Ab initio electronic circular dichroism of fullerenes, single-walled carbon nanotubes, and ligand-protected metal nanoparticles.

The versatility and applicability of a time-perturbed density functional method implemented within the SIESTA program package to calculate electronic circular dichroism of diverse nanoparticles is discussed. Results for nanostructures, such as fullerenes, single-wall carbon nanotubes, as well as metallic nanoparticles composed of up to hundreds of atoms were examined by comparison with previously reported experimental and theoretical results. In all cases, the calculated electronic circular dichroism shows very good consistency with other calculations, and a remarkable agreement with experiments. It is concluded that such a high-level method provides theoretical support for the quantification, understanding, and prediction of chirality and its measurement in nanostructures. It is expected that this information would be useful to motivate further experimental studies and interpretation of optical activity in terms of electronic circular dichroism in novel nanostructures.

Active stabilization of a pseudoheterodyne scattering scanning near field optical microscope.

Scattering scanning near-field optical microscopes (s-SNOMs) based on pseudoheterodyne detection and operating at ambient conditions typically suffer from instabilities related to the variable optical path length of the interferometer arms. These cause strong oscillations in the measured optical amplitude and phase comparable with those of the signal and, thus, resulting in dramatic artifacts. Besides hampering the comparison between the topography and the optical measurements, such oscillations may lead to misinterpretations of the physical phenomena occurring at the sample surface, especially for nanostructured materials. Here, we propose a stabilizing method based on interferometer phase control, which improves substantially the image quality and allows the correct extraction of optical phase and amplitude for both micro- and nanostructures. This stabilization method expands the measurement capabilities of s-SNOM to any slowly time-dependent phenomena that require long-term stability of the system. We envisage that active stabilization will increase the technological significance of s-SNOMs and will have far-reaching applications in the field of heat transfer and nanoelectronics.

Designing the plasmonic response of shell nanoparticles: spectral representation.

A spectral representation formalism in the quasistatic limit is developed to study the optical response of nanoparticles, such as nanospheres, nanospheroids, and concentric nanoshells. A transfer matrix theory is formulated for systems with an arbitrary number of shells. The spectral representation formalism allows us to analyze the optical response in terms of the interacting surface plasmons excited at the interfaces by separating the contributions of the geometry from those of the dielectric properties of each shell and surroundings. Neither numerical nor analytical methods can do this separation. These insights into the physical origin of the optical response of multishelled nanoparticles are very useful for engineering systems with desired properties for applications in different fields ranging from materials science and electronics to medicine and biochemistry.

On the origin of the optical activity displayed by chiral-ligand-protected metallic nanoclusters.

Ligand-protected metallic clusters exhibit optical activity when chiral molecules are used as protecting units. Various mechanisms, such as the inherently chiral metallic cluster core, the dissymmetric field effect, and the chiral footprint model, have been proposed as possible explanations of the nonzero circular dichroism (CD) spectra found for these nanoscale materials. This communication presents a first-principles theoretical study of the CD spectrum of the [Au(25)(SR)(18)](-) cluster that was undertaken to gain insight into the physicochemical origin of the optical activity measured for the glutathione-protected [Au(25)(SG)(18)](-) cluster. The calculated CD spectrum of the cysteine-protected cluster, with R(cys) = C(beta)H(2)-C(alpha)H(NH(2))-COOH, shows good agreement with the experimental data obtained for the glutathione-protected cluster. Analysis of the calculated CD spectra of the peculiar two-shell metallic core and the two distinct thiolate-Au binding modes existing in the [Au(25)(SR(cys))(18)](-) cluster showed that the weak CD signal due to the slight distortion of cluster core is enhanced by the dissymmetric location of the ligands forming the Au-S binding modes. This result shows that the mechanisms proposed to explain the optical activity of chiral-ligand-protected metallic clusters cannot be differentiated but are acting concurrently. It is also predicted that the CD line shape should be highly sensitive to the orientation of the thiolate ligands forming the cluster protecting layer and to the stability of the thiolate-Au binding modes.

Unfolding method for periodic twisted systems with commensurate Moiré patterns.

We present a general unfolding method for the electronic bands of systems with double-periodicity. Within density functional theory with atomic orbitals as basis-set, our method takes into account two symmetry operations of the primitive cell: a standard expansion and a single rotation, letting to elucidate the physical effects associated to the mutual interactions between systems with more than one periodicity. As a result, our unfolding method allows studying the electronic properties of vertically stacked two-dimensional homo- or heterostructures. We apply our method to study [Formula: see text] single-layer graphene, [Formula: see text] twisted single-layer graphene, and [Formula: see text] graphene- [Formula: see text] tungsten disulfide heterostructure with an interlayer angle of [Formula: see text]. Our unfolding method allows observing typical mini gaps reported in heterostructures, as well as other electronic deviations from pristine structures, impossible to distinguish without an unfolding method. We anticipate that this unfolding method can be useful to compare with experiments to elucidate the electronic properties of two-dimensional homo- or heterostructures, where the interlayer angle can be considered as an additional parameter.

Diffractive dipolar coupling in non-Bravais plasmonic lattices.

Honeycomb plasmonic lattices are paradigmatic examples of non-Bravais lattices. We experimentally measure surface lattice resonances in effectively free-standing honeycomb lattices composed of silver nanospheres. By combining numerical simulations with analytical methods, we analyze the dispersion relation and the near-field properties of these modes along high symmetry trajectories. We find that our results can be interpreted in terms of dipole-only interactions between the two non-equivalent triangular sublattices, which naturally lead to an asymmetric near-field distribution around the nanospheres. We generalize the interaction between the two sublattices to the case of variable adjacent interparticle distance within the unit cell, highlighting symmetry changes and diffraction degeneracy lifting associated to the transition between Bravais and non-Bravais lattices.

Theoretical study of surface plasmon resonances in hollow gold-silver double-shell nanostructures.

A theoretical model has been developed to study the optical properties of metallic multishell structures on the nanometer scale. The Mie theory was generalized for multiconcentric spherical shell nanostructures and employed to determine the effects and importance of the different parameters of the system such as thickness, size, and other material properties, for instance, the medium index of refraction. A unique hollow gold-silver double-shell structure is used as an example to test the model developed with recent experiments. The surface plasmon resonance (SPR) absorption spectrum of this structure has been calculated as a function of various parameters, including shell thickness and diameter. Using parameters similar to those previously reported experimentally, very good agreement has been found between calculated and experimentally measured SPR spectra, which validates the model. The results provide new insights into the fundamental properties of complex metal nanostructures that give us the ability to control the optical response, which has important implications in the synthesis of new metal nanostructures as well as their application in emerging technologies.

Large optical birefringence by anisotropic silver nanocomposites.

A large optical birefringence of oriented Ag nanoellipsoids embedded in silica was measured using an ellipsometric technique. The two main surface plasmon resonances associated with the axes of the ellipsoid were tuned, allowing us to quantify the light transmission through the samples when placed and rotated between crossed and parallel polarizers. This birefringence can be physically associated with the selective optical absorption of one component of the linear polarization of the incident light with respect to the anisotropic axis of the sample, depending on the wavelength used to perform the measurement.

Atomic structure of small and intermediate-size silver nanoclusters.

Molecular dynamic simulations were performed to study the morphology and binding energy of the most stable isomers of silver clusters with diameters of less than 2 nm. A 5-fold symmetry was found in most cases, and a novel morphology for the clusters of 39 and 116 silver atoms was identified. This morphology can be understood in terms of decahedral and icosahedral geometries, which are intercalated, as we explain in detail. These kind of structures have been observed for gold and now are predicted for small and intermediate silver nanoparticles.

How to control optical activity in organic-silver hybrid nanoparticles.

The mechanisms that originate and control optical activity in organic-metal hybrid nanoparticles (NPs) are identified using a time-perturbed density functional theory. Electronic circular dichroism (CD) is studied in terms of the intrinsic chirality of the ligands, the number of ligands and the induced chirality by the arrangement of the ligands on the NP. Left-handed cysteine and achiral methylthio ligands adsorbed on an icosahedral silver NP are investigated. The analysis of CD allows the identification of the spectral regions when the induced chirality by the ligand array dominates over the intrinsic chirality of the ligands, determining conditions for CD control and enlargement. These results would be significant in the discussion of experimental CD spectra of organic-metal hybrid NPs, which might allow the development of new strategies to improve the sensitivity of chiroptical spectroscopies for the identification of bio and organic molecules.

Chiral atomically thin films.

Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg µm(-1)) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

Optical absorbance of colloidal suspensions of silver polyhedral nanoparticles.

The optical absorption of colloidal suspensions made of silver nanoparticles with polyhedral shapes is studied experimentally and theoretically. The influence of the shape on the optical response is investigated by comparing the measured absorbance with theoretical results for icosahedral, decahedral, and cuboctahedral silver nanoparticles. The theoretical spectra are obtained within the discrete dipole approximation. We find that colloidal suspensions of silver nanoparticles with a small dispersion of size distribution show very few structural shapes.

Metallic influence on the atomic structure and optical activity of ligand-protected nanoparticles: a comparison between Ag and Au.

Using time-perturbed density functional theory the optical activity of metal-thiolate compounds formed by highly symmetric Ag and Au nanoparticles (NPs) and a methyl-thiol molecule is studied after performing atomic optimizations and electronic calculations upon adsorption. Many different sites and orientations of the adsorbed molecule on icosahedral Ag and Au NPs of 55 atoms are considered. Upon molecular adsorption atomic distortions on Au NPs are induced while not on Ag, which causes higher molecular adsorption energies in Au than in Ag. Structural distortions and the specific molecular adsorption site and orientation result in chiral metal-thiolate NPs. Ag and Au compounds with similar chirality, according to Hausdorff chirality measurements, show different optical activity signatures, where circular dichroism spectra of Au NPs are more intense. These dissimilarities are attributed in part to the differences in the electronic density of states, which are a consequence of relativistic effects and the atomic distortion. It is concluded that the optical activity of Ag and Au compounds is due to different mechanisms, while in Au it is mainly due to the atomic distortion of the metallic NPs induced after molecular adsorption, in Ag it is defined by the adsorption site and molecular orientation with respect to the NP symmetry.

Optical activity of achiral ligand SCH3 adsorbed on achiral Ag55 clusters: relationship between adsorption site and circular dichroism.

The electronic circular dichroism (CD) spectra of a methyl-thiol adsorbed at different sites on an icosahedral silver nanoparticle is studied by using time-perturbed density functional theory. Despite that separately molecule and nanoparticle are achiral and consequently optically inactive, the Ag(55)-SCH(3) compound emerges with a new symmetry, which may be chiral or not depending on the adsorption site and orientation of the molecule. It is found that chirality is favored when the thiol is adsorbed between two atoms of different coordination number. Chiral compounds have characteristic CD spectra in the UV-visible region, where Ag(55) shows optical absorption but SCH(3) does not; revealing that highly degenerated molecular-like electronic states of Ag(55) are modified by the presence of the molecule inducing optical activity. It is concluded that CD line-shapes and magnitude strongly depend on the site where the adsorption takes place, while its intensity is modulated by the molecule orientation.

Optically active metal nanoparticles.

Optical activity and its relation with chiral metal nanoparticles are revised in this tutorial review. The experimental evidence as well as the different mechanisms to explain the optical activity of ligand-protected nanoparticles are described, emphasizing the aspects that provide insights into this novel phenomenon at the nanoscale. The perspectives of this research field and a list of unsolved problems are presented. This tutorial review provides information for an interdisciplinary community working in synthesis, characterization and utilization of chiral metal nanoparticles.