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

Kohji Nakamura, Yukie Kitaoka, Toru Akiyama, Tomonori Ito, M. Weinert, and A. J. Freeman
Phys. Rev. B 85, 235129 – Published 18 June 2012

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 D4h symmetry: We find three stationary states of 3Eg, 3A2g, and 3B2g symmetries of the Fe2+ ion, and total-energy calculations clearly demonstrate that the ground state is 3A2g. By contrast, a columnar stacking of the FePc molecules (α-FePc) is found to change the ground state to 3Eg due to hybridization between adjacent molecules.

  • Figure
  • Figure
  • Figure
  • Figure
  • Received 13 September 2011

DOI:https://doi.org/10.1103/PhysRevB.85.235129

©2012 American Physical Society

Authors & Affiliations

Kohji Nakamura*, Yukie Kitaoka, Toru Akiyama, and Tomonori Ito

  • Department of Physics Engineering, Mie University, Tsu, Mie 514-8507, Japan

M. Weinert

  • Department of Physics, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, USA

A. J. Freeman

  • Department of Physics and Astronomy, Northwestern University, Evanston, Illinois 60208, USA

  • *kohji@phen.mie-u.ac.jp

Article Text (Subscription Required)

Click to Expand

References (Subscription Required)

Click to Expand
Issue

Vol. 85, Iss. 23 — 15 June 2012

Reuse & Permissions
Access Options
CHORUS

Article Available via CHORUS

Download Accepted Manuscript
Author publication services for translation and copyediting assistance advertisement

Authorization Required


×
×

Images

×

Sign up to receive regular email alerts from Physical Review B

Log In

Cancel
×

Search


Article Lookup

Paste a citation or DOI

Enter a citation
×