Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory

Abstract

Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in rst-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on ve dierent metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT+vdW^surf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we nd a mean average deviation of 0.06 Å and 0.16 eV, respectively. This conrms the DFT+vdW^surf method as an accurate and ecient approach to treat HIOSs. A detailed discussion identies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface

“…The same behavior was recently observed for benzene/Ag(111) 36 ; in this case, the adsorption energy obtained with HSE+MBD was in better agreement with experimental results than that obtained with the PBE+MBD method. In our case, for anthracene/Ag(111), the adsorption energy obtained using the HSE+MBD method (E ads =−1.18 eV) is still within range of the experimental values reported for other oligoacenes, such as benzene, naphthalene and pentacene, adsorbed on the Ag(111) surface (0.68-1.5 eV) 9,[36][37][38] .…”

Comparison of the periodic slab approach with the finite cluster description of metal–organic interfaces at the example of PTCDA on Ag(110)

“…). Following Woodruff, we designate this distance as “XSW (coherent) position,” d A , noting that “vertical (molecular) adsorption height,” “surface molecule distance,” “bonding distance” and “perpendicular height” are used synonymously in the literature. d A is calculated as where represents the distance between atom A and the plane of the lowest Ag‐layer in the cluster, n is the number of Ag‐layers in the cluster and is the distance between vertical Ag layers as obtained from the periodic slab‐supercell calculations (see Fig.…”

“…Several interesting studies of metal‐organic interfaces are found in the literature, where the interactions of a variety of organic π ‐systems, such as pentacene, perylene derivatives or phthalocyanines, have been studied on the low index planes of noble metals, namely Ag, Cu and Au . In this paper, we will restrict the discussion to the adsorption of Perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTCDA) on the Ag(110) surface which is a prototype system as its adsorption characteristics have been studied extensively . Combined LEED‐ARPES (Low Energy Electron Diffraction; Angle‐Resolved Photoelectron Spectroscopy), and NIXSW (Normal Incidence X‐Ray Standing Waves) studies of the PTCDA/Ag(110) system provide detailed information about the orientation of the molecule on the substrate and the adsorption heights of respective atoms.…”

Assessment of van der Waals inclusive density functional theory methods for layered electroactive materials

“…8 and 9). Typically, molecules on metal surfaces, [10][11][12][13][14][15][16][17][18] three-and twodimensional solids, [19][20][21][22] and molecular complexes 23,24 a) Electronic mail: alozano@bcamath.org have become the workhorse paradigm for examining the impact of vdW forces on the binding of weakly interacting systems. A general outcome from these investigations is that the inclusion of vdW forces to GGA functionals often results in improved binding energies and adsorption distances that are in better agreement with available experimental data.…”