In all theoretical treatments of electron transport through single molecules between two metal electrodes, a clear distinction has to be made between a coherent transport regime with a strong coupling throughout the junction and a Coulomb blockade regime in which the molecule is only weakly coupled to both leads. The former case where the tunnelling barrier is considered to be delocalized across the system can be well described with common mean-field techniques based on density functional theory (DFT), while the latter case with its two distinct barriers localized at the interfaces usually requires a multideterminant description. There is a third scenario with just one barrier localized inside the molecule which we investigate here using a variety of quantum-chemical methods by studying partial charge shifts in biphenyl radical ions induced by an electric field at different angles to modulate the coupling and thereby the barrier within the $π$-system. We find steps rounded off at the edges in the charge versus field curves for weak and intermediate coupling, whose accurate description requires a correct treatment of both exchange and dynamical correlation effects is essential. We establish that DFT standard functionals fail to reproduce this feature, while a long range corrected hybrid functional fares much better, which makes it a reasonable choice for a proper DFT-based transport description of such single barrier systems
High Frequency EPR Spectra of [Fe8O2(OH)12(tacn)6]Br8. A Critical Appraisal of the Barrier for the Reorientation of the Magnetization in Single Molecule Magnets
The kinetic transport of electrons through graphene magnetic barriers is studied theoretically in presence of an external time harmonic scalar potential. The transmission coefficients are calculated in the framework of the non-perturbative Floquet theory using transfer matrix method. The time dependent scalar potential is found to suppress the usual Fabry-Perot oscillations occurring in the transmission through a constant vector potential barrier (corresponding to two oppositely directed delta-function magnetic barriers). Two types of asymmetric Fano resonances (FR) are noted and are discussed…
We study a polar molecule immersed into a superfluid environment, such as a helium nanodroplet or a Bose-Einstein condensate, in the presence of an intense electrostatic field. We show that coupling of the molecular pendular motion, induced by the field, to the fluctuating bath leads to formation of pendulons -- spherical harmonic librators dressed by a field of many-particle excitations. We study the behavior of the pendulon in a broad range of molecule-bath and molecule-field interaction strengths, and reveal that its spectrum features series of instabilities which are absent in the field-fr…
Coupled colloidal quantum dot (CQD) dimers represent a new class of artificial molecules composed of fused core/shell semiconductor nanocrystals. The electronic coupling and wavefunction hybridization is enabled by the formation of an epitaxial connection with a coherent lattice between the shells of the two neighboring quantum dots where the shell material and its dimensions dictate the quantum barrier characteristics for the charge carriers. Herein we introduce a colloidal approach to control the neck formation at the interface between the two CQDs in such artificial molecular constructs. Th…
Self-assembled InAs quantum dots (QDs), which have long hole-spin coherence times and are amenable to optical control schemes, have long been explored as building blocks for qubit architectures. One such design consists of vertically stacking two QDs to create a quantum dot molecule (QDM) and using the spin-mixing properties of "molecule-like" coupled hole states for all-optical qubit manipulation. In this article, the first of two papers, we introduce the incorporation of dilute GaBiAs alloys in the barrier region between the two dots. GaBiAs is expected to increase the spin-mixing of the mol…
Iodine (I$_2$) molecules embedded in He nanodroplets are aligned by a 160 ps long laser pulse. The highest degree of alignment, occurring at the peak of the pulse and quantified by $\langle \cos^2 θ_{2D} \rangle$, is measured as a function of the laser intensity. The results are well described by $\langle \cos^2 θ_{2D} \rangle$ calculated for a gas of isolated molecules each with an effective rotational constant of 0.6 times the gas-phase value, and at a temperature of 0.4 K. Theoretical analysis using the angulon quasiparticle to describe rotating molecules in superfluid helium rationalizes w…
Configuration transitions of individual molecules and atoms on surfaces are traditionally described with energy barriers and attempt rates using an Arrhenius law. This approach yields consistent energy barrier values, but also attempt rates orders of magnitude below expected oscillation frequencies of particles in the meta-stable state. Moreover, even for identical systems, the measurements can yield values differing from each other by orders of magnitude. Using low temperature scanning tunnelling microscopy (STM) to measure an individual dibutyl-sulfide molecule (DBS) on Au(111), we show that…
Seeing inside a Plasmonic Nanogap: Few-molecule Orientation and Preferential Adsorption
Ecole Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院）；Center for Quantum Science and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院量子科学与工程中心）
We show that ordered monolayers of organic molecules stabilized by hydrogen bonding on the surface of exfoliated few-layer hexagonal boron nitride (hBN) flakes may be incorporated into van der Waals heterostructures with integral few-layer graphene contacts forming a molecular/2D hybrid tunneling diode. Electrons can tunnel from through the hBN/molecular barrier under an applied voltage VSD and we observe molecular electroluminescence from an excited singlet state with an emitted photon energy > eVSD, indicating up-conversion by energies up to ~ 1 eV. We show that tunnelling electrons excite e…
Magnetic tunnel junctions with wide band gap semiconductor ZnTe barrier were fabricated. A very low barrier height and sizable magnetoresistance were observed in the Fe/ZnTe/Fe junctions at room temperature. The nonlinear I-V characteristic curve confirmed the observed magnetoresistance is due to spin-dependent tunneling effect. Temperature dependent study indicated that the total conductance of the junction is dominated by direct tunneling, with only a small portion from the hopping conduction through the defect states inside the barrier.
The spin dynamics of Tb(OETAP)$_2$ single ion magnets was investigated by means of muon spin resonance ($μ$SR) both in the bulk material as well as when the system is embedded into PEDOT:PSS polymer conductor. The characteristic spin fluctuation time is characterized by a high temperature activated trend, with an energy barrier around 320 K, and by a low temperature tunneling regime. When the single ion magnet is embedded into the polymer the energy barrier only slightly decreases and the fluctuation time remains of the same order of magnitude even at low temperature. This finding shows that t…
Theories that are used to extract energy-landscape information from single-molecule pulling experiments in biophysics are all invariably based on Kramers' theory of thermally-activated escape rate from a potential well. As is well known, this theory recovers the Arrhenius dependence of the rate on the barrier energy, and crucially relies on the assumption that the barrier energy is much larger than $k_{B}T$ (limit of comparatively low thermal fluctuations). As was already shown in Dudko, Hummer, Szabo Phys. Rev. Lett. (2006), this approach leads to the unphysical prediction of dissociation tim…
