Opportunities and limitations of transition voltage spectroscopy: a theoretical analysis

In molecular charge transport, transition voltage spectroscopy (TVS) holds the promise that molecular energy levels can be explored at bias voltages lower than required for resonant tunneling. We investigate the theoretical basis of this novel tool, using a generic model. In particular, we study the length dependence of the conducting frontier orbital and of the 'transition voltage' as a function of length. We show that this dependence is influenced by the amount of screening of the electrons in the molecule, which determines the voltage drop to be located at the contacts or across the entire molecule. We observe that the transition voltage depends significantly on the length, but that the ratio between the transition voltage and the conducting frontier orbital is approximately constant only in strongly screening (conjugated) molecules. Uncertainty about the screening within a molecule thus limits the predictive power of TVS. We furthermore argue that the relative length independence of the transition voltage for non-conjugated chains is due to strong localization of the frontier orbitals on the end groups ensuring binding of the rods to the metallic contacts. Finally, we investigate the characteristics of TVS in asymmetric molecular junctions. If a single level dominates the transport properties, TVS can provide a good estimate for both the level position and the degree of junction asymmetry. If more levels are involved the applicability of TVS becomes limited.Comment: 8 pages, 12 figure

Interference enhanced thermoelectricity in quinoid type structures

Quantum interference (QI) effects in molecular junctions may be used to obtain large thermoelectric responses. We study the electrical conductance G and the thermoelec- tric response of a series of molecules featuring a quinoid core using density functional theory (DFT), as well as a semi-empirical interacting model Hamiltonian describing the {\pi}-system of the molecule which we treat in the GW approximation. Molecules with a quinoid type structure are shown to have two distinct destructive QI features close to the frontier orbital energies. These manifest themselves as two dips in the transmission, that remain separated, even when either electron donating or withdraw- ing side groups are added. We find that the position of the dips in the transmission and the frontier molecular levels can be chemically controlled by varying the electron donating or withdrawing character of the side groups as well as the conjugation length inside the molecule. This feature results in a very high thermoelectric power factor S^2G and figure of merit ZT, where S is the Seebeck coefficient, making quinoid type molecules potential candidates for efficient thermoelectric devices.Comment: 22 pages, 11 figure

Electric-field control of interfering transport pathways in a single-molecule anthraquinone transistor

It is understood that molecular conjugation plays an important role in charge transport through single-molecule junctions. Here, we investigate electron transport through an anthraquinone based single-molecule three-terminal device. With the use of an electric-field induced by a gate electrode, the molecule is reduced resulting into a ten-fold increase in the off-resonant differential conductance. Theoretical calculations link the change in differential conductance to a reduction-induced change in conjugation, thereby lifting destructive interference of transport pathways.Comment: Nano Letters (2015

Electrical control of spin dynamics in finite one-dimensional systems

We investigate the possibility of the electrical control of spin transfer in monoatomic chains incorporating spin-impurities. Our theoretical framework is the mixed quantum-classical (Ehrenfest) description of the spin dynamics, in the spirit of the s-d-model, where the itinerant electrons are described by a tight-binding model while localized spins are treated classically. Our main focus is on the dynamical exchange interaction between two well-separated spins. This can be quantified by the transfer of excitations in the form of transverse spin oscillations. We systematically study the effect of an electrostatic gate bias V_g on the interconnecting channel and we map out the long-range dynamical spin transfer as a function of V_g. We identify regions of V_g giving rise to significant amplification of the spin transmission at low frequencies and relate this to the electronic structure of the channel.Comment: 9 pages, 11 figure

Spatially Resolved Excitation of Rydberg Atoms and Surface Effects on an Atom Chip

We demonstrate spatially resolved, coherent excitation of Rydberg atoms on an atom chip. Electromagnetically induced transparency (EIT) is used to investigate the properties of the Rydberg atoms near the gold coated chip surface. We measure distance dependent shifts (~10 MHz) of the Rydberg energy levels caused by a spatially inhomogeneous electric field. The measured field strength and distance dependence is in agreement with a simple model for the electric field produced by a localized patch of Rb adsorbates deposited on the chip surface during experiments. The EIT resonances remain narrow (< 4 MHz) and the observed widths are independent of atom-surface distance down to ~20 \mum, indicating relatively long lifetime of the Rydberg states. Our results open the way to studies of dipolar physics, collective excitations, quantum metrology and quantum information processing involving interacting Rydberg excited atoms on atom chips

Two phase transitions in the fully frustrated XYXY model

The fully frustrated $XY$ model on a square lattice is studied by means of Monte Carlo simulations. A Kosterlitz-Thouless transition is found at $T_{\rm KT} \approx 0.446$, followed by an ordinary Ising transition at a slightly higher temperature, $T_c \approx 0.452$. The non-Ising exponents reported by others, are explained as a failure of finite size scaling due to the screening length associated with the nearby Kosterlitz-Thouless transition.Comment: REVTEX file, 8 pages, 5 figures in uuencoded postscrip

Image effects in transport at metal-molecule interfaces

We present a method for incorporating image-charge effects into the description of charge transport through molecular devices. A simple model allows us to calculate the adjustment of the transport levels, due to the polarization of the electrodes as charge is added to and removed from the molecule. For this, we use the charge distributions of the molecule between two metal electrodes in several charge states, rather than in gas phase, as obtained from a density-functional theory-based transport code. This enables us to efficiently model level shifts and gap renormalization caused by image-charge effects, which are essential for understanding molecular transport experiments. We apply the method to benzene di-amine molecules and compare our results with the standard approach based on gas phase charges. Finally, we give a detailed account of the application of our approach to porphyrin-derivative devices recently studied experimentally by Perrin et al. [Nat. Nanotechnol. 8, 282 (2013)], which demonstrates the importance of accounting for image-charge effects when modeling transport through molecular junctions

Conditional phase shift from a quantum dot in a pillar microcavity

Large conditional phase shifts from coupled atom-cavity systems are a key requirement for building a spin photon interface. This in turn would allow the realisation of hybrid quantum information schemes using spin and photonic qubits. Here we perform high resolution reflection spectroscopy of a quantum dot resonantly coupled to a pillar microcavity. We show both the change in reflectivity as the quantum dot is tuned through the cavity resonance, and measure the conditional phase shift induced by the quantum dot using an ultra stable interferometer. These techniques could be extended to the study of charged quantum dots, where it would be possible to realise a spin photon interface

Emulsification in binary liquids containing colloidal particles: a structure-factor analysis

We present a quantitative confocal-microscopy study of the transient and final microstructure of particle-stabilised emulsions formed via demixing in a binary liquid. To this end, we have developed an image-analysis method that relies on structure factors obtained from discrete Fourier transforms of individual frames in confocal image sequences. Radially averaging the squared modulus of these Fourier transforms before peak fitting allows extraction of dominant length scales over the entire temperature range of the quench. Our procedure even yields information just after droplet nucleation, when the (fluorescence) contrast between the two separating phases is scarcely discernable in the images. We find that our emulsions are stabilised on experimental time scales by interfacial particles and that they are likely to have bimodal droplet-size distributions. We attribute the latter to coalescence together with creaming being the main coarsening mechanism during the late stages of emulsification and we support this claim with (direct) confocal-microscopy observations. In addition, our results imply that the observed droplets emerge from particle-promoted nucleation, possibly followed by a free-growth regime. Finally, we argue that creaming strongly affects droplet growth during the early stages of emulsification. Future investigations could clarify the link between quench conditions and resulting microstructure, paving the way for tailor-made particle-stabilised emulsions from binary liquids.Comment: http://iopscience.iop.org/0953-8984/22/45/455102

Phase transition in ultrathin magnetic films with long-range interactions: Monte Carlo simulation of the anisotropic Heisenberg model

Ultrathin magnetic films can be modeled as an anisotropic Heisenberg model with long-range dipolar interactions. It is believed that the phase diagram presents three phases: An ordered ferromagnetic phase I, a phase characterized by a change from out-of-plane to in-plane in the magnetization II, and a high-temperature paramagnetic phase III. It is claimed that the border lines from phase I to III and II to III are of second order and from I to II is first order. In the present work we have performed a very careful Monte Carlo simulation of the model. Our results strongly support that the line separating phases II and III is of the BKT type.Comment: 7 page