Density functional theory investigations of molecules on surfaces : from nano-electronics to catalysis

Abstract

In this thesis, a wide breadth of topics related to the field of surface science are addressed using density functional theory (DFT). Specifically, five studies with relevance to molecular electronics and heterogeneous catalysis are presented, with a particular focus on interadsorbate interactions, reactivity and characterisation of molecules on transition metal surfaces. The first part of this work focuses on giving strong theoretical underpinning to the atomic-scale observations provided by scanning tunnelling microscopy (STM) experiments conducted by my group colleagues. The theoretical calculations presented here provide support to the experimental evidences but also serve to unravel information that is inaccessible from the experiments. On the one hand, the variety of results obtained in this thesis using standard DFT methods serve to highlight the capabilities of the computationally low-demanding methods for modelling processes occurring on metal surfaces. On the other hand, we notice that these workhorse methods in DFT have inherent limitations for providing an accurate description of some properties, in particular binding energies. This, further improvements in the level of theory are necessary for advancing the computational accuracy of standard DFT methods in materials science. The second part of this thesis is devoted to highlight the high level of accuracy obtained by the new theoretical approaches in the field of materials science. Due to the recent implementation of new algorithms combined with the increasing computer power that is available to the scientific community, these sophisticated methods are becoming more accessible for modelling solid-state systems. Here, the recent implementation of the random-phase approximation (RPA) for solids is employed to perform to benchmark study on the adsorption of benzene on different close-packed transition metal surfaces. The development of new theoretical tools is also essential to improve our predictive capabilities in surface science. A novel approach to correct vibrational intensities by including anharmonicities using density functional perturbation theory (DFPT) is proposed. The new method is tested for the adsorption of different organic molecules on various transition metal surfaces. The results obtained by this implementation demonstrate excellent improvements for predicting accurate spectra of molecules on surfaces.