Direct Imaging of Molecular Orbitals of Metal Phthalocyanines on Metal Surfaces with an O2-Functionalized Tip of a Scanning Tunneling Microscope
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High-resolution scanning tunneling microscope images of iron phthalocyanine and zinc phthalocyanine molecules on Au(111) have been obtained using a functionalized tip of a scanning tunneling microscope (STM), and show rich intramolecular features that are not observed using clean tips. Ab initio density functional theory calculations and extended Hückel theory calculations revealed that the imaging of detailed electronic states is due specifically to the decoration of the STM tip with O2. The detailed structures are differentiated only when interacting with the highly directional orbitals of the oxygen molecules adsorbed on a truncated, [111]-oriented tungsten tip. Our results indicate a method for increasing the resolution in generic scans and thus, have potential applications in fundamental research based on high-resolution electronic states of molecules on metals, concerning, for example, chemical reactions, and catalysis mechanisms.
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Direct Imaging of Molecular Orbitals of Metal Phthalocyanines on Metal Surfaces with an O2-Functionalized Tip of a Scanning Tunneling Microscope
)
Abstract
High-resolution scanning tunneling microscope images of iron phthalocyanine and zinc phthalocyanine molecules on Au(111) have been obtained using a functionalized tip of a scanning tunneling microscope (STM), and show rich intramolecular features that are not observed using clean tips. Ab initio density functional theory calculations and extended Hückel theory calculations revealed that the imaging of detailed electronic states is due specifically to the decoration of the STM tip with O2. The detailed structures are differentiated only when interacting with the highly directional orbitals of the oxygen molecules adsorbed on a truncated, [111]-oriented tungsten tip. Our results indicate a method for increasing the resolution in generic scans and thus, have potential applications in fundamental research based on high-resolution electronic states of molecules on metals, concerning, for example, chemical reactions, and catalysis mechanisms.
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Acknowledgements
This project is supported by the Natural Science Foundation of China (NSFC), the Chinese National "973" project of the Ministry of Science and Technology (MOST), the Chinese Academy of Sciences and the Shanghai Supercomputer Center. H. T. acknowledges the "Centre de Calcul en Midi-Pyrenees"(CALMIP) for computational resources. H. T. also thanks Sébastien Gauthier for useful discussions.
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