Electron beams in Scanning Transmission Electron Microscopes (STEMs) can be used as a tool to induce movement on nanoparticles. Employing a classical-electrodynamics approach, it has been reported that the linear momentum transfer from a STEM-beam electron to a metallic spherical nanoparticle can be either repulsive or attractive towards the swift electron trajectory. This is in qualitative agreement with experimental observations. The interaction time between a swift electron and a nanoparticle is typically on the order of attoseconds. Hence, the electromagnetic response of the nanoparticle at short times is of utmost importance. However, it has been reported that the dielectric function employed in previous studies presented a non-causal pre-echo at the attosecond timescale, which might have lead to incorrect unphysical results. Therefore, the validity of these linear momentum transfer results should be revisited. In this theoretical work, we study the non-causality effects on the linear momentum transferred from a swift electron to a metallic nanoparticle, made of either aluminum or gold. Using an efficient numerical methodology, we found that non-causality, as well as deficient numerical convergence, may lead to incorrect repulsive linear momentum transfer results. Contrary to what previous theoretical studies have reported, our results show that the linear momentum transfer from a swift electron to spherical aluminum and gold nanoparticles, with radius 1 nm, is always attractive.
In the framework of swift heavy ion - matter interaction, the thermal spike has proved its worth since nearly two decades. This paper deals with the necessary refinement of the computation due to the kind of materials involved i.e. nanomaterials such as multilayered systems or composite films constitued of nanocylinders or nanospheres embedded in matrix. The three dimensional computation of the thermal spike model is applied for the first time in layers containing spherical nanoparticles embedded in a silica matrix. The temperature profile calculated at each point (x,y,z) of the target for tim…
The effect of smooth shape changes of metallic nanoparticles on localized surface plasmon resonances is assessed with a boundary integral equation method. The boundary integral equation method allows compact expressions of nanoparticle polarizability which is expressed as an eigenmode sum of terms that depends on the eigenvalues and eigenfunctions of the integral operator associated to the boundary integral equation method. Shape variations change not only the eigenvalues but also their coupling weights to the electromagnetic field. Thus, rather small changes in the shape may induce large vari…
We present an approach to master the well-known challenge of calculating the contribution of d-bands to plasmon-induced hot carrier rates in metallic nanoparticles. We generalise the widely used spherical well model for the nanoparticle wavefunctions to flat d-bands using the envelope function technique. Using Fermi's golden rule, we calculate the generation rates of hot carriers after the decay of the plasmon due to transitions from either a d-band state to an sp-band state or from an sp-band state to another sp-band state. We apply this formalism to spherical silver nanoparticles with radii …
Structural and energy stability results for a new class of decahedral structural motif termed decmon (Montejano's decahedra) are presented. After making proper truncations to the regular icosahedron, this structural motif presents exposed <100> and <111> facets, whose energetic competition make the structures very stable. It is also identified structural transitions as a function of the cluster size, the appearing and competition of surface reconstruction, and an outline for a path transformation from the Mackay icosahedra (I_h) to the regular decahedra (D_h) symmetry structures, as well as ex…
With a focus on platinum nanoparticles of different sizes (diameter of 1-9 nm) and shapes, we sequence their geometrical genome by recording the relative occurrence of all the non equivalent active site, classified according to the number of neighbours in their first and second coordination shell. The occurrence of sites is morphology and size dependent, with significant changes in the relative occurrence up to 9 nm. Our geometrical genome sequencing approach is immediately transferable to address the effects of the morphological polydispersivity in size-selected samples and the influence of t…
The self-assembly of metallic nanoparticles is a promising route to metasurfaces with unique properties for many optical applications, such as surface-enhanced spectroscopy, light manipulation, and sensing. We present an in-depth theoretical study of the optical properties of mono- and bilayers assembled from gold and silver nanoparticles. With finite-difference time-domain simulations, we predict the occurrence of two plasmon modes, a bright and a dark mode, which exhibit symmetric and antisymmetric dipole configurations between the layers, respectively. The dark mode resonance energy depends…
Motivated by the recent development of quantitative structure-activity relationship (QSAR) methods in the area of nanotoxicology, we proposed an approach to develop additional descriptors based on results of first principles calculations. For evaluation of the biochemical activity of metallic nanoparticles, we consider two processes: ion extraction from the surface of a specimen to aqueous media and water dissociation on the surface. We performed calculations for a set of metals (Al, Fe, Cu, Ag, Au, Pt). Taking into account the diversity of atomic structures of real metallic nanoparticles, we …
The atomistic structure of metallic glasses is closely related to properties such as strength and ductility. Here, Ni1-xBx metallic glass nanoparticles of two different sizes are compressed under quasi-hydrostatic high-pressure conditions in order to understand structural changes under stress. The structural changes in the nanoparticles were tracked using in situ high-pressure X-ray diffraction (XRD). The ambient pressure pair-distribution functions generated from XRD showed that the smaller sized nanoparticles had a more compact amorphous structure with lower coordination number. XRD showed t…
We demonstrate a remarkable equivalence in structure measured by total X-ray scattering methods between very small metallic nanoparticles and bulk metallic glasses (BMGs), thus connecting two disparate fields, shedding new light on both. Our results show that for nanoparticle diameters <5 nm the structure of Ni nanoparticles changes from fcc to the characteristic BMG-like structure, despite them being formed from a single element, an effect we call nano-metallic glass (NMG) formation. However, high-resolution TEM images of the NMG clusters exhibit lattice fringes indicating a locally well-orde…
We present a novel approach for finding and evaluating structural models of small metallic nanoparticles. Rather than fitting a single model with many degrees of freedom, the approach algorithmically builds libraries of nanoparticle clusters from multiple structural motifs, and individually fits them to experimental PDFs. Each cluster-fit is highly constrained. The approach, called cluster-mining, returns all candidate structure models that are consistent with the data as measured by a goodness of fit. It is highly automated, easy to use, and yields models that are more physically realistic an…
Understanding and mastering the mechanical properties of metallic nanoparticles is crucial for their use in a wide range of applications. In this context, we use atomic-scale (Molecular Dynamics) and continuous (Finite Elements) calculations to investigate in details gold nanoparticles under deformation. By combining these two approaches, we show that the elastic properties of such nanoobjects are driven by their size but, above all, by their shape. This outcome was achieved by introducing a descriptor in the analysis of our results enabling to distinguish among the different nanoparticle shap…
Harnessing hot electrons and holes resulting from the decay of localized surface plasmons in nanomaterials has recently led to new devices for photovoltaics, photocatalysis and optoelectronics. Properties of hot carriers are highly tunable and in this work we investigate their dependence on the material, size and environment of spherical metallic nanoparticles. In particular, we carry out theoretical calculations of hot carrier generation rates and energy distributions for six different plasmonic materials (Na, K, Al, Cu, Ag and Au). The plasmon decay into hot electron-hole pairs is described …
We show how standard Metadynamics coupled with classical Molecular Dynamics can be successfully ap- plied to sample the configurational and free energy space of metallic and bimetallic nanopclusters via the implementation of collective variables related to the pair distance distribution function of the nanoparticle itself. As paradigmatic examples we show an application of our methodology to Ag147, Pt147 and their alloy AgshellPtcore at 1:1 and 2:1 chemical compositions. The proposed scheme is not only able to reproduce known structural transformation pathways, as the five and the six square-d…
Metallic nanoparticles have been used as catalysts for various reactions, and the huge literature on the subject is hard to overlook. In many applications, the nanoparticles must be affixed to a colloidal carrier for easy handling during catalysis. These "passive carriers" (e.g., dendrimers) serve for a controlled synthesis of the nanoparticles and prevent coagulation during catalysis. Recently, hybrids from nanoparticles and polymers have been developed that allow us to change the catalytic activity of the nanoparticles by external triggers. In particular, single nanoparticles embedded in a t…
The validity of the linear elasticity theory is examined at the nanometer scale by investigating the vibrational properties of silver and gold nanoparticles whose diameters range from about 1.5 to 4 nm. Comparing the vibration modes calculated by elasticity theory and atomistic simulation based on the Embedded Atom Method, we first show that the anisotropy of the stiffness tensor in elastic calculation is essential to ensure a good agreement between elastic and atomistic models. Second, we illustrate the reduction of the number of vibration modes due to the diminution of the number of atoms wh…
Nanoscale inhomogeneities are typical for numerous metallic alloys and crucially important for their practical applications. At the same time, stabilization mechanisms of such a state are poorly understood. We present a general overview of the problem, together with a more detailed discussion of the prototype example, namely, Guinier-Preston zones in Al-based alloys. It is shown that coherent strain due to a misfit between inclusion and host crystal lattices plays a decisive role in the emergence of the inhomogeneous state. We suggest a model explaining formation of ultrathin plates (with the …
The electromagnetic interaction between Ag nanoparticles on the top of the Si substrate and the incident light has been studied by numerical simulations. It is found that the presence of a dielectric layer with different thickness leads to varied resonance wavelength and scattering cross section, and consequently shifted photocurrent response over all wavelengths. These different behaviors are determined by whether the dielectric layer is beyond the domain where the near field of nanoparticles takes effect, and geometrical optics effects must be taken into account. It is revealed that for part…
We study the optical properties of gold nanoparticles coated with a nematic liquid crystal whose director field is distributed around the nanoparticle according to the anchoring conditions at the surface of the nanoparticle. The distribution of the nematic liquid crystal is obtained by minimization of the corresponding Frank free-energy functional whilst the optical response is calculated by the discrete-dipole approximation. We find, in particular, that the anisotropy of the nematic liquid-crystal coating does not affect much the (isotropic) optical response of the nanoparticle. However, for …
We determined a full 3D atomic structure of a dumbbell-shaped Pt nanoparticle formed by a coalescence of two nanoclusters using deep learning assisted atomic electron tomography. Formation of double twin boundary was clearly observed at the interface, while substantial anisotropy and disorder were also found throughout the nanodumbbell. This suggests that the diffusion of interfacial atoms mainly governed the coalescence process, but other dynamic processes such as surface restructuring and plastic deformation were also involved. A full 3D strain tensor was clearly mapped, which allows direct …
Wereport the results of a sequence of magnetisation and magneto-optical studies on laser ablated thin films of ZnCoAlO and ZnCoO that contain a small amount of metallic cobalt. The results are compared to those expected when all the magnetization is due to isolated metallic clusters of cobalt and with an oxide sample that is almost free from metallic inclusions. Using a variety of direct magnetic measurements and also magnetic circular dichroism we find that there is ferromagnetism within both the oxide and the metallic inclusions, and furthermore that these magnetic components are exchange-co…
A detailed investigation of the electronic - and magneto - transport properties of Nd0.8Sr0.2MnO3 with the variation of grain size (down to 42 nm) is presented here. Interestingly, we observe that the ferromagnetic insulating state is suppressed and a metallic state is stabilized as the grain size of the sample is reduced. As a result, metal insulator transition is observed in this low doped manganite which is insulating in nature in its bulk form. Destabilization of polaronic order in the ferromagnetic insulating state due to enhanced surface disorder on grain size reduction has been attribut…
Atomistic simulations are performed to probe the anisotropic deformation in the compressions of face-centred-cubic metallic nanoparticles. In the elastic regime, the compressive load-depth behaviors can be characterized by the classical Hertzian model or flat punch model, depending on the surface configuration beneath indenter. On the onset of plasticity, atomic-scale surface steps serve as the source of heterogeneous dislocation in nanoparticle, which is distinct from indenting bulk materials. Under [111] compression, the gliding of jogged dislocation takes over the dominant plastic deformati…
Controlled integration of metallic nanoparticles (NPs) onto photonic nanostructures enables realization of complex devices for extreme light confinement and enhanced light-matter interaction. This can be achieved combining Nanoparticle-on-Mirror (NPoM) nanocavities with the light manipulation capabilities of micron-scale metallic antennas and/or photonic integrated waveguides. However, metallic nanoparticles are usually deposited via drop-casting, which prevents their accurate positioning. Here we present a methodology for precise transfer and positioning of individual NPs onto different photo…
Within first-principles density functional theory (DFT) frameworks, accurate but fast prediction of electronic structures of nanoparticles (NPs) remains challenging. Herein, we propose a machine-learning architecture to rapidly but reasonably predict electronic density of states (DOS) patterns of metallic NPs via a combination of principal component analysis (PCA) and the crystal graph convolutional neural network (CGCNN). By applying PCA, one can convert a mathematically high-dimensional DOS image to a low-dimensional vector. The CGCNN plays a key role in reflecting the effects of local atomi…
Silver-doped ZnO nanoparticles were successfully fabricated at $400\,^{\circ}\mathrm{C}$ via a simple and rapid method based on short time solid state milling and calcination of precursor powders. The effect of Ag dilute doping on the structural, optical, and photocatalytic properties of ZnO nanoparticles was investigated by X-ray diffraction (XRD), UV-vis spectrophotometer and photoluminescence (PL) spectroscopy.~X-ray analysis revealed that Ag doped ZnO solidified in hexagonal wurtzite structure.~ The intensity of deep level emission was reduced with increasing silver doping in PL measuremen…
While most of the experimental studies are dealing with partially oxidized metallic nanosolids, their behaviour is not well understood theoretically. To this end we utilized molecular dynamics simulation and charge-optimized many-body potential to probe melting of Cu nanoparticles and nanowires with and without a monolayer of Cu$_2$O as a shell. It is shown that partially oxidized nanosolids present a different melting behaviour than the widely accepted picture of melting, and especially different than surface melting. (i) For both types of nanosolids we observed inward diffusion of $\sim$40\%…
A swift chemical route to synthesize Co-doped SnO$_2$ nanopowders is described. Pure and highly stable Sn$_{1-x}$Co$_x$O$_{2-δ}$ (0 $\le$ x $\le$ 0.15) crystalline nanoparticles were synthesized, with mean grain sizes < 5 nm and the dopant element homogeneously distributed in substitutional sites of the SnO$_2$ matrix. The UV-visible diffuse reflectance spectra of the Sn$_{1-x}$Co$_x$O$_{2-δ}$ samples reveal red shifts, the optical bandgap energies decreasing with increasing Co concentration. The Urbach energies of the samples were calculated and correlated with their bandgap energies. The pho…
DNA origami is a novel self-assembly technique allowing one to form various 2D shapes and position matter with nanometer accuracy. It has been used to coordinate placement of nanoscale objects, both organic and inorganic; to make molecular motors and walkers; and to create optically active nanostructures. Here we use DNA origami templates to engineer Surfaced Enhanced Raman Scattering (SERS) substrates. Specifically, gold nanoparticles were selectively attached to the corners of rectangular origami and subsequently enlarged via solution-based metal deposition. The resulting assemblies were des…
