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

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:
; ;  [1] ;  [2] ; ; ;  [3]
  1. Department of Physics, University of Wisconsin-Madison, 1150 University Ave., Madison, Wisconsin 53706 (United States)
  2. Department of Energy Conversion and Storage, Technical University of Denmark, 4000 Roskilde (Denmark)
  3. Natural Sciences Department, University of Wisconsin-Superior, Belknap and Catlin, Superior, Wisconsin 54880 (United States)
Publication Date:
OSTI Identifier:
22253421
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 11; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
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