Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets

Journal Article · Fri Mar 21 00:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4868552· OSTI ID:22253421

Johnson, Phillip S.; Boukahil, Idris; García-Lastra, J. M. ^[1]; Kennedy, Colton K.; Jersett, Nathan J.; Cook, Peter L. ^[2]

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1. Department of Energy Conversion and Storage, Technical University of Denmark, 4000 Roskilde (Denmark)
2. Natural Sciences Department, University of Wisconsin-Superior, Belknap and Catlin, Superior, Wisconsin 54880 (United States)

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.

• OSTI ID: 22253421
• Journal Information: Journal of Chemical Physics, Vol. 140, Issue 11; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
CRYSTAL FIELD
DENSITY FUNCTIONAL METHOD
MULTIPLETS
PHTHALOCYANINES
POLARIZATION
PORPHYRINS
SOLAR CELLS
TRANSITION ELEMENTS
X-RAY SPECTROSCOPY