Héctor Vázquez

Submolecular Resolution by Variation of the Inelastic Electron Tunneling Spectroscopy Amplitude and its Relation to the AFM/STM Signal

Bruno de la Torre,1, 2, ∗ Martin Švec,1, 2 Giuseppe Foti,1 Ondřej Krejč́ı,1, 3 Prokop Hapala,1 Aran Garcia-Lekue,4, 5 Thomas Frederiksen,4, 5 Radek Zbořil,2 Andres Arnau,4 Héctor Vázquez,1 and Pavel Jeĺınek1, 2, 4, † 1Institute of Physics, Academy of Sciences of the Czech Republic, v.v.i., Cukrovarnická 10, 162 00 Prague, Czech Republic 2Regional Centre of Advanced Technologies and Materials, Palacký University, Olomouc, Czech Republic. 3Charles University, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 180 00, Prague, Czech Republic 4Donostia International Physics Center (DIPC), Paseo Manuel Lardizabal 4, E-20018 San Sebastian, Spain 5Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain

Tip-induced gating of molecular levels in carbene-based junctions

We study the conductance of N-heterocyclic carbene-based (NHC) molecules on gold by means of first-principles calculations based on density-functional theory and non-equilibrium Greens functions. We consider several tip structures and find a strong dependence of the position of the NHC molecular levels with the atomistic structure of the tip. The position of the lowest unoccupied molecular orbital (LUMO) can change by almost 0.8 eV with tip shape. Through an analysis of the net charge transfer, electron redistribution and work function for each tip structure, we rationalize the LUMO shifts in terms of the sum of the work function and the maximum electrostatic potential arising from charge rearrangement. These differences in the LUMO position, effectively gating the molecular levels, result in large conductance variations. These findings open the way to modulating the conductance of NHC-based molecular circuits through the controlled design of the tip atomistic structure.

Voltage-dependent conductance states of a single-molecule junction

Ag-Sn-phthalocyanine-Ag junctions are shown to exhibit three conductance states. While the junctions are conductive at low bias, their impedance drastically increases above a critical bias. Two-level fluctuations occur at intermediate bias. These characteristics may be used to protect a nanoscale circuit. Further experiments along with calculations reveal that the self-limiting conductance of the junctions is due to reversible changes of the junction geometry.

Large Converse Piezoelectric Effect Measured on a Single Molecule on a Metallic Surface

The converse piezoelectric effect is a phenomenon in which mechanical strain is generated in a material due to an applied electrical field. In this work, we demonstrate the converse piezoelectric effect in single heptahelicene-derived molecules on the Ag(111) surface using atomic force microscopy (AFM) and total energy density functional theory (DFT) calculations. The force-distance spectroscopy acquired over a wide range of bias voltages reveals a linear shift of the tip-sample distance at which the contact between the molecule and tip apex is established. We demonstrate that this effect is caused by the bias-induced deformation of the spring-like scaffold of the helical polyaromatic molecules. We attribute this effect to coupling of a soft vibrational mode of the molecular helix with a vertical electric dipole induced by molecule-substrate charge transfer. In addition, we also performed the same spectroscopic measurements on a more rigid o-carborane dithiol molecule on the Ag(111) surface. In this case, we identify a weaker linear electromechanical response, which underpins the importance of the helical scaffold on the observed piezoelectric response.

Stable Au–C bonds to the substrate for fullerene-based nanostructures

We report on the formation of fullerene-derived nanostructures on Au(111) at room temperature and under UHV conditions. After low-energy ion sputtering of fullerene films deposited on Au(111), bright spots appear at the herringbone corner sites when measured using a scanning tunneling microscope. These features are stable at room temperature against diffusion on the surface. We carry out DFT calculations of fullerene molecules having one missing carbon atom to simulate the vacancies in the molecules resulting from the sputtering process. These modified fullerenes have an adsorption energy on the Au(111) surface that is 1.6 eV higher than that of C60 molecules. This increased binding energy arises from the saturation by the Au surface of the bonds around the molecular vacancy defect. We therefore interpret the observed features as adsorbed fullerene-derived molecules with C vacancies. This provides a pathway for the formation of fullerene-based nanostructures on Au at room temperature.

Adsorbate-driven cooling of carbene-based molecular junctions

We study the role of an NH2 adsorbate on the current-induced heating and cooling of a neighboring carbene-based molecular circuit. We use first-principles methods of inelastic tunneling transport based on density functional theory and non-equilibrium Green’s functions to calculate the rates of emission and absorbtion of vibrations by tunneling electrons, the population of vibrational modes and the energy stored in them. We find that the charge rearrangement resulting from the adsorbate gates the carbene electronic structure and reduces the density of carbene states near the Fermi level as a function of bias. These effects result in the cooling of carbene modes at all voltages compared to the “clean” carbene-based junction. We also find that the direct influence of adsorbate states is significantly smaller and tends to heat adsorbate vibrations. Our results highlight the important role of molecular adsorbates not only on the electronic and elastic transport properties but also on the current-induced energy exchange and stability under bias of single-molecule circuits.