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Graphene on SiO 2 enables fabrication of Si-technology-compatible devices, but a transfer of these devices from other substrates and direct growth have severe limitations due to a relatively small grain size or device-contamination. Here, we show an efficient, transfer-free way to integrate centimeter-scale, single-crystal graphene, of a quality suitable for electronic devices, on an insulating SiO 2 film. Starting with single-crystal graphene grown epitaxially on Ru(0001), a SiO 2 film is grown under the graphene by stepwise intercalation of silicon and oxygen. Thin (∼1 nm) crystalline or thicker (∼2 nm) amorphous SiO 2 has been produced. The insulating nature of the thick amorphous SiO 2 is verified by transport measurements. The device-quality of the corresponding graphene was confirmed by the observation of Shubnikov-de Haas oscillations, an integer quantum Hall effect, and a weak antilocalization effect within in situ fabricated Hall bar devices. This work provides a reliable platform for applications of large-scale, high-quality graphene in electronics.

Controlling electronic transport through a single-molecule junction is crucial for molecular electronics or spintronics. In magnetic molecular devices, the spin degree-of-freedom can be used to this end since the magnetic properties of the magnetic ion centers fundamentally impact the transport through the molecules. Here we demonstrate that the electron pathway in a single-molecule device can be selected between two molecular orbitals by varying a magnetic field, giving rise to a tunable anisotropic magnetoresistance up to 93%. The unique tunability of the electron pathways is due to the magnetic reorientation of the transition metal center, resulting in a re-hybridization of molecular orbitals. We obtain the tunneling electron pathways by Kondo effect, which manifests either as a peak or a dip line shape. The energy changes of these spin-reorientations are remarkably low and less than one millielectronvolt. The large tunable anisotropic magnetoresistance could be used to control electronic transport in molecular spintronics.

The silver-nucleoside complex [Ag(i)-( N 3-cytidine) 2 ], 1 , self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-helix with a continuous silver core. Electrical measurements on 1 show that despite having Ag···Ag distances within <5% of the metallic radii, the material is electrically insulating. This is due to the electronic structure which features a filled valence band, an empty conduction band dominated by the ligand, and a band gap of 2.5 eV. Hence, as-prepared, such Ag(i)-DNA systems should not be considered molecular nanowires but, at best, proto-wires. The structural features seen in 1 are essentially retained in the corresponding organogel which exhibits thixotropic self-healing that can be attributed to the reversible nature of the intermolecular interactions. Photo-reduced samples of the gel exhibit luminescence confirming that these poly-cytidine sequences appropriately pre-configure silver ions for the formation of quantum-confined metal clusters in line with contemporary views on DNA-templated clusters. Microscopy data reveals the resulting metal cluster/particles are approximately spherical and crystalline with lattice spacing (111) similar to bulk Ag.

Pristine graphene is known to be nonmagnetic due to its π-conjugated electron system. However, we find that localized magnetic moments can be generated by chemically attaching boron atoms to the graphene sheets. Such spin-polarized states are evidenced by the spin-split of the density of states (DOS) peaks near the Fermi level in scanning tunneling spectroscopy (STS). In the vicinity of several coadsorbed boron atoms, the Coulomb repulsion between multiple spins leads to antiferromagnetic coupling for the induced spin states in the graphene lattice, manifesting itself as an increment of spin-down state at specific regions. Experimental observations and interpretations are rationalized by extensive density functional theory (DFT) simulations.

Scanning probe instruments in conjunction with a very low temperature environment have revolutionized the ability of building, functionalizing, and analysing two dimensional interfaces in the last twenty years. In addition, the availability of fast, reliable, and increasingly sophisticated methods to simulate the structure and dynamics of these interfaces allow us to capture even very small effects at the atomic and molecular level. In this review we shall focus largely on metal surfaces and organic molecular compounds and show that building systems from the bottom up and controlling the physical properties of such systems is no longer within the realm of the desirable, but has become day to day reality in our best laboratories.

The quantum efficiency or the rate of conversion of incident photon to free electron in photosynthesis is known to be extremely high. It has long been thought that the origin of this efficiency are molecular vibrations leading to a very fast separation of electrons and holes within the involved molecules. However, molecular vibrations are commonly in the range above 100 meV, which is too high for excitations in an ambient environment. Here, we analyze experimental spectra of single organic molecules on metal surfaces at ∼4 K, which often exhibit a pronounced dip. We show that measurements on iron(II) [tetra-(pentafluorophenyl)]porphyrin resolve this single dip at 4 K into a series of step-shaped inelastic excitations at 0.4 K. Via extensive spectral maps under applied magnetic fields and corresponding theoretical analysis we find that the dip is due to ultralow-energy vibrations of the molecular frame, typically in the range below 20 meV. The result indicates that ultralow energy vibrations in organic molecules are much more common than currently thought and may be all-pervasive for molecules above a certain size.

In biomineralization, inorganic materials are formed with remarkable control of the shape and morphology. Chirality, as present in the biomolecular world, is therefore also common for biominerals. Biomacromolecules, like proteins and polysaccharides, are in direct contact with the mineral phase and act as modifiers during nucleation and crystal growth. Owing to their homochirality--they exist only as one of two possible mirror-symmetric isomers--their handedness is often transferred into the macroscopic shape of the biomineral crystals, but the way in which handedness is transmitted into achiral materials is not yet understood at the atomic level. By using the submolecular resolution capability of scanning tunnelling microscopy, supported by photoelectron diffraction and density functional theory, we show how the chiral 'buckybowl' hemibuckminsterfullerene arranges copper surface atoms in its vicinity into a chiral morphology. We anticipate that such new insight will find its way into materials synthesis techniques.

The site-dependent g factor of a single magnetic molecule, with intramolecular resolution, is demonstrated for the first time by low-temperature, high-magnetic-field scanning tunneling microscopy of dehydrogenated Mn-phthalocyanine molecules on Au(111). This is achieved by exploring the magnetic-field dependence of the extended Kondo effect at different atomic sites of the molecule. Importantly, an inhomogeneous distribution of the g factor inside a single molecule is revealed. Our results open up a new route to access local spin properties within a single molecule.

We studied the mechanism of half-metallicity (HM) formation in transition-metal-doped conjugated carbon based structures by first-principles electronic structure simulations. It is found that the HM is a rather complex phenomenon, determined by the ligand field splitting of d-orbitals of the transition metal atoms, the exchange splitting and the number of valence electrons. Since most of the conjugated carbon based structures possess ligands with intermediate strength, the ordering of the d-orbital splitting is similar in all structures, and the HM properties evolve according to the number of valence electrons. Based on this insight we predict that Cr-, Fe- and Co-doped graphyne will show HM, while Mn- and Ni-doped graphyne will not. By tuning the number of valence electrons, we are thus able to control the emergence of HM and control the energy gaps evolving in the majority or minority spin channels.

Silicene, a two-dimensional (2D) honeycomb structure similar to graphene, has been successfully fabricated on an Ir(111) substrate. It is characterized as a (√7×√7) superstructure with respect to the substrate lattice, as revealed by low energy electron diffraction and scanning tunneling microscopy. Such a superstructure coincides with the (√3×√3) superlattice of silicene. First-principles calculations confirm that this is a (√3×√3)silicene/(√7×√7)Ir(111) configuration and that it has a buckled conformation. Importantly, the calculated electron localization function shows that the silicon adlayer on the Ir(111) substrate has 2D continuity. This work provides a method to fabricate high-quality silicene and an explanation for the formation of the buckled silicene sheet.

The reversible control of a single spin of an atom or a molecule is of great interest in Kondo physics and a potential application in spin based electronics. Here we demonstrate that the Kondo resonance of manganese phthalocyanine molecules on a Au(111) substrate have been reversibly switched off and on via a robust route through attachment and detachment of single hydrogen atom to the magnetic core of the molecule. As further revealed by density functional theory calculations, even though the total number of electrons of the Mn ion remains almost the same in the process, gaining one single hydrogen atom leads to redistribution of charges within 3d orbitals with a reduction of the molecular spin state from S = 3/2 to S = 1 that directly contributes to the Kondo resonance disappearance. This process is reversed by a local voltage pulse or thermal annealing to desorb the hydrogen atom.

In this work, we have computationally modeled the adsorption of 1,3-diiodobenzene (meta-diiodobenzene or m-DIB) on Cu(1 1 0) by means of density functional theory including van der Waals interaction using Grimme's method. We have compared the adsorption energies and structures of 23 possible configurations of the physisorbed molecule. Furthermore, we have simulated STM images for the four most stable configurations using the Tersoff-Hamann approach at different bias voltages. We find that all the adsorption orientations have comparable energy, and we discuss the relative probabilities of experimental observation. We find that the adsorption induces small distortions in the molecular structure of the adsorbate and in some cases an adsorption-induced symmetry breakdown occurs. We also find evidence that the most stable arrangement is actually a bistable system with interesting symmetry properties., (Copyright © 2012 Wiley Periodicals, Inc.)

A key requirement for the future applicability of molecular electronics devices is a resilience of their properties to mechanical deformation. At present, however, there is no fundamental understanding of the origins of mechanical properties of molecular films. Here we use quinacridone, which possesses flexible carbon side chains, as a model molecular system to address this issue. Eight molecular configurations with different molecular coverage are identified by scanning tunneling microscopy. Theoretical calculations reveal quantitatively the roles of different molecule-molecule and molecule-substrate interactions and predict the observed sequence of configurations. Remarkably, we find that a single Young's modulus applies for all configurations, the magnitude of which is controlled by side chain length, suggesting a versatile avenue for tuning not only the physical and chemical properties of molecular films but also their elastic properties., (© 2012 American Chemical Society)

Chloropentane forms asymmetric ('A') and symmetric ('S') pairs on Si(100)-2×1, differing in the direction of curvature of one pentane tail. Surprisingly this renders the rate of thermal reaction of 'A' fifteen times greater than 'S' in chlorinating room-temperature silicon. Correspondingly, for electron-induced reaction the energy threshold for A is 1 eV less than for S.

Adsorbates on metals, but not previously on semiconductors, have been observed to display long-range repulsive interactions. On metals, due to efficient dissipation, the repulsions are weak, typically on the order of 5 meV at 10 Å. On the 7×7 reconstruction of the Si(111) surface, charge transport through the surface has been demonstrated by others using charge injection by STM tips. Here we show that for both physisorbed brominated molecules, and for chemisorbed Br-atoms, induced charge-transfer in the Si(111)-7×7 surface can lead to a strong repulsive interaction between adsorbates, calculated as 200 meV at 13.4 Å. This large repulsive interaction must be channeled through the surface since it causes widely spaced "one-per-corner-hole" patterns of physisorption (three cases--directly observed here) and subsequent chemisorption (four cases observed). The patterns were observed by ultrahigh vacuum scanning tunneling microscopy for four different brominated hydrocarbon adsorbates; 1,2-dibromoethane, 1-bromopropane, 1-bromopentane, and bromobenzene, deposited individually on the surface. In every case, adsorbates were overwhelmingly more likely to be found singly than multiply adjacent to a corner-hole, constituting a distinctive pattern having a probability p = 7 × 10(-5) compared to a random distribution.

If a molecule controls the length of some other moiety, it can be termed a "molecular caliper". Here we image individual molecular calipers of this type by scanning tunneling microscopy. These consist of linear polymers of p-diiodobenzene, (pDIB)n, of varying length, 0.7-2.9 nm, physisorbed on Cu(110) at 4.6 K. Through electron-induced reaction these chemically imprint their terminal I-atoms on the copper, 0.7 nm further apart than their initial separations. The physisorbed monomer or polymer, therefore, constitutes a molecular-caliper with variable terminal I..I separation. The localized nature of the I-atom reaction at the copper surface relative to the parent molecule, constitutes a novel finding reported here. It ensures that the separation of the I-atoms in the physisorbed molecular caliper correlates with their subsequent separation when chemisorbed at the surface.

The recoil of adsorbates away (desorption) and towards (reaction) surfaces is well known. Here, we describe the long-range recoil of adsorbates in the plane of a surface, and accordingly the novel phenomenon of reactions occurring at a substantial distance from the originating event. Three thermal and three electron-induced surface reactions are shown by scanning tunnelling microscopy to propel their physisorbed ethylenic products across the rough surface of Si(100) over a distance of up to 200 Å before an attachment reaction. The recoil energy in the ethylenic products comes from thermal exoergicity or from electronic excitation of chemisorbed alkenes. We propose that the mechanism of migration is a rolling motion, because the recoiling molecule overcomes raised surface obstacles. Electronic excitation of propene causes directional recoil and often end-to-end inversion, suggesting cartwheeling. Ab initio calculations of the halogenation and electron-induced reactions support a model in which asymmetric forces between the molecule and the surface induce rotation and therefore migration.

The fabrication of nano devices at surfaces makes conflicting demands of mobility for self-assembly (SA) and immobility for permanence. The solution proposed in earlier work from this laboratory involved pattern formation in physisorbed molecules by SA, followed by localized reaction to chemically imprint the pattern substantially unchanged, a procedure we termed molecular-scale imprinting (MSI). Here, as proof of generality we extended this procedure, previously applied to imprinting circles on Si(111)-7 × 7, to SA lines of 1-chloropentane (CP) on Si(100)-2 × 1. The physisorbed lines consisted of pairs of CP that grew perpendicular to the Si dimer rows, as shown by scanning tunneling microscopy and ab initio theory. Chemical reaction of these lines with the surface was triggered in separate experiments by three different modes of energization: heat, electrons, or light. In all cases the CP molecules underwent MSI with a Si atom beneath so that the physisorbed lines of CP pairs were imprinted as chemisorbed lines of Cl pairs.

Oxygen vacancies on metal oxide surfaces have long been thought to play a key role in the surface chemistry. Such processes have been directly visualized in the case of the model photocatalyst surface TiO(2)(110) in reactions with water and molecular oxygen. These vacancies have been assumed to be neutral in calculations of the surface properties. However, by comparing experimental and simulated scanning tunneling microscopy images and spectra, we show that oxygen vacancies act as trapping centers and are negatively charged. We demonstrate that charging the defect significantly affects the reactivity by following the reaction of molecular oxygen with surface hydroxyl formed by water dissociation at the vacancies. Calculations with electronically charged hydroxyl favor a condensation reaction forming water and surface oxygen adatoms, in line with experimental observations. This contrasts with simulations using neutral hydroxyl where hydrogen peroxide is found to be the most stable product.

The controlled imprinting of surfaces with specified patterns is important in the development of nanoscale devices. Previously, such patterns were created using self-assembled physisorbed adsorbate molecules that can be stabilized on the surface by subsequent chemical bonding. Here we show a first step towards use of the bonding within a surface to propagate reactions for patterning, namely the cooperative reaction of adjacent silicon atoms. We exploit the double-bonded silicon dimer pairs present on the surface of Si(100)-2×1 and show that the halogenation of one silicon atom (induced by electrons or heat) results in cooperative halogenation of the neighbouring silicon atom with unit efficiency. The reactants used were two 1-halopentane molecules physisorbed over a pair of silicon atoms. This cooperative pair of halogenation reactions was shown by ab initio calculation to be sequential on a timescale of femtoseconds.

Whereas all 230 three-dimensional space groups occur in organic crystals, out of only 17 plane groups some highly symmetric ones such as p31m have not yet been observed in two-dimensional (2D) crystals of organic molecules. Here a kagome network with p31m symmetry is reported for cobalt phthalocyanine on Cu(111). This unusual structure results from substrate-induced reduction of molecular symmetry and substrate-mediated interaction via quantum interference of surface electrons. These interactions provide additional control over the symmetry of 2D crystals of phthalocyanines and lead to a variety of other symmetries in self-assembled arrays.

We report a theoretical study of hydroxyl vacancies in aluminosilicate and aluminogermanate single-walled metal-oxide nanotubes. Defects are introduced on both sides of the tube walls and lead to occupied and empty states in the band gap which are highly localized both in energy and in real space. Different magnetization states are found depending on both the chemical composition and the specific side with respect to the tube cavity. The defect-induced perturbations to the pristine electronic structure are related to the electrostatic polarization across the tube walls and the ensuing change in Lewis acid-base reactivity. A general approach towards a quantitative evaluation of both the polarization across the tube walls and the tube excluded volume is also proposed and discussed on an electrostatic basis.

From an interplay between simultaneously recorded noncontact atomic force microscopy and scanning tunneling microscopy images and simulations based on density functional theory, we reveal the location of single hydrogen species in the surface and subsurface layers of rutile TiO2. Subsurface hydrogen atoms (H(sub)) are found to reside in a stable interstitial site as subsurface OH groups detectable in scanning tunneling microscopy as a characteristic electronic state but imperceptible to atomic force microscopy. The combined atomic force microscopy, scanning tunneling microscopy, and density functional theory study demonstrates a general scheme to reveal near surface defects and interstitials in poorly conducting materials.

Molecule-based functional devices on surfaces may take advantage of bistable molecular switches. The conformational dynamics and efficiency of switches are radically different on surfaces compared to the liquid phase. We present a design of molecular layers which enables bistable switching on a surface and, for the first time, demonstrate control of a single switch in a dense and ordered array at the spatial limit. Up and down motion of a central Sn ion through the frame of a phthalocyanine molecule is achieved via resonant electron or hole injection into molecular orbitals.

Heads or tails? The evolution of structural and electronic properties of tin-phthalocyanine films has been analyzed for sub-monolayer to multilayer coverage using low-temperature scanning tunneling microscopy. Two molecular conformations are observed: randomly dispersed for the first layer, and islands with a single conformation in subsequent layers.

In low-temperature scanning tunneling microscopy (STM) experiments a cerium adatom on Ag(100) possesses two discrete states with significantly different apparent heights. These atomic switches also exhibit a Kondo-like feature in spectroscopy experiments. By extensive theoretical simulations we find that this behavior is due to diffusion of hydrogen from the surface onto the Ce adatom in the presence of the STM tip field. The cerium adatom possesses vibrational modes of very low energy (3-4 meV) and very high efficiency (≥20%), which are due to the large changes of Ce states in the presence of hydrogen. The atomic vibrations lead to a Kondo-like feature at very low bias voltages.

One-dimensional nanostructures at silicon surfaces have potential applications in nanoscale devices. Here we propose a mechanism of dipole-directed assembly for the growth of lines of physisorbed dipolar molecules. The adsorbate chosen was a halide, in preparation for the patterned imprinting of halogen atoms. Using scanning tunnelling microscopy, physisorbed 1,5-dichloropentane on Si(100)-2x1 was shown to self-assemble at room temperature into molecular lines that grew predominantly perpendicular to the Si-dimer rows. Line formation was triggered by the displacement of surface charge by the dipolar adsorbate. Experimental and simulated scanning tunnelling microscopy images were in agreement for a range of positive and negative bias voltages. The geometry of the physisorbed molecules and nature of their binding were evident from the scanning tunnelling microscopy images, as interpreted by scanning tunnelling microscopy simulation.

We demonstrate that the giant spin contrast observed by scanning tunneling microscopy for double-layer Coislands on Pt(111) is caused by adsorbates at the apex of the Cr-coated W tip. The most likely candidate, in ab initio simulations, is hydrogen. Here, the electron charge is highly polarized by the adjacent Cr layers. The hydrogen adsorption site is shown to change from hollow to on top due to the electric field at the tip apex, created by the tunnel voltage.

The adsorption of semifluorinated alkanethiols on Au/mica was studied by scanning tunneling microscopy (STM). The adlayer structure produced is based on a p(2 x 2) structure though lines of molecules displayed extensive kinks and bends. In addition, a considerable variation in the contrast of molecular features is found. Molecular modeling calculations confirm that, for the fluorinated thiols, inequivalently adsorbed molecules within a p(2 x 2) registry are present, an aspect that endows the local structure of the adlayer with a higher flexibility in comparison to nonfluorinated thiols, where one adsorption site is strongly favored in a (radical 3 x radical 3) R30 degrees structure. Simulated STM imaging on the optimized systems successfully recovered the effects on the molecular feature contrast induced by the flexibility of the fluorinated thiol adlayer.

The controlled anchoring of molecular building blocks on appropriate templates is a major prerequisite for the rational design and fabrication of supramolecular architectures on surfaces. We report on a particularly selective adsorption process of hexa-peri-hexabenzocoronene on Au(111), which leads to well-controlled adsorption position and orientation of the polycyclic aromatic hydrocarbons. Scanning tunneling microscopy reveals selective adsorption on monatomic steps in the fcc stacking regions with a specific orientation of 18 degrees between the molecular axis and the step normal. Ab initio calculations for various adsorption sites reveal the lowest total energy for adsorption on a kink site. Energy considerations and the excellent agreement between experimental and simulated images show that adsorption on kink sites is responsible for the specific adsorption angle.

We have observed on-off switching of scanning tunneling microscope current flow to silicon adatoms of the Si(111)-(7 x 7) surface that are enclosed within a bistable dimeric corral of self-assembled chlorododecane molecules. These thermally activated oscillations amounted to an order of magnitude change in the current. Theory showed that small changes in molecular configuration could cause alterations in the corralled adatom's electronic energy by as much as 1 eV due to local field effects, accounting for the observed current switching.

With the approach presented herein, a large aromatic pi-system is synthesized, which shows extraordinarily high solubility and an effective suppression of aggregation. This was due to a distortion of the aromatic core by bulky tert-butyl groups and the solubilizing effects of alkyl chains in the corona of the aromatic core. Therefore not only the processing and cleaning of the materials with standard laboratory techniques became possible, but moreover the first structure-rich UV/vis and a resolved (1)H NMR spectra for an aromatic system two times larger than hexa-peri-hexabenzocoronene were recorded. The bulk properties in an extruded fiber as well as on the surface showed a columnar self-assembly including a phase in which a homeotropic alignment on a substrate was observed, which turns the material into an interesting candidate for future applications in electronic devices.

By means of scanning tunneling microscopy and density functional theory calculations, we studied the water formation reaction on the Rh(110) surface when exposing the (2 x 1)p2mg-O structure to molecular hydrogen, characterizing each of the structures that form on the surface during the reaction. First the reaction propagates on the surface as a wave front, removing half of the initial oxygen atoms. The remaining 0.5 monolayers of O atoms rearrange in pairs, forming a c(2 x 4) structure. Second, as the reaction proceeds, areas of an intermediate structure with c(2 x 2) symmetry appear and grow at the expense of the c(2 x 4) phase, involving all the oxygen atoms present on the surface. Afterward, the c(2 x 2) islands shrink, indicating that complete hydrogenation occurs at their edges, leaving behind a clean rhodium substrate. Two possible models for the c(2 x 2) structure, where not only the arrangement but also the chemical identity is different, are given. The first one is a mixed H + O structure, while the second one resembles the half-dissociated water layer already proposed on other metal surfaces. In both models, the high local oxygen coverage is achieved by the formation of a hexagonal network of hydrogen bonds.

Electrical transport through molecules has been much studied since it was proposed that individual molecules might behave like basic electronic devices, and intriguing single-molecule electronic effects have been demonstrated. But because transport properties are sensitive to structural variations on the atomic scale, further progress calls for detailed knowledge of how the functional properties of molecules depend on structural features. The characterization of two-terminal structures has become increasingly robust and reproducible, and for some systems detailed structural characterization of molecules on electrodes or insulators is available. Here we present scanning tunnelling microscopy observations and classical electrostatic and quantum mechanical modelling results that show that the electrostatic field emanating from a fixed point charge regulates the conductivity of nearby substrate-bound molecules. We find that the onset of molecular conduction is shifted by changing the charge state of a silicon surface atom, or by varying the spatial relationship between the molecule and that charged centre. Because the shifting results in conductivity changes of substantial magnitude, these effects are easily observed at room temperature.

The chiral molecule (R,R)-tartaric acid adsorbed on nickel surfaces creates highly enantioselective heterogeneous catalysts, but the nature of chiral modification remains unknown. Here, we report on the behavior of this chiral molecule with a defined Ni(110) surface. A combination of reflection absorption infrared spectroscopy, scanning tunneling microscopy, and periodic density functional theory calculations reveals a new mode of chiral induction. At room temperatures and low coverages, (R,R)-tartaric acid is adsorbed in its bitartrate form with two-point bonding to the surface via both carboxylate groups. The molecule is preferentially located above the 4-fold hollow site with each carboxylate functionality adsorbed at the short bridge site via O atoms placed above adjacent Ni atoms. However, repulsive interactions between the chiral OH groups of the molecule and the metal atoms lead to severely strained adsorption on the bulk-truncation Ni(110) surface. As a result, the most stable adsorption structure is one in which this adsorption-induced stress is alleviated by significant relaxation of surface metal atoms so that a long distance of 7.47 A between pairs of Ni atoms can be accommodated at the surface. Interestingly, this leads the bonding Ni atoms to describe a chiral footprint at the surface for which all local mirror symmetry planes are destroyed. Calculations show only one chiral footprint to be favored by the (R,R)-tartaric acid, with the mirror adsorption site being unstable by 6 kJ mol(-1). This energy difference is sufficient to enable the same local chiral reconstruction and motif to be sustained over 90% of the system, leading to an overall highly chiral metal surface.