First-principles and semi-empirical van der Waals study of thymine on Cu(110) surface

Abstract

In this study we investigated by means of density functional theory calculations the adsorption geometry and bonding mechanism of a single thymine (C$_5$H$_6$N$_2$O$_2$) molecule on Cu(110) surface. In the most stable energetic configuration, the molecular plane is oriented perpendicular to substrate along the $[1\bar{1}0]$ direction. For this adsorption geometry, the thymine molecule interacts with the surface via a deprotonated nitrogen atom and two oxygen ones such that the bonding mechanism involves a strong hybridization between the highest occupied molecular orbitals (HOMOs) and the d-states of the substrate. In the case of a parallel adsorption geometry, the long-range van der Waals interactions play an important role on both the molecule-surface geometry and adsorption energy. Their specific role was analyzed by means of a semi-empirical and the seamless methods. In particular, for a planar configuration, the inclusion of the dispersion effects dramatically changes the character of the adsorption process from physisorption to chemisorption. Finally, we predict the real-space topography of the molecule-surface interface by simulating scanning tunneling microscopy (STM) images. From these simulations we anticipate that only certain adsorption geometries can be imaged in STM experiments.