Ron Naaman

Spin Selectivity in Electron Transmission Through Self-Assembled Monolayers of Double-Stranded DNA

Photoelectrons emitted from a DNA-covered gold surface can have an unbalanced spin population of up to 60%. In electron-transfer processes, spin effects normally are seen either in magnetic materials or in systems containing heavy atoms that facilitate spin-orbit coupling. We report spin-selective transmission of electrons through self-assembled monolayers of double-stranded DNA on gold. By directly measuring the spin of the transmitted electrons with a Mott polarimeter, we found spin polarizations exceeding 60% at room temperature. The spin-polarized photoelectrons were observed even when the photoelectrons were generated with unpolarized light. The observed spin selectivity at room temperature was extremely high as compared with other known spin filters. The spin filtration efficiency depended on the length of the DNA in the monolayer and its organization.

Coulomb explosion imaging of small molecules.

Most of our knowledge of the structures of free molecules comes from indirect observations that focus on other properties (for example, energy or mass spectra) that depend on structure. Recently, a new method has been developed that instead yields geometrical images of individual molecules. This method takes advantage of the large Coulomb repulsion of the nuclei within molecules rapidly stripped of their electrons. The first experiments with this new technique have already revealed structural images of several important species, such as positively charged methane ions.

Magnetism induced by the organization of self-assembled monolayers

Unique occurrence of magnetism is shown, in which magnetism appears ex nihilo, when organic molecules are self-assembled as monolayers on gold substrate. The molecules as well as the substrate, when they stand alone, are diamagnetic. Using a superconducting quantum interference device type magnetometer we obtained direct evidence that close-packed organized thio-organic films adsorbed on gold substrates possess magnetic properties at room temperature. The films studied show very high specific magnetization, up to many tens Bohr magnetons per adsorbed molecule, with a very small hysteresis. It is highly anisotropic and shows almost no temperature dependence. The magnetism observed is related to charge transfer between the organic layer and the metal substrate. Yet, the uniqueness here is that many spins are polarized per adsorbed molecules. The magnetic effect is related to the two dimensional organization of the organic molecules on the metal substrate which might explain the high anisotropy.

Immobilizing a Drop of Water: Fabricating Highly Hydrophobic Surfaces that Pin Water Droplets

We describe the fabrication of a patterned, hydrophobic silicon substrate that can pin a water droplet despite its large contact angle. Arrays of nm tips in silicon were fabricated by reactive ion etching using polymer masks defined by photolithography. A droplet sitting on one class of these substrates did not fall even after the substrate was turned upside-down. The production allows the fabrication of large arrays of tips with a one-step simple etching process, along with silanization, to achieve a substrate with both very large contact and tilting angles.

Chiral-Induced Spin Selectivity Effect

The chiral-induced spin selectivity (CISS) effect was recently established experimentally and theoretically. Here, we review some of the new findings and discuss applications that can result from special properties of this effect, like the reduction of the elastic backscattering in electron transfer through chiral molecules. The CISS effect opens the possibility of using chiral molecules in spintronics applications and for providing a deeper understanding of spin-selective processes in biology.

Ultraviolet absorption spectroscopy of dissociating molecules: Effects of cluster formation on the photodissociation of CH3I

The ultraviolet absorption spectra of jet‐cooled CH3I, (CH3I)2, and (CH3I)n, n>2 are measured in the valence A state and the Rydberg B state. A significant blue shift of the valence state is observed upon cluster formation. The magnitude of this shift yields a dimer bond strength of at least 500 cm−1 which implies extensive dimer formation at room temperature and moderate pressures. The methyl iodide B‐state spectrum consists of a single progression in the ν2 mode. Dimerization retards the predissociation and therefore increases the excited state lifetime; consequently many new modes are observed which in the monomer are coupled to the dissociation. The implications of this result to the photodissociation dynamics are discussed. The Rydberg spectra of (CH3I)n, n>2 show asymmetric line shapes which may be due to interferences between the B state and an underlying continuum. The nature of these interferences and the possible indentity of this continuum are discussed.

The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

Using a dissymmetrically-perturbed particle-in-a-box model, we demonstrate that the induced optical activity of chiral monolayer protected clusters, such as Whettens Au28(SG)16 glutathione-passivated gold nanoclusters (J. Phys. Chem. B, 2000, 104, 2630-2641), could arise from symmetric metal cores perturbed by a dissymmetric or chiral field originating from the adsorbates. This finding implies that the electronic states of the nanocluster core are chiral, yet the lattice geometries of these cores need not be geometrically distorted by the chiral adsorbates. Based on simple chiral monolayer protected cluster models, we rationalize how the adsorption pattern of the tethering sulfur atoms has a substantial effect on the induced CD in the NIR spectral region, and we show how the chiral image charge produced in the core provides a convenient means of visualizing dissymmetric perturbations to the achiral gold nanocluster core.

Spin Specific Electron Conduction through DNA Oligomers

Spin-based properties, applications, and devices are commonly related to magnetic effects and to magnetic materials. Most of the development in spintronics is currently based on inorganic materials. Despite the fact that the magnetoresistance effect has been observed in organic materials, until now spin selectivity of organic based spintronics devices originated from an inorganic ferromagnetic electrode and was not determined by the organic molecules themselves. Here we show that conduction through double-stranded DNA oligomers is spin selective, demonstrating a true organic spin filter. The selectivity exceeds that of any known system at room temperature. The spin dependent resistivity indicates that the effect cannot result solely from the atomic spin-orbit coupling and must relate to a special property resulting from the chirality symmetry. The results may reflect on the importance of spin in determining electron transfer rates through biological systems.

Direct detection of low-concentration NO in physiological solutions by a new GaAs-based sensor.

Nitric oxide (NO) acts as a signal molecule in the nervous system, as a defense against infections, as a regulator of blood pressure, and as a gate keeper of blood flow to different organs. In vivo, it is thought to have a lifetime of a few seconds. Therefore, its direct detection at low concentrations is difficult. We report on a new type of hybrid, organic-semiconductor, electronic sensor that makes detection of nitric oxide in physiological solution possible. The mode of action of the device is described to explain how its electrical resistivity changes as a result of NO binding to a layer of native hemin molecules. These molecules are self-assembled on a GaAs surface to which they are attached through a carboxylate binding group. The new sensor provides a fast and simple method for directly detecting NO at concentrations down to 1 microM in physiological aqueous (pH=7.4) solution at room temperature.

Spintronics and Chirality: Spin Selectivity in Electron Transport Through Chiral Molecules

Recent experiments have demonstrated that the electron transmission yield through chiral molecules depends on the electron spin orientation. This phenomenon has been termed the chiral-induced spin selectivity (CISS) effect, and it provides a challenge to theory and promise for organic molecule-based spintronic devices. This article reviews recent developments in our understanding of CISS. Different theoretical models have been used to describe the effect; however, they all presume an unusually large spin-orbit coupling in chiral molecules for the effect to display the magnitudes seen in experiments. A simplified model for an electrons transport through a chiral potential suggests that these large couplings can be manifested. Techniques for measuring spin-selective electron transport through molecules are overviewed, and some examples of recent experiments are described. Finally, we present results obtained by studying several systems, and we describe the possible application of the CISS effect for memory devices.