Planar Clusters Research Articles

The route to MBxNyCz molecular wheels: II. Results using accurate functionals and basis sets

Applying ab initio quantum chemical methods, molecular wheels composed of metal and light atoms were investigated. High quality basis sets 6-31G*, TZPV, and cc-pVTZ as well as exchange and non-local correlation functionals B3LYP, BP86 and B3P86 were used. The ground-state energy and structures of cyclic planar and pyramidal clusters TiBn (for n = 3–10) were computed. In addition, the relative stability and electronic structures of molecular wheels TiBxNyCz (for x, y, z = 0–10) and MBnC10−n (for n = 2 to 5 and M = Sc to Zn) were determined. This paper sustains a follow-up study to the previous one of Boustani and Pandey [Solid State Sci. 14 (2012) 1591], in which the calculations were carried out at the HF-SCF/STO3G/6-31G level of theory to determine the initial stability and properties. The results show that there is a competition between the 2D planar and the 3D pyramidal TiBn clusters (for n = 3–8). Different isomers of TiB10 clusters were also studied and a structural transition of 3D-isomer into 2D-wheel is presented. Substitution boron in TiB10 by carbon or/and nitrogen atoms enhances the stability and leads toward the most stable wheel TiB3C7. Furthermore, the computations show that Sc, Ti and V at the center of the molecular wheels are energetically favored over other transition metal atoms of the first row.

Thermoelectric Properties and Conduction Mechanism of CaCu3Ti4O12 Ceramics at High Temperatures

The Seebeck coefficient and electrical conductivity of CaCu3Ti4O12 (CCTO) ceramics were measured and analyzed in the high temperature range of 300°C to 800°C, and then the electrical conduction mechanism was investigated by using a combination of experimental data fitting and first-principles calculations. The Seebeck coefficient of the CCTO ceramic sintered at 1050°C is negative with largest absolute value of ∼650 μV/K at 300°C, and the electrical conductivity is 2–3 orders greater than the value reported previously by other researchers. With increasing sintering temperature, the Seebeck coefficient decreases while the electrical conductivity increases. The temperature dependence of the electrical conductivity follows the rule of adiabatic hopping conduction of small polarons. The calculated density of states of CCTO indicates that the conduction band is mainly contributed by the antibonding states of Cu 3d electrons, therefore small-polaron hopping between CuO4 square planar clusters was proposed. Possible ways to further improve the thermoelectric properties of CCTO are also discussed.

Stability of equilibrium points in a CR3BP with oblate bodies enclosed by a circular cluster of material points

We have investigated an improved version of the classic restricted three-body problem where both primaries are considered oblate and are enclosed by a homogeneous circular planar cluster of material points centered at the mass center of the system. In this dynamical model we have examined the effect on the number and on the linear stability of the equilibrium locations of the small particle due to both, the primaries’ oblateness and the potential created by the circular cluster. We have drawn the zero-velocity surfaces and we have found that in addition to the usual five Lagrangian equilibrium points of the classic restricted three-body problem, there exist two new collinear points L n1,L n2 due to the potential from the circular cluster of material points. Numerical investigations reveal that with the increase in the mass of the circular cluster of material points, L n2 comes nearer to the more massive primary, while L n1 moves away from it. Owing to oblateness of the bodies, L n1 comes nearer to the more massive primary, while L n2 moves towards the less massive primary. The collinear equilibrium points remain unstable, while the triangular points are stable for 0<μ<μ c and unstable for $\mu_{c} \le \mu \le \frac{1}{2}$ , where μ c is the critical mass ratio influenced by oblateness of the primaries and the potential from the circular cluster of material points. The oblateness and the circular cluster of material points have destabilizing tendency.

Mechanism for C–I Bond Dissociation in Iodoethane, Iodobenzene, and Iodoethene for the C–C Cross Coupling Reactions over Gold Clusters

The mechanisms for the C–I bond dissociation in iodoethane, iodobenzene, and iodoethene over the subnanometer sized gold clusters were studied using density functional theory. Au3, Au4, Au14, and Au20 clusters and their cations were used as the models to investigate the effects of the size, geometry, and electronic charge on the catalysis of the reaction. Our calculations predict that both iodoethane and iodobenzene interact with the gold through the lone pair on iodine with the small planar clusters activating the reaction more effectively through the formation of strong adducts and low barrier heights. Clusters with large HOMO–LUMO gaps act as poor catalysts owing to the quantum size effects. Even though the cationic clusters bind to the reactants more strongly due to their enhanced Lewis acidity, they also require higher activation energy. However, the catalysis by cations and 3D clusters has a smaller endergonicity which would be desirable in the subsequent steps in cross/homo coupling reactions. In t...

On the way to the highest coordination number in the planar metal-centred aromatic Ta©B10− cluster: Evolution of the structures of TaBn− (n = 3–8)

The structures and chemical bonding of TaB(n)(-) (n = 3-8) clusters are investigated systematically to elucidate the formation of the planar metal-centred aromatic borometallic cluster, Ta©B10(-) (the © sign is used to designate the central position of the doped atom in monocyclic structures in M©B(n)-type planar clusters), which was found previously to have the highest coordination number for a metal atom in a planar geometry. Photoelectron spectroscopy is combined with ab initio calculations to determine the global minima of the TaB(n)(-) clusters. We find that from TaB3(-) to TaB5(-) the boron atoms nucleate around the central Ta atom to form fan-like structures. A structural transition occurs at TaB6(-), which is found to have a hexagonal structure, but with a boron atom in the centre and the Ta atom on the periphery. TaB7(-) is shown to have a three-dimensional boat-like structure, which can be viewed as a Ta atom coordinated to an elongated B7 cluster from above. The global minimum of the TaB8(-) cluster is found to be pyramidal with the Ta atom interacting with a B8 monocyclic ring. Starting from this structure, additional boron atoms simply enlarge the boron ring to form the slightly pyramidal TaB9(-) cluster and eventually the perfectly planar Ta-centred B10-ring aromatic cluster, Ta©B10(-). It is shown that boron atoms do not nucleate smoothly around a Ta atom on the way to the decacoordinated Ta©B10 (-) molecular wheel, but rather the competition between B-B interactions and Ta-B interactions determines the most stable structures of the smaller TaB(n)(-) (n = 3-8) clusters.

The seismogenic zone in the Central Costa Rican Pacific margin: high-quality hypocentres from an amphibious network

Transition from subduction of normal to thickened oceanic crust occurs in the central portion of the Costa Rican margin, where large interplate earthquakes (M * 7) and abundant interseismic seismicity have been associated with subduction of bathymetric highs. We relocated *1,300 earthquakes recorded for 6 months by a combined on- and offshore seismological network using probabilistic earthquake relocation in a 3D P-wave velocity model. Most of the seismicity originated at the seismogenic zone of the plate boundary, appearing as an 18° dipping, planar cluster from 15 to 25–30 km depth, beneath the continental shelf. Several reverse focal mechanisms were resolved within the cluster. The upper limit of this interseismic interplate seismicity seems to be controlled primarily by the overlying-plate thickness and coherency, which in turn is governed by the erosional processes and fluid release and escape at temperatures lower than *100 to 120° C along the plate boundary. The downdip limit of the stick–slip behaviour collocates with relative low temperatures of *150 to 200° C, suggesting that it is controlled by serpentinization of the mantle wedge. The distribution of the interseismic interplate seismicity is locally modified by the presence of subducted seamounts at different depths. Unlike in northern Costa Rica, rupture of large earthquakes in the last two decades seems to coincide with the area defined by the interseismic interplate seismicity.

Operational limit of a planar DC magnetron cluster source due to target erosion

The binary collision-based two dimensional SDTrimSP-2D model has been used to simulate the erosion process of a Cu target and its influence on the operational limit of a planar DC magnetron nanocluster source. The density of free metal atoms in the aggregation region influences the cluster formation and cluster intensity during the target lifetime. The density of the free metal atoms in the aggregation region can only be predicted by taking into account (i) the angular distribution of the sputtered flux from the primary target source and (ii) relative downwards shift of the primary source of sputtered atoms during the erosion process. It is shown that the flux of the sputtered atoms smoothly decreases with the target erosion.

Boron as intruder in planar gold clusters. How does its presence modify reactivity?

In this paper, our main objective is to analyze the effect of one boron atom on the properties of gold clusters. To this end, a density functional study of gold–boron clusters is carried out. Gold–boron clusters are obtained by substituting one gold atom with one boron atom in planar gold clusters consisting of up to nine atoms. The systems being studied (AuN (with N=2–8)) are investigated using the electron donor–acceptor electronegativities and the electrostatic potential surface (EPS). In order to investigate the influence of the boron atom on the reactivity of gold clusters, the reaction of gold–boron clusters with H+, OH and OH− was analyzed in terms of Gibbs free energies, and compared with the reactivity of pure gold clusters. Generally, gold–boron clusters represent better electron donors than gold clusters, and the presence of the boron atoms enhances the reactivity of the clusters. The active sites of Au clusters are Au while those of AuNB clusters are the B atoms. This is important for future applications of these systems.

Theoretical and Experimental Insights into the Origin of the Catalytic Activity of Subnanometric Gold Clusters: Attempts to Predict Reactivity with Clusters and Nanoparticles of Gold

Particle size is one of the key parameters determining the unexpected catalytic activity of gold, with reactivity improving as the particle gets smaller. While this is valid in the 1-5 nm range, chemists are now investigating the influence of particle size in the subnanometer regime. This is due to recent advances in both characterization techniques and synthetic routes capable of stabilizing these size-controlled gold clusters. Researchers reported in early studies that small clusters or aggregates of a few atoms can be extremely active in some reactions, while 1-2 nm nanoparticles are catalytically more efficient for other reactions. Furthermore, the possibility that small gold clusters generated in situ from gold salts or complexes could be the real active species in homogeneous gold-catalyzed organic reactions should be considered. In this Account, we address two questions. First, what is the origin of the enhanced reactivity of gold clusters on the subnanometer scale? And second, how can we predict the reactions where small clusters should work better than larger nanoparticles? Both geometric factors and electronic or quantum size effects become important in the subnanometer regime. Geometric reasons play a key role in hydrogenation reactions, where only accessible low coordinated neutral Au atoms are needed to dissociate H2. The quantum size effects of gold clusters are important as well, as clusters formed by only a few atoms have discrete molecule-like electronic states and their chemical reactivity is related to interactions between the cluster's frontier molecular orbitals and those of the reactant molecules. From first principles calculations, we predict an enhanced reactivity of small planar clusters for reactions involving activation of CC multiple bonds in alkenes and alkynes through Lewis acid-base interactions, and a better catalytic performance of 3D gold nanoparticles in redox reactions involving bond dissociation by oxidative addition and new bond formation by reductive elimination. In oxidation reactions with molecular O2, initial dissociation of O2 into basic oxygen atoms would be more effectively catalyzed by gold nanoparticles of ∼1 nm diameter. In contrast, small planar clusters should be more active for reactions following a radical pathway involving peroxo or hydroperoxo intermediates. We have experimentally confirmed these predictions for a series of Lewis acid and oxidation reactions catalyzed by gold clusters and nanoparticles either in solution or supported on solid carriers.

A 10-connected coordination network based on the planar tetranuclear cobalt cluster building blocks: synthesis, structure, and magnetism

A coordination polymer [Co 4 (μ 2 -H 2 O) 2 (1,4-ndc) 4 (dpp) 2 ] n ( 1 ) with the 1,4-naphthalenedicarboxylic acid (1,4-H 2 ndc) and 1,3-di(4-pyridyl)propane (dpp) mixed ligands has been synthesized and structurally and magnetically characterized. Compound 1 features a 3D framework based on the tetranuclear [Co 4 (μ 2 -H 2 O) 2 (COO) 6 ] secondary building units (SBUs) where the four cobalt ions are coplanar. The 3D coordination network of 1 is a rare 10-connected network of (3 6 ·4 34 ·5 3 ·6 2 ) topology based on the tetranuclear cobalt cluster nodes. Magnetic measurements on compound 1 indicate that there is a net antiferromagnetic coupling among the Co(II) ions. A ten-connected coordination network [Co 4 (μ 2 -H 2 O) 2 (1,4-ndc) 4 (dpp) 2 ] n has been synthesized and structurally and magnetically characterized. • Co(II) coordination polymer • Planar tetranuclear cobalt cluster • 10-connected network of (3 6 ·4 34 ·5 3 ·6 2 ) topology • Magnetism

Size-selective self-assembly of magnetic Mn nanoclusters on Si(111)

We show by first-principles calculations two types of magnetic magic Mn clusters on the Si(111)-(7 × 7) surface. The first is a small triangular Mn7 cluster stabilized by the solid-centered Mn-Si3 bonds on the top layer, and the second is a large hexagonal Mn13 cluster favored by the confining potential wells of the faulted half unit cells on the Si(111) surface. These two structural models are distinct from that of the planar group-III clusters on Si(111) and produce simulated scanning tunneling microscopy images in reasonable agreement with recent experimental observations. These results offer key insights for understanding the complex energetic landscape on the Si(111)-(7 × 7) surface, which is critical to precisely controlled growth of Mn nanocluster arrays with specific size, magnetic moment, and good uniformity.

Solving a similarity transformation between two reference frames using hybrid geometric control features

A similarity-based transformation has been routinely applied in various fields of geosciences with the main purpose of integrating spatial information across different reference frames. Current approaches for solving the indirect problem (i.e., parameter estimation) of a similarity transformation are primarily point-based approaches, meaning that point correspondence between the original and transformed frames (namely control points) is required. Although it can also be seen that transformation solutions have been reached by means of other features, they have been mainly presented on the basis of a single feature, or, at most a few features, thus exploiting only limited geometric information inside the data. In this study, an integrated technique for solving the transformation parameters is developed using not only point features but also linear and planar features and clusters of point clouds with implicit or explicit features. In addition, this approach provides a closed-form solution for a transformation and, consequently, does not require an appropriate starting value to initiate the transformation parameter estimation. An illustration is given in numerical tests of how the proposed approach is able to process various kinds of control features and gives a reliable result with high computational efficiency. Accordingly, a flexible and automatic determination of a 3-D similarity transformation can be achieved by implementing this technique. Potential applications include geodetic datum transformations, reference analysis of LiDAR point clouds, extraction of features from LiDAR surveying or satellite image data, and registration of digital vector maps in GIS.

Interaction of ethylene glycol–water clusters with aromatic surfaces

The gas phase geometries of ethylene glycol–water (EGmWn) (where m = 0–4, n = 0–4; m + n ≤ 4) clusters adsorbed on a fragment of carbon nanotube have been investigated using density functional theory based M05-2X and ωB97XD methods employing various basis sets. With a view to assess the effect of curvature on the hydrogen bonding pattern between ethylene glycol and water molecules, calculations on intermolecular complexes comprising a planar aromatic surface and EGmWn clusters have been carried out. Results obtained from the electronic structure calculations and Bader's electron density analysis reveal that C–H⋯π, O–H⋯π and lone pair⋯π interactions are predominant in the stabilization of EGmWn and the corresponding complexes with fragments of a carbon nanotube and graphene. Further, the role of the π-cloud on the stability of EGmWn is illustrated by comparing the interaction energies of clusters in the presence and absence of an aromatic surface.

Transition-Metal-Centered Monocyclic Boron Wheel Clusters (M©Bn): A New Class of Aromatic Borometallic Compounds

Atomic clusters have intermediate properties between that of individual atoms and bulk solids, which provide fertile ground for the discovery of new molecules and novel chemical bonding. In addition, the study of small clusters can help researchers design better nanosystems with specific physical and chemical properties. From recent experimental and computational studies, we know that small boron clusters possess planar structures stabilized by electron delocalization both in the σ and π frameworks. An interesting boron cluster is B(9)(-), which has a D(8h) molecular wheel structure with a single boron atom in the center of a B(8) ring. This ring in the D(8h)-B(9)(-) cluster is connected by eight classical two-center, two-electron bonds. In contrast, the cluster's central boron atom is bonded to the peripheral ring through three delocalized σ and three delocalized π bonds. This bonding structure gives the molecular wheel double aromaticity and high electronic stability. The unprecedented structure and bonding pattern in B(9)(-) and other planar boron clusters have inspired the designs of similar molecular wheel-type structures. But these mimics instead substitute a heteroatom for the central boron. Through recent experiments in cluster beams, chemists have demonstrated that transition metals can be doped into the center of the planar boron clusters. These new metal-centered monocyclic boron rings have variable ring sizes, M©B(n) and M©B(n)(-) with n = 8-10. Using size-selected anion photoelectron spectroscopy and ab initio calculations, researchers have characterized these novel borometallic molecules. Chemists have proposed a design principle based on σ and π double aromaticity for electronically stable borometallic cluster compounds, featuring a highly coordinated transition metal atom centered inside monocyclic boron rings. The central metal atom is coordinatively unsaturated in the direction perpendicular to the molecular plane. Thus, chemists may design appropriate ligands to synthesize the molecular wheels in the bulk. In this Account, we discuss these recent experimental and theoretical advances of this new class of aromatic borometallic compounds, which contain a highly coordinated central transition metal atom inside a monocyclic boron ring. Through these examples, we show that atomic clusters can facilitate the discovery of new structures, new chemical bonding, and possibly new nanostructures with specific, advantageous properties.

B30H8, B39H9 2−, B42H10, B48H10, and B72H12: polycyclic aromatic snub hydroboron clusters analogous to polycyclic aromatic hydrocarbons

Calculations performed at the ab initio level using the recently reported planar concentric π-aromatic B(18)H(6)(2+)(1) [Chen Q et al. (2011) Phys Chem Chem Phys 13:20620] as a building block suggest the possible existence of a new class of B(3n)H(m) polycyclic aromatic hydroboron (PAHB) clusters-B(30)H(8)(2), B(39)H(9)(2-)(3), B(42)H(10)(4/5), B(48)H(10)(6), and B(72)H(12)(7)-which appear to be the inorganic analogs of the corresponding C(n)H(m) polycyclic aromatic hydrocarbon (PAHC) molecules naphthalene C(10)H(8), phenalenyl anion C(13)H(9)(-), phenanthrene/anthracene C(14)H(10), pyrene C(16)H(10), and coronene C(24)H(12), respectively, in a universal atomic ratio of B:C = 3:1. Detailed canonical molecular orbital (CMO), adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses indicate that, as they are hydrogenated fragments of a boron snub sheet [Zope RR, Baruah T (2010) Chem Phys Lett 501:193], these PAHB clusters are aromatic in nature, and exhibit the formation of islands of both σ- and π-aromaticity. The predicted ionization potentials of PAHB neutrals and electron detachment energies of small PAHB monoanions should permit them to be characterized experimentally in the future. The results obtained in this work expand the domain of planar boron-based clusters to a region well beyond B(20), and experimental syntheses of these snub B(3n)H(m) clusters through partial hydrogenation of the corresponding bare B(3n) may open up a new area of boron chemistry parallel to that of PAHCs in carbon chemistry.

B22– and B23–: All-Boron Analogues of Anthracene and Phenanthrene

Clusters of boron atoms exhibit intriguing size-dependent structures and chemical bonding that are different from bulk boron and may lead to new boron-based nanostructures. We report a combined photoelectron spectroscopic and ab initio study of the 22- and 23-atom boron clusters. The joint experimental and theoretical investigation shows that B(22)(-) and B(23)(-) possess quasi-planar and planar structures, respectively. The quasi-planar B(22)(-) consists of fourteen peripheral atoms and eight interior atoms in a slightly buckled triangular lattice. Chemical bonding analyses of the closed-shell B(22)(2-) species reveal seven delocalized π orbitals, which are similar to those in anthracene. B(23)(-) is a perfectly planar and heart-shaped cluster with a pentagonal cavity and a π-bonding pattern similar to that in phenanthrene. Thus, B(22)(-) and B(23)(-), the largest negatively charged boron clusters that have been characterized experimentally to date, can be viewed as all-boron analogues of anthracene and phenanthrene, respectively. The current work shows not only that boron clusters are planar at very large sizes but also that they continue to yield surprises and novel chemical bonding analogous to specific polycyclic aromatic hydrocarbons.

RECONSTRUCTION OF 3D VECTOR MODELS OF BUILDINGS BY COMBINATION OF ALS, TLS AND VLS DATA

Abstract. Airborne Laser Scanning (ALS), Terrestrial Laser Scanning (TLS) and Vehicle based Laser Scanning (VLS) are widely used as data acquisition methods for 3D building modelling. ALS data is often used to generate, among others, roof models. TLS data has proven its effectiveness in the geometric reconstruction of building façades. Although the operating algorithms used in the processing chain of these two kinds of data are quite similar, their combination should be more investigated. This study explores the possibility of combining ALS and TLS data for simultaneously producing 3D building models from bird point of view and pedestrian point of view. The geometric accuracy of roofs and façades models is different due to the acquisition techniques. In order to take these differences into account, the surfaces composing roofs and façades are extracted with the same algorithm of segmentation. Nevertheless the segmentation algorithm must be adapted to the properties of the different point clouds. It is based on the RANSAC algorithm, but has been applied in a sequential way in order to extract all potential planar clusters from airborne and terrestrial datasets. Surfaces are fitted to planar clusters, allowing edge detection and reconstruction of vector polygons. Models resulting from TLS data are obviously more accurate than those generated from ALS data. Therefore, the geometry of the roofs is corrected and adapted according to the geometry of the corresponding façades. Finally, the effects of the differences between raw ALS and TLS data on the results of the modeling process are analyzed. It is shown that such combination could be used to produce reliable 3D building models.

Plasmon Transmutation: Inducing New Modes in Nanoclusters by Adding Dielectric Nanoparticles

Planar clusters of coupled plasmonic nanoparticles support nanoscale electromagnetic "hot spots" and coherent effects, such as Fano resonances, with unique near and far field signatures, currently of prime interest for sensing applications. Here we show that plasmonic cluster properties can be substantially modified by the addition of individual, discrete dielectric nanoparticles at specific locations on the cluster, introducing new plasmon modes, or transmuting existing plasmon modes to new ones, in the resulting metallodielectric nanocomplex. Depositing a single carbon nanoparticle in the junction between a pair of adjacent nanodisks induces a metal-dielectric-metal quadrupolar plasmon mode. In a ten-membered cluster, placement of several carbon nanoparticles in junctions between multiple adjacent nanoparticles introduces a collective magnetic plasmon mode into the Fano dip, giving rise to an additional subradiant mode in the metallodielectric nanocluster response. These examples illustrate that adding dielectric nanoparticles to metallic nanoclusters expands the number and types of plasmon modes supported by these new mixed-media nanoscale assemblies.

Experimental and computational evidence of octa- and nona-coordinated planar iron-doped boron clusters: Fe©B8− and Fe©B9−

We report the observation of two Fe-doped boron clusters with wheel-type structures, containing an octa-coordinate (C8v-Fe©B8−) and a nona-coordinate (D9h-Fe©B9−) Fe atom. The clusters were produced in a laser vaporization supersonic molecular beam and characterized by combined photoelectron spectroscopy and ab initio studies. Chemical bonding analyses revealed that in the ground state both clusters are doubly (σ + π) aromatic and that the iron atom interacts with the peripheral boron ring exclusively through delocalized bonds. These findings provide further support to the design principle for metal-doped boron clusters with highly symmetric molecular wheel-type structures.

Adsorption of cobalt on graphene: Electron correlation effects from a quantum chemical perspective

In this work, we investigate the adsorption of a single cobalt atom (Co) on graphene by means of the complete active space self-consistent field approach, additionally corrected by the second-order perturbation theory. The local structure of graphene is modeled by a planar hydrocarbon cluster (C$_{24}$H$_{12}$). Systematic treatment of the electron correlations and the possibility to study excited states allow us to reproduce the potential energy curves for different electronic configurations of Co. We find that upon approaching the surface, the ground-state configuration of Co undergoes several transitions, giving rise to two stable states. The first corresponds to the physisorption of the adatom in the high-spin $3d^74s^2$ ($S=3/2$) configuration, while the second results from the chemical bonding formed by strong orbital hybridization, leading to the low-spin $3d^9$ ($S=1/2$) state. Due to the instability of the $3d^9$ configuration, the adsorption energy of Co is small in both cases and does not exceed 0.35 eV. We analyze the obtained results in terms of a simple model Hamiltonian that involves Coulomb repulsion ($U$) and exchange coupling ($J$) parameters for the 3$d$ shell of Co, which we estimate from first-principles calculations. We show that while the exchange interaction remains constant upon adsorption ($\simeq1.1$ eV), the Coulomb repulsion significantly reduces for decreasing distances (from 5.3 to 2.6$\pm$0.2 eV). The screening of $U$ favors higher occupations of the 3$d$ shell and thus is largely responsible for the interconfigurational transitions of Co. Finally, we discuss the limitations of the approaches that are based on density functional theory with respect to transition metal atoms on graphene, and we conclude that a proper account of the electron correlations is crucial for the description of adsorption in such systems.