Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO{sub 2}(110)

Journal Article · Sat Apr 21 04:00:00 EDT 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3699072· OSTI ID:22047199

Shun, Yu; Ahmadi, Sareh; Adibi, Pooya Tabib Zadeh; Chow, Winnie; Goethelid, Mats ^[1]; Sun, Chenghua ^[2]; Pietzsch, Annette ^[3]

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1. Materials Physics, ICT, Royal Institute of Technology, Electrum 229, SE-16440 Stockholm (Sweden)
2. University of Queensland, ARC Centre of Excellence for Functional Nanomaterials and Centre for Computational Molecular Science, Australia Institute for Bioengineering and Nanotechnology, University of Queensland, Qld 4072 (Australia)
3. Max-lab, Lund University, Box 118, SE- 22100 Lund (Sweden)

The d-orbital contribution from the transition metal centers of phthalocyanine brings difficulties to understand the role of the organic ligands and their molecular frontier orbitals when it adsorbs on oxide surfaces. Here we use zinc phthalocyanine (ZnPc)/TiO{sub 2}(110) as a model system where the zinc d-orbitals are located deep below the organic orbitals leaving room for a detailed study of the interaction between the organic ligand and the substrate. A charge depletion from the highest occupied molecular orbital is observed, and a consequent shift of N1s and C1s to higher binding energy in photoelectron spectroscopy (PES). A detailed comparison of peak shifts in PES and near-edge X-ray absorption fine structure spectroscopy illustrates a slightly uneven charge distribution within the molecular plane and an inhomogeneous charge transfer screening between the center and periphery of the organic ligand: faster in the periphery and slower at the center, which is different from other metal phthalocyanine, e.g., FePc/TiO{sub 2}. Our results indicate that the metal center can substantially influence the electronic properties of the organic ligand at the interface by introducing an additional charge transfer channel to the inner molecular part.

• OSTI ID: 22047199
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 136; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION
ABSORPTION SPECTROSCOPY
BINDING ENERGY
LIGANDS
MOLECULAR ORBITAL METHOD
PHOTOELECTRON SPECTROSCOPY
PHTHALOCYANINES
TITANIUM OXIDES
TRANSITION ELEMENTS
X-RAY SPECTROSCOPY
ZINC