en | ELF | |
| dc.title.en | The role of P 3s2 lone pair (E) in structure, properties and phase transitions of black phosphorus. Stereochemistry and ab initio topology analyses | |
| dc.type | Article de revue | en_US |
| dc.identifier.doi | 10.1016/j.solidstatesciences.2019.106068 | en_US |
| dc.subject.hal | Chimie/Matériaux | en_US |
| bordeaux.journal | Solid State Sciences | en_US |
| bordeaux.page | 106068 | en_US |
| bordeaux.volume | 100 | en_US |
| bordeaux.hal.laboratories | Laboratoire des Composites Thermo Structuraux (LCTS) - UMR 5801 | en_US |
| bordeaux.institution | Université de Bordeaux | en_US |
| bordeaux.institution | CNRS | en_US |
| bordeaux.institution | CEA | en_US |
| bordeaux.peerReviewed | oui | en_US |
| bordeaux.inpress | non | en_US |
| bordeaux.import.source | dissemin | |
| hal.identifier | hal-03294295 | |
| hal.version | 1 | |
| hal.date.transferred | 2021-07-21T13:07:26Z | |
| hal.export | true | |
| workflow.import.source | dissemin | |
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