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Molecules 2014, 19(3), 2969-2992; doi:10.3390/molecules19032969

Understanding the Adsorption of CuPc and ZnPc on Noble Metal Surfaces by Combining Quantum-Mechanical Modelling and Photoelectron Spectroscopy

1
Department of Physics, National University of Singapore, 2 Science Drive 3, 117542, Singapore
2
Graduate School of Advanced Integration Science, Chiba University, 1- 33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
3
Institute of Solid State Physics, Graz University of Technology, Petersgasse 16, 8010 Graz, Austria
4
Department of Chemical and Petroleum Engineering, University of Pittsburgh, 1249 Benedum Hall, Pittsburgh, PA 15261, USA
5
Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynska Dolina, SK-84215 Bratislava, Slovakia
6
Slovak Academy of Sciences, Institute of Inorganic Chemistry, Dubravska cesta 9, SK-84236 Bratislava, Slovakia
7
Faculty of Physics, University of Vienna, Sensengasse 8/12, 1090 Vienna, Austria
These authors contributed equally to this work.
Present address: Department of Materials and Interfaces, Weizmann Institute of Science, Rehovoth 76100, Israel.
*
Authors to whom correspondence should be addressed.
Received: 16 January 2014 / Revised: 24 February 2014 / Accepted: 26 February 2014 / Published: 7 March 2014
(This article belongs to the Special Issue Photoelectron Spectroscopy)
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Abstract

Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.
Keywords: phthalocyanine; metal/organic interface; van der Waals interaction; quantum-mechanical simulation; band-structure; hybrid functional; ultraviolet photoelectron spectroscopy phthalocyanine; metal/organic interface; van der Waals interaction; quantum-mechanical simulation; band-structure; hybrid functional; ultraviolet photoelectron spectroscopy
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MDPI and ACS Style

Huang, Y.L.; Wruss, E.; Egger, D.A.; Kera, S.; Ueno, N.; Saidi, W.A.; Bucko, T.; Wee, A.T.; Zojer, E. Understanding the Adsorption of CuPc and ZnPc on Noble Metal Surfaces by Combining Quantum-Mechanical Modelling and Photoelectron Spectroscopy. Molecules 2014, 19, 2969-2992.

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