Several examples of metallic electron-doped polycyclic aromatic hydrocarbons (PAHs) molecular crystals have recently been experimentally proposed. Some of them have superconducting components, but most other details are still unknown beginning with structure and the nature of metallicity. We carried out ab initio density functional calculations for La-Phenanthrene (La-PA), here meant to represent a generic case of three-electron doping, to investigate structure and properties of a conceptually simple case. To our surprise we found first of all that the lowest energy state is not metallic but band insulating, with a disproportionation of two inequivalent PA molecular ions and a low P1 symmetry, questioning the common assumption that three electrons will automatically metallize a PAH crystal. Our best metallic structure is metastable and slightly higher in energy, and retains equivalent PA ions and a higher P2(1) symmetry-the same generally claimed for metallic PAHs. We show that a "dimerizing" periodic distortion opens very effectively a gap in place of a symmetry related degeneracy of all P2(1) structures near the Fermi level, foreshadowing a possible role of that special intermolecular phonon in superconductivity of metallic PAHs. A Hubbard-Frohlich model describing that situation is formulated for future studies.
Electron-doped organics: Charge-disproportionate insulators and Hubbard-Frohlich metals
Fabrizio Michele;Tosatti Erio
2013
Abstract
Several examples of metallic electron-doped polycyclic aromatic hydrocarbons (PAHs) molecular crystals have recently been experimentally proposed. Some of them have superconducting components, but most other details are still unknown beginning with structure and the nature of metallicity. We carried out ab initio density functional calculations for La-Phenanthrene (La-PA), here meant to represent a generic case of three-electron doping, to investigate structure and properties of a conceptually simple case. To our surprise we found first of all that the lowest energy state is not metallic but band insulating, with a disproportionation of two inequivalent PA molecular ions and a low P1 symmetry, questioning the common assumption that three electrons will automatically metallize a PAH crystal. Our best metallic structure is metastable and slightly higher in energy, and retains equivalent PA ions and a higher P2(1) symmetry-the same generally claimed for metallic PAHs. We show that a "dimerizing" periodic distortion opens very effectively a gap in place of a symmetry related degeneracy of all P2(1) structures near the Fermi level, foreshadowing a possible role of that special intermolecular phonon in superconductivity of metallic PAHs. A Hubbard-Frohlich model describing that situation is formulated for future studies.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
