title: Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets.
abstract: Polarization-dependent X-ray absorption spectroscopy is combined with density functional calculations and atomic multiplet calculations to determine the crystal field parameters 10Dq, Ds, and Dt of transition metal phthalocyanines and octaethylporphyrins (Mn, Fe, Co, Ni). The polarization dependence facilitates the assignment of the multiplets in terms of in-plane and out-of-plane orbitals and avoids ambiguities. Crystal field values from density functional calculations provide starting values close to the optimum fit of the data. The resulting systematics of the crystal field can be used for optimizing electron-hole separation in dye-sensitized solar cells.
authors.affiliation: Department of Physics, University of Wisconsin-Madison, 1150 University Ave., Madison, Wisconsin 53706, USA.
authors.forename: Phillip S
authors.initials: PS
authors.lastname: Johnson
authors.affiliation: Department of Energy Conversion and Storage, Technical University of Denmark, 4000 Roskilde, Denmark.
authors.forename: J M
authors.initials: JM
authors.lastname: García-Lastra
authors.affiliation: Natural Sciences Department, University of Wisconsin-Superior, Belknap and Catlin, Superior, Wisconsin 54880, USA.
authors.forename: Colton K
authors.initials: CK
authors.lastname: Kennedy
authors.affiliation: Natural Sciences Department, University of Wisconsin-Superior, Belknap and Catlin, Superior, Wisconsin 54880, USA.
authors.forename: Nathan J
authors.initials: NJ
authors.lastname: Jersett
authors.affiliation: Department of Physics, University of Wisconsin-Madison, 1150 University Ave., Madison, Wisconsin 53706, USA.
authors.forename: Idris
authors.initials: I
authors.lastname: Boukahil
authors.affiliation: Department of Physics, University of Wisconsin-Madison, 1150 University Ave., Madison, Wisconsin 53706, USA.
authors.forename: F J
authors.initials: FJ
authors.lastname: Himpsel
authors.affiliation: Natural Sciences Department, University of Wisconsin-Superior, Belknap and Catlin, Superior, Wisconsin 54880, USA.
authors.forename: Peter L
authors.initials: PL
authors.lastname: Cook