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

Autor(en)

Yu Li Huang, Elisabeth Wruss, David A. Egger, Satoshi Kera, Nobuo Ueno, Wissam A. Saidi, Tomas Bucko, Andrew T. S. Wee, Egbert Zojer

Abstrakt

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.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

National University of Singapore (NUS), Chiba University, Technische Universität Graz, University of Pittsburgh, Univerzita Komenského v Bratislave, Slovenian Academy of Sciences and Arts

Journal

Molecules

Band

19

Seiten

2969-2992

Anzahl der Seiten

24

ISSN

1420-3049

DOI

https://doi.org/10.3390/molecules19032969

Publikationsdatum

03-2014

Peer-reviewed

Ja

ÖFOS 2012

103025 Quantenmechanik, 103036 Theoretische Physik, 103015 Kondensierte Materie, 103009 Festkörperphysik

Schlagwörter

ASJC Scopus Sachgebiete

Drug Discovery, Analytical Chemistry, Chemistry (miscellaneous), Molecular Medicine, Physical and Theoretical Chemistry, Pharmaceutical Science, Organic Chemistry

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/aede0c08-17de-480c-ab0c-fe488bcfdf55