This seminar addresses the topic of the physical and chemical characterization of complex surfaces and 
interfaces by means of DFT-based simulations, showing how the interplay between theory and experiment 
can shed light on their properties. In the first part of the seminar, recent progresses on the modelling of two-
dimensional dichalcogenides and oxide thin films will be shown. In the second part, the main findings on the 
functionalization of metal- and metal oxide surfaces with N-heterocyclic molecules will be illustrated.

Mixed-dimensional van der Waals heterostructures formed by molecular assemblies and 2D materials 
provide a novel platform for fundamental nanoscience and future nanoelectronics applications. A 
prototypical hybrid heterostructure between pentacene molecules and 2D MoS2 nanocrystals was prepared 
by deposition on Au(111) and characterized both experimentally and computationally. The defective nature 
of the MoS2/Au interface,[1] and the simulation of pentacene adsorption[2] reveal intriguing structural, 
physical and chemical properties.

A comparative DFT study of single (K, Au, and Pt) atoms adsorption over a wide range of metal-supported 
oxide ultrathin films (MgO on Ag and Mo, ZnO on Cu, Ag, and Au, SiO on Pt and Ru, TiO on Ag and Pt, ZrO on 
Pt and ZrPt) will be next presented. The strength of the adsorption is shown to depend on a complex interplay 
between charge transfer phenomena, morphology, and chemical nature of the oxide film.[3]

Moving from single atoms to metal particles at the nanoscale, the stability and activity of sandwich-like 
architectures where a Pd nanoparticle is complexed by 2D TiO2 nanosheets are discussed.[4]

N-Heterocyclic Carbenes (NHCs) and olefins (NHOs) are prone to form strong chemical bonds on metal 
surfaces, thanks to their pronounced electron-donor character, which enables their use in surface 
functionalization for various applications, from gas sensing to optoelectronics and (photo)catalysis. We went 
beyond the paradigmatic case of Au(111), widely studied in the literature, to investigate NHCs and NHOs 
adsorption, diffusion, and assembly on copper and copper oxide surfaces.[5-7]

[1] Tumino et al., Nature of Point Defects in Single-Layer MoS2 Supported on Au(111), J. Phys. Chem. C 2020, 124, 12424 
[2] Tumino et al., Interface-Driven Assembly of Pentacene/MoS2 Lateral Heterostructures, J. Phys. Chem. C 2022, 126, 1132 
[3] Tosoni et al., Bonding properties of isolated metal atoms on two-dimensional oxides, J. Phys. Chem. C 2020, 124, 20960 
[4] Tosoni et al., Structures and properties of Pd nanoparticles intercalated in layered TiO2: A computational study, Cat. Today 2021, 
392, 96 
[5] Navarro et al., Growth of N‐heterocyclic carbene assemblies on Cu (100) and Cu (111): from single molecules to magic‐number 
islands, Angew. Chem.-Int. Edit. 2022, 30, e202202127 
[6] Navarro et al., Covalent adsorption of N-heterocyclic carbenes on a copper oxide surface, J. Am. Chem. Soc. 2022, 144, 16267  
[7] Landwehr et al., N-Heterocyclic Olefins on Cu(111)- Adsorption, Orientation and Electronic Influence, 2023, submitted