A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work we demonstrate the importance of collective van der Waals d
ispersion effects beyond the pairwise approximation for organic--inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Phys. Rev. Lett. 108, 236402 (2012); J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid (PTCDA), and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate--surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.
We study chaotic orbits of conservative low--dimensional maps and present numerical results showing that the probability density functions (pdfs) of the sum of $N$ iterates in the large $N$ limit exhibit very interesting time-evolving statistics. In
some cases where the chaotic layers are thin and the (positive) maximal Lyapunov exponent is small, long--lasting quasi--stationary states (QSS) are found, whose pdfs appear to converge to $q$--Gaussians associated with nonextensive statistical mechanics. More generally, however, as $N$ increases, the pdfs describe a sequence of QSS that pass from a $q$--Gaussian to an exponential shape and ultimately tend to a true Gaussian, as orbits diffuse to larger chaotic domains and the phase space dynamics becomes more uniformly ergodic.
