Constraint density functional calculations for multiplets in a ligand-field applied to Fe-phthalocyanine

Kohji Nakamura, Yukie Kitaoka, Toru Akiyama, Tomonori Ito, M. Weinert, Arthur J Freeman

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Multiplets in a ligand field are treated within total-energy density-functional calculations by imposing density-matrix constraints on the d-orbital occupation numbers consistent with the local site and state symmetries. We demonstrate the utility of this approach for the case of isolated Fe phthalocyanine (FePc) molecules with overall D 4h symmetry: We find three stationary states of 3E g, 3A 2g, and 3B 2g symmetries of the Fe2 + ion, and total-energy calculations clearly demonstrate that the ground state is 3A 2g. By contrast, a columnar stacking of the FePc molecules (α-FePc) is found to change the ground state to 3E g due to hybridization between adjacent molecules.

Original languageEnglish
Article number235129
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume85
Issue number23
DOIs
Publication statusPublished - Jun 18 2012

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Density functional theory
fine structure
Ligands
Ground state
ligands
Molecules
symmetry
molecules
ground state
occupation
flux density
Ions
orbitals
phthalocyanine
ions
energy

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Electronic, Optical and Magnetic Materials

Cite this

Constraint density functional calculations for multiplets in a ligand-field applied to Fe-phthalocyanine. / Nakamura, Kohji; Kitaoka, Yukie; Akiyama, Toru; Ito, Tomonori; Weinert, M.; Freeman, Arthur J.

In: Physical Review B - Condensed Matter and Materials Physics, Vol. 85, No. 23, 235129, 18.06.2012.

Research output: Contribution to journalArticle

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