J. I. Pascual

Selectivity in vibrationally mediated single-molecule chemistry

The selective excitation of molecular vibrations provides a means to directly influence the speed and outcome of chemical reactions. Such mode-selective chemistry has traditionally used laser pulses to prepare reactants in specific vibrational states to enhance reactivity or modify the distribution of product species. Inelastic tunnelling electrons may also excite molecular vibrations and have been used to that effect on adsorbed molecules, to cleave individual chemical bonds and induce molecular motion or dissociation. Here we demonstrate that inelastic tunnelling electrons can be tuned to induce selectively either the translation or desorption of individual ammonia molecules on a Cu(100) surface. We are able to select a particular reaction pathway by adjusting the electronic tunnelling current and energy during the reaction induction such that we activate either the stretching vibration of ammonia or the inversion of its pyramidal structure. Our results illustrate the ability of the scanning tunnelling microscope to probe single-molecule events in the limit of very low yield and very low power irradiation, which should allow the investigation of reaction pathways not readily amenable to study by more conventional approaches.

Charged and metallic molecular monolayers through surface-induced aromatic stabilization

Large π-conjugated molecules, when in contact with a metal surface, usually retain a finite electronic gap and, in this sense, stay semiconducting. In some cases, however, the metallic character of the underlying substrate is seen to extend onto the first molecular layer. Here, we develop a chemical rationale for this intriguing phenomenon. In many reported instances, we find that the conjugation length of the organic semiconductors increases significantly through the bonding of specific substituents to the metal surface and through the concomitant rehybridization of the entire backbone structure. The molecules at the interface are thus converted into different chemical species with a strongly reduced electronic gap. This mechanism of surface-induced aromatic stabilization helps molecules to overcome competing phenomena that tend to keep the metal Fermi level between their frontier orbitals. Our findings aid in the design of stable precursors for metallic molecular monolayers, and thus enable new routes for the chemical engineering of metal surfaces.

Long-Range Repulsive Interaction between Molecules on a Metal Surface Induced by Charge Transfer

The adsorption of a molecular electron donor on Au(111) is characterized by the spontaneous formation of a superlattice of monomers spaced several nanometers apart. The coverage-dependent molecular pair distributions obtained from scanning tunneling microscopy data reveal an intermolecular long-range repulsive potential, which decreases as the inverse of the molecular separation. Density functional theory calculations show a charge accumulation in the molecules due to electron donation into the metal. Our results suggest that electrostatic repulsion between molecules persists on the surface of a metal.

Competition of Superconducting Phenomena and Kondo Screening at the Nanoscale

A manganese complex adsorbed on a superconducting lead surface creates a mosaic of two magnetic ground states. Magnetic and superconducting interactions couple electrons together to form complex states of matter. We show that, at the atomic scale, both types of interactions can coexist and compete to influence the ground state of a localized magnetic moment. Local spectroscopy at 4.5 kelvin shows that the spin-1 system formed by manganese-phthalocyanine (MnPc) adsorbed on Pb(111) can lie in two different magnetic ground states. These are determined by the balance between Kondo screening and superconducting pair-breaking interactions. Both ground states alternate at nanometer length scales to form a Moiré-like superstructure. The quantum phase transition connecting the two (singlet and doublet) ground states is thus tuned by small changes in the molecule-lead interaction.

Resolution of site-specific bonding properties of C60 adsorbed on Au(111)

We have performed a careful study of the adsorption of C60 molecules on a Au(111) surface by using scanning tunneling microscopy and spectroscopy at room temperature. In coincidence with results from other techniques, differential conductance spectra give a value of 2.3 eV for the HOMO–LUMO gap of a monomolecular layer, with the LUMO level located at 0.6 eV above the Fermi level as a consequence of electronic charge transfer from the substrate into the molecule. Small differences in position (and shape) of the LUMO-derived resonance, in the order of 0.1 eV, are found on molecules adsorbed at step edges. We consider the Smoluchowski effect, i.e., the interaction of the molecules with a charge-depleted region, to explain the observed differences in their bonding nature. On some molecules forming part of bidimensional fullerene islands, similar differences were also detected with spatially resolved scanning tunneling spectroscopy, giving rise to a 2×2 commensurate structure of the molecular adlayer with resp...

Formation of dispersive hybrid bands at an organic-metal interface

An electronic band with quasi-one-dimensional dispersion is found at the interface between a monolayer of a charge-transfer complex (TTF-TCNQ) and a Au(111) surface. Combined local spectroscopy and numerical calculations show that the band results from a complex mixing of metal and molecular states. The molecular layer folds the underlying metal states and mixes with them selectively, through the TTF component, giving rise to anisotropic hybrid bands. Our results suggest that, by tuning the components of such molecular layers, the dimensionality and dispersion of organic-metal interface states can be engineered.

Resonant electron heating and molecular phonon cooling in single C60 junctions

We study heating and heat dissipation of a single C(60) molecule in the junction of a scanning tunneling microscope by measuring the electron current required to thermally decompose the fullerene cage. The power for decomposition varies with electron energy and reflects the molecular resonance structure. When the scanning tunneling microscope tip contacts the fullerene the molecule can sustain much larger currents. Transport simulations explain these effects by molecular heating due to resonant electron-phonon coupling and molecular cooling by vibrational decay into the tip upon contact formation.

Spectroscopy of C60 single molecules: the role of screening on energy level alignment

In this paper we investigate the electronic properties of single molecules by means of low-temperature scanning tunneling spectroscopy (STS). We focus on C60 molecules deposited on a Au(111) surface at different substrate temperatures and mixed with two different hydrocarbons. In this way we change the fullerene interaction with the surface and/or the dipolar response of the molecular neighborhood to charging events. We explore the dependence of the energy level alignment on the molecular surroundings. The results confirm an already established picture in photoelectron spectroscopy.

Role of Spin in Quasiparticle Interference

Quasiparticle interference patterns measured by scanning tunneling microscopy can be used to study the local electronic structure of metal surfaces and high-temperature superconductors. Here, we show that even in nonmagnetic systems the spin of the quasiparticles can have a profound effect on the interference patterns. On Bi(110), where the surface state bands are not spin degenerate, the patterns are not related to the dispersion of the electronic states in a simple way. In fact, the features which are expected for the spin-independent situation are absent and the observed interference patterns can be interpreted only by taking spin-conserving scattering events into account.

Protection of excited spin states by a superconducting energy gap

When a paramagnetic molecule is placed on a superconducting surface the lifetime of its spin excitations increases dramatically. This effect, caused by the depletion of the electronic states within the energy gap at the Fermi level, could find application in coherent spin manipulation.