Spin dynamics and chirality induced spin selectivity.

By now, it is well known that chiral molecules can affect the spin of electrons passing through. In addition, the magnetization of, e.g., nanomagnets covered by chiral molecules can be affected by the presence of molecules. We are studying the mechanisms that explain various observations involving combinations of magnets and chiral molecules. We find that there exists a molecule induced contribution to the magnetic anisotropy of the magnets. Out of equilibrium, when electrons are actually being transported through a nano-magnet covered with chiral molecules, a molecule induced torque acting on the magnetization is emerging. It is of the spin-transfer-torque kind, already discussed in other parts of spintronics. This current induced torque can help explain the observed breaking of the Onsager reciprocity principle in experiments involving magnets and chiral molecules.

Observation of Biradical Spin Coupling through Hydrogen Bonds.

Investigation of intermolecular electron spin interaction is of fundamental importance in both science and technology. Here, radical pairs of all-trans retinoic acid molecules on Au(111) are created using an ultralow temperature scanning tunneling microscope. Antiferromagnetic coupling between two radicals is identified by magnetic-field-dependent spectroscopy. The measured exchange energies are from 0.1 to 1.0 meV. The biradical spin coupling is mediated through O─H⋯O hydrogen bonds, as elucidated from analysis combining density functional theory calculation and a modern version of valence bond theory.

Chiral-Induced Spin Selectivity in Capacitively Coupled Molecules.

The chiral-induced spin selectivity (CISS) effect is usually associated with electrons passing through chiral molecules. There are a number of experiments where external electrical fields rearrange electrons inside otherwise isolated molecules, allegedly also generating spin polarization of the molecule. There are theoretical suggestions of pairs of molecules generating spin polarizations in each other due to fluctuating electrical dipoles. This paper critically theoretically evaluates such spin-dependent charge reorganization (SDCR) effects. We find that such effects are not ruled out in principle, but they are very small and probably not detectable.

Single-particle combinatorial multiplexed liposome fusion mediated by DNA.

Combinatorial high-throughput methodologies are central for both screening and discovery in synthetic biochemistry and biomedical sciences. They are, however, often reliant on large-scale analyses and thus limited by a long running time and excessive materials cost. We here present a single-particle combinatorial multiplexed liposome fusion mediated by DNA for parallelized multistep and non-deterministic fusion of individual subattolitre nanocontainers. We observed directly the efficient (>93%) and leakage free stochastic fusion sequences for arrays of surface-tethered target liposomes with six freely diffusing populations of cargo liposomes, each functionalized with individual lipidated single-stranded DNA and fluorescently barcoded by a distinct ratio of chromophores. The stochastic fusion resulted in a distinct permutation of fusion sequences for each autonomous nanocontainer. Real-time total internal reflection imaging allowed the direct observation of >16,000 fusions and 566 distinct fusion sequences accurately classified using machine learning. The high-density arrays of surface-tethered target nanocontainers (~42,000 containers per mm2) offers entire combinatorial multiplex screens using only picograms of material.

Theory of Chirality Induced Spin Selectivity: Progress and Challenges.

A critical overview of the theory of the chirality-induced spin selectivity (CISS) effect, that is, phenomena in which the chirality of molecular species imparts significant spin selectivity to various electron processes, is provided. Based on discussions in a recently held workshop, and further work published since, the status of CISS effects-in electron transmission, electron transport, and chemical reactions-is reviewed. For each, a detailed discussion of the state-of-the-art in theoretical understanding is provided and remaining challenges and research opportunities are identified.

Theory of Chiral Induced Spin Selectivity.

A general theory of the chiral induced spin selectivity (CISS) effect is presented. It is based on the fact that the spin-orbit (SO) coupling is small, a few meV, for the light atoms, which make up typical chiral molecules in experiments. We present a theorem based on the Onsager reciprocal principle, which states that the CISS effect vanishes when thermally averaging over all electron states. This zero result is avoided by the very nonthermal character of the incoming optically generated electrons in experimental realizations. Despite the small SO-coupling, the presence of accidental degeneracies in the molecular spectrum yields a sizable spin polarization. The CISS effect in the presence of magnetic leads is special. We prove that, in a situation with one magnetic lead, the other lead will become magnetized. This results from the interplay between the spin-orbit coupling in the chiral molecule and the magnetized lead. Numerical calculations for realistic chiral molecules confirm the theory.

Kondo blockade due to quantum interference in single-molecule junctions.

Molecular electronics offers unique scientific and technological possibilities, resulting from both the nanometre scale of the devices and their reproducible chemical complexity. Two fundamental yet different effects, with no classical analogue, have been demonstrated experimentally in single-molecule junctions: quantum interference due to competing electron transport pathways, and the Kondo effect due to entanglement from strong electronic interactions. Here we unify these phenomena, showing that transport through a spin-degenerate molecule can be either enhanced or blocked by Kondo correlations, depending on molecular structure, contacting geometry and applied gate voltages. An exact framework is developed, in terms of which the quantum interference properties of interacting molecular junctions can be systematically studied and understood. We prove that an exact Kondo-mediated conductance node results from destructive interference in exchange-cotunneling. Nonstandard temperature dependences and gate-tunable conductance peaks/nodes are demonstrated for prototypical molecular junctions, illustrating the intricate interplay of quantum effects beyond the single-orbital paradigm.

Current-induced runaway vibrations in dehydrogenated graphene nanoribbons.

We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from the rest of carbon atoms. The electrical current can couple the dimer motion in a coherent fashion. The coupling, which is mediated by nonconservative and pseudo-magnetic current-induced forces, change the atomic dynamics, and thereby show their signature in this simple system. We study the atomic dynamics and current-induced vibrational instabilities using a simplified eigen-mode analysis. Our study illustrates how armchair nanoribbons can serve as a possible testbed for probing the current-induced forces.

Current-induced forces and hot spots in biased nanojunctions.

We investigate theoretically the interplay of current-induced forces (CIFs), Joule heating, and heat transport inside a current-carrying nanoconductor. We find that the CIFs, due to the electron-phonon coherence, can control the spatial heat dissipation in the conductor. This yields a significant asymmetric concentration of excess heating (hot spot) even for a symmetric conductor. When coupled to the electrode phonons, CIFs drive different phonon heat flux into the two electrodes. First-principles calculations on realistic biased nanojunctions illustrate the importance of the effect.

Single molecule activity measurements of cytochrome P450 oxidoreductase reveal the existence of two discrete functional states.

Electron transfer between membrane spanning oxidoreductase enzymes controls vital metabolic processes. Here we studied for the first time with single molecule resolution the function of P450 oxidoreductase (POR), the canonical membrane spanning activator of all microsomal cytochrome P450 enzymes. Measurements and statistical analysis of individual catalytic turnover cycles shows POR to sample at least two major functional states. This phenotype may underlie regulatory interactions with different cytochromes P450 but to date has remained masked in bulk kinetics. To ensure that we measured the inherent behavior of POR, we reconstituted the full length POR in "native like" membrane patches, nanodiscs. Nanodisc reconstitution increased stability by ∼2-fold as compared to detergent solubilized POR and showed significantly increased activity at biologically relevant ionic strength conditions, highlighting the importance of studying POR function in a membrane environment. This assay paves the way for studying the function of additional membrane spanning oxidoreductases with single molecule resolution.

Charge transfer and current fluctuations in single layer graphene transistors modified by self-assembled C60 adlayers.

Flicker noise in a "fullerene + graphene" hybrid transistor is investigated to reveal the electrical coupling between the graphene channel and C60 adsorbates. The charge trapping and detrapping events at the C60 /graphene interface induce current fluctuations in the devices. The evolution of noise characteristics at varying temperatures indicates the different contributions related to Coulomb scattering and charge exchange kinetics.

Electrical annealing and temperature dependent transversal conduction in multilayer reduced graphene oxide films for solid-state molecular devices.

The transversal conductance through thin multi-layered films of reduced graphene oxide was studied as a function of temperature in a solid-state device setup designed for molecular electronic measurements. Upon cooling to cryogenic temperatures, the resistivity of the films increased by about three orders of magnitude compared to the value at room temperature, and this temperature dependence was described by a variable range hopping model. Above a certain threshold voltage the films could be annealed electrically at low temperatures. This electrical annealing resulted in a dramatic decrease in resistivity by up to four orders of magnitude. Upon reheating, the conductivity of the annealed films displayed an almost negligible temperature dependence. These results are promising for the application of reduced graphene oxide as a soft top-contact layer for molecular monolayer devices in the solid-state.

Single enzyme studies reveal the existence of discrete functional states for monomeric enzymes and how they are "selected" upon allosteric regulation.

Allosteric regulation of enzymatic activity forms the basis for controlling a plethora of vital cellular processes. While the mechanism underlying regulation of multimeric enzymes is generally well understood and proposed to primarily operate via conformational selection, the mechanism underlying allosteric regulation of monomeric enzymes is poorly understood. Here we monitored for the first time allosteric regulation of enzymatic activity at the single molecule level. We measured single stochastic catalytic turnovers of a monomeric metabolic enzyme (Thermomyces lanuginosus Lipase) while titrating its proximity to a lipid membrane that acts as an allosteric effector. The single molecule measurements revealed the existence of discrete binary functional states that could not be identified in macroscopic measurements due to ensemble averaging. The discrete functional states correlate with the enzyme's major conformational states and are redistributed in the presence of the regulatory effector. Thus, our data support allosteric regulation of monomeric enzymes to operate via selection of preexisting functional states and not via induction of new ones.

Laserlike vibrational instability in rectifying molecular conductors.

We study the damping of molecular vibrations due to electron-hole pair excitations in donor-acceptor (D-A) type molecular rectifiers. At finite voltage additional nonequilibrium electron-hole pair excitations involving both electrodes become possible, and contribute to the stimulated emission and absorption of phonons. We point out a generic mechanism for D-A molecules, where the stimulated emission can dominate beyond a certain voltage due to the inverted position of the D and A quantum resonances. This leads to current-driven amplification (negative damping) of the phonons similar to laser action. We investigate the effect in realistic molecular rectifier structures using first-principles calculations.

Current-induced dynamics in carbon atomic contacts.

BACKGROUND: The effect of electric current on the motion of atoms still poses many questions, and several mechanisms are at play. Recently there has been focus on the importance of the current-induced nonconservative forces (NC) and Berry-phase derived forces (BP) with respect to the stability of molecular-scale contacts. Systems based on molecules bridging electrically gated graphene electrodes may offer an interesting test-bed for these effects. RESULTS: We employ a semi-classical Langevin approach in combination with DFT calculations to study the current-induced vibrational dynamics of an atomic carbon chain connecting electrically gated graphene electrodes. This illustrates how the device stability can be predicted solely from the modes obtained from the Langevin equation, including the current-induced forces. We point out that the gate offers control of the current, independent of the bias voltage, which can be used to explore current-induced vibrational instabilities due the NC/BP forces. Furthermore, using tight-binding and the Brenner potential we illustrate how Langevin-type molecular-dynamics calculations including the Joule heating effect for the carbon-chain systems can be performed. Molecular dynamics including current-induced forces enables an energy redistribution mechanism among the modes, mediated by anharmonic interactions, which is found to be vital in the description of the electrical heating. CONCLUSION: We have developed a semiclassical Langevin equation approach that can be used to explore current-induced dynamics and instabilities. We find instabilities at experimentally relevant bias and gate voltages for the carbon-chain system.

Blowing the fuse: Berry's phase and runaway vibrations in molecular conductors.

We examine a molecular bridge connecting two metallic electrodes. We find that an electronic current passing across the bridge can cause a vibrational instability of the molecule, which ultimately can lead to a breakdown of the bridge. This instability is generated by a hitherto never considered mechanism, which surprisingly involves the quantum mechanical phase of the electronic waves, the "Berry phase". This mechanism works for highly conducting bridges, and contrary to breakdown by traditional Joule heating, this instability is deterministic and occurs at certain critical voltages. We demonstrate the new mechanism using state-of-the-art ab initio calculations on realistic molecular bridges.

Electrical manipulation of spin states in a single electrostatically gated transition-metal complex.

We demonstrate an electrically controlled high-spin (S = 5/2) to low-spin (S = 1/2) transition in a three-terminal device incorporating a single Mn(2+) ion coordinated by two terpyridine ligands. By adjusting the gate-voltage we reduce the terpyridine moiety and thereby strengthen the ligand-field on the Mn-atom. Adding a single electron thus stabilizes the low-spin configuration and the corresponding sequential tunnelling current is suppressed by spin-blockade. From low-temperature inelastic cotunneling spectroscopy, we infer the magnetic excitation spectrum of the molecule and uncover also a strongly gate-dependent singlet-triplet splitting on the low-spin side. The measured bias-spectroscopy is shown to be consistent with an exact diagonalization of the Mn-complex, and an interpretation of the data is given in terms of a simplified effective model.

Amphipathic motifs in BAR domains are essential for membrane curvature sensing.

BAR (Bin/Amphiphysin/Rvs) domains and amphipathic alpha-helices (AHs) are believed to be sensors of membrane curvature thus facilitating the assembly of protein complexes on curved membranes. Here, we used quantitative fluorescence microscopy to compare the binding of both motifs on single nanosized liposomes of different diameters and therefore membrane curvature. Characterization of members of the three BAR domain families showed surprisingly that the crescent-shaped BAR dimer with its positively charged concave face is not able to sense membrane curvature. Mutagenesis on BAR domains showed that membrane curvature sensing critically depends on the N-terminal AH and furthermore that BAR domains sense membrane curvature through hydrophobic insertion in lipid packing defects and not through electrostatics. Consequently, amphipathic motifs, such as AHs, that are often associated with BAR domains emerge as an important means for a protein to sense membrane curvature. Measurements on single liposomes allowed us to document heterogeneous binding behaviour within the ensemble and quantify the influence of liposome polydispersity on bulk membrane curvature sensing experiments. The latter results suggest that bulk liposome-binding experiments should be interpreted with great caution.

How curved membranes recruit amphipathic helices and protein anchoring motifs.

Lipids and several specialized proteins are thought to be able to sense the curvature of membranes (MC). Here we used quantitative fluorescence microscopy to measure curvature-selective binding of amphipathic motifs on single liposomes 50-700 nm in diameter. Our results revealed that sensing is predominantly mediated by a higher density of binding sites on curved membranes instead of higher affinity. We proposed a model based on curvature-induced defects in lipid packing that related these findings to lipid sorting and accurately predicted the existence of a new ubiquitous class of curvature sensors: membrane-anchored proteins. The fact that unrelated structural motifs such as alpha-helices and alkyl chains sense MC led us to propose that MC sensing is a generic property of curved membranes rather than a property of the anchoring molecules. We therefore anticipate that MC will promote the redistribution of proteins that are anchored in membranes through other types of hydrophobic moieties.

Nanoelectromechanical switch operating by tunneling of an entire C60 molecule.

We present a solid state single molecule electronic device where switching between two states with different conductance happens predominantly by tunneling of an entire C60 molecule. This conclusion is based on a novel statistical analysis of approximately 10(5) switching events. The analysis yields (i) the relative contribution of tunneling, current induced heating and thermal fluctuations to the switching mechanism, (ii) the voltage dependent energy barrier (approximately 100-200 meV) separating the two states of the switch and (iii) the switching attempt frequency, omega0, corresponding to a 2.8 meV mode, which is most likely rotational.