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Energetic and optical properties of plasmonic nanocrystals strongly depend on their sizes, shapes, and composition. Whereas using plasmonic nanoparticles in biotesting has become routine, applications of plasmonics in energy are still early in development. Here, we investigate hot electron (HE) generation and related electromagnetic effects in both mono- and bi-metallic nanorods (NRs) and focus on one promising type of bi-metallic nanocrystals - core-shell Au-Ag nanorods. The spectra of the NRs are broadband, highly tunable with their geometry, and have few plasmon resonances. In this work, we provide a new quantum formalism describing the HE generation in bi-metallic nanostructures. Interestingly, we observe that the HE generation rate at the UV plasmon resonance of Au-Ag NRs appears to be very high. These HEs are highly energetic and suitable for carbon-fuel reactions. Simultaneously, the HE generation at the longitudinal plasmon (L-plasmon) peaks, which can be tuned from the yellow to near-IR, depends on the near-field and electromagnetic Mie effects, limiting the HE efficiencies for the long and large NRs. These properties of the L-plasmon relate to all kinds of NRs (Au, Ag, and Au-Ag). We also consider the generation of the interband d-holes in Au and Ag, since the involvement of the d-band is crucial for the energetic properties of UV plasmons. The proposed formalism is an important development for the description of bi-metallic (or tri-metallic, or more complex) nanostructures, and it paves the way to the efficient application of the plasmonic HEs and hot holes in sensing, nanotechnology, photocatalysis, and electrophotochemistry.

In this work, we use artificial neural networks (ANNs) to recognize the material composition, sizes of nanoparticles and their concentrations in different media with high accuracy, solely from the absorbance spectrum of a macroscopic sample. We construct ANNs operating in the following two schemes. The first scheme is designed to recognize the dimensions and refractive indices of dielectric scatterers in mixed ensembles. The second ANN model simultaneously recognizes the dimensions of gold nanospheres in a mixture and the refractive index of a matrix. A challenge in the first scheme arises at and near the invisibility point, i.e., when the refractive index of nanoparticles is close to that of the medium. Of course, particle recognition in this regime faces fundamental physical limitations. However, such recognition near the invisibility point is possible, and our study reveals its unique properties. Interestingly, the recognition process for the refractive index in the vicinity of the invisibility point shows very small errors. In contrast, the errors for the recognition of the radius grow strongly near this point. Another regime with limited recognition occurs when the extinction spectra are not unique and can correspond to different realizations of nanoparticle mixtures. Regarding multi-particle or polydisperse solutions, the ML-based models should in such cases be rationally restricted to maintain the feasibility of the recognition process. Overall, the recognition schemes proposed and investigated by us can find their applications in the field of sensing.

Chirality, either of light or matter, has proved to be very practical in biosensing and nanophotonics. However, the fundamental understanding of its temporal dynamics still needs to be discovered. A realistic setup for this are the so-called metastructures, since they are optically active and are built massively, hence rendering an immediate potential candidate. Here we propose and study the electromagnetic-optical mechanism leading to chiral optical imprinting on metastructures. Induced photothermal responses create anisotropic permittivity modulations, different for left or right circularly polarized light, leading to temporal-dependent chiral imprinting of hot-spots, namely imprinting of chirality. The above effect has not been observed yet, but it is within reach of modern experimental approaches. The proposed nonlinear chiroptical effect is general and should appear in any anisotropic material; however, we need to design a particular geometry for this effect to be strong. These new chiral time-dependent metastructures may lead to a plethora of applications., Comment: Main (29 pages, 6 figures) and supplemental (46 pages, 35 figures)

Developing colloidal plasmonic nanomaterials with high carrier density that show optical resonances and photochemical activity extending from the visible to the mid-infrared (MIR) ranges remains a challenging pursuit. Here, we report the fabrication of titanium nitride (TiN) nanobars obtained using a two step procedure based on a wet chemical route synthesis of TiO2 nanowires and their subsequent high temperature annealing in ammonia flow. Electromagnetic simulations of the resulting TiN nanobars reveal a rich set of optical resonances featuring transverse, longitudinal and mixed transverse longitudinal plasmonic modes that cover energies from the visible to MIR region. TiN nanobars decorated with Pt co catalyst nanocrystals show enhanced photocatalytic hydrogen evolution activity in comparison to both isotropic TiN nanospheres of similar size and TiN nanocubes under near infrared excitation at 940 nm due to the enhanced hot electron generation. We also demonstrate that plasmonic TiN nanobars can be used for the detection of furfural molecular vibrations by providing a strong surface enhanced infrared absorption (SEIRA) effect in the MIR region., Comment: 78 pages, 4 Figures main article, 39 Figures for Supporting Information

In plasmonics, and particularly in plasmonic photochemistry, the effect of hot-electron generation is an exciting phenomenon driving new fundamental and applied research. However, obtaining a microscopic description of the hot-electron states represents a challenging problem, limiting our capability to design efficient nanoantennas exploiting these excited carriers. This paper addresses this limitation and studies the spatial distributions of the photophysical dynamic parameters controlling the local surface photochemistry on a plasmonic nanocrystal. We found that the generation of energetic electrons and holes in small plasmonic nanocrystals with complex shapes is strongly position-dependent and anisotropic, whereas the phototemperature across the nanocrystal surface is nearly uniform. Our formalism includes three mechanisms for the generation of excited carriers: the Drude process, the surface-assisted generation of hot-electrons in the sp-band, and the excitation of interband d-holes. Our computations show that the hot-carrier generation originating from these mechanisms reflects the internal structure of hot spots in nanocrystals with complex shapes. The injection of energetic carriers and increased surface phototemperature are driving forces for photocatalytic and photo-growth processes on the surface of plasmonic nanostructures. Therefore, developing a consistent microscopic theory of such processes is necessary for designing efficient nanoantennas for photocatalytic applications.

Chirality is a fundamental feature in all domains of nature, ranging from particle physics over electromagnetism to chemistry and biology. Chiral objects lack a mirror plane and inversion symmetry and therefore cannot be spatially aligned with their mirrored counterpart, their enantiomer. Both natural molecules and artificial chiral nanostructures can be characterized by their light-matter interaction, which is reflected in circular dichroism (CD). Using DNA origami, we assemble model meta-molecules from multiple plasmonic nanoparticles, representing meta-atoms accurately positioned in space. This allows us to reconstruct piece by piece the impact of varying macromolecular geometries on their surrounding optical near fields. Next to the emergence of CD signatures in the instance that we architect a third dimension, we design and implement sign flipping signals through addition or removal of single particles in the artificial molecules. Our data and theoretical modelling reveal the hitherto unrecognized phenomenon of chiral plasmonic-dielectric coupling, explaining the intricate electromagnetic interactions within hybrid DNA-based plasmonic nanostructures., Comment: Article and Supporting Information

This article deals with the development of an interactive up-to-date Pacific Islands Web GIS Atlas. It focuses on the compilation of spatial data from the twelve member countries of the University of the South Pacific (Cook Islands, Fiji Islands, Kiribati Islands, Marshall Islands, Nauru, Niue, Tonga, Tuvalu, Tokelau, Solomon Islands, Vanuatu, and Western Samoa). A previous bitmap web Atlas was created in 1996, and was a pilot activity investigating the potential for using Geographical Information Systems (GIS) in the South Pacific. The objective of the new atlas is to provide sets of spatial and attributive data and maps for use of educators, students, researchers, policy makers and other relevant user groups and the public. GIS is a highly flexible and dynamic technology that allows the construction and analysis of maps and data sets from a variety of sources and formats. Nowadays, GIS application has moved from local and client-server applications to a three-tier architecture: Client (Web Browser) -- Application Web Map Server -- Spatial Data Warehouses. The objective of this project is to produce an Atlas that will include interactive maps and data on an Application Web Map Server. Intergraph products such as GeoMedia Professional, Web Map and Web Publisher have been selected for the web atlas production and design. In an interactive environment, an atlas will be composed from a series of maps and data profiles, which will be based on legend entries, queries, hot spots and cartographic tools. Only the first stage of development of the atlas and related technological solutions are outlined in this article., Comment: Project report article to Intergraph. (GeoMedia Research Laboratory Initiative)

Nature has developed striking light-powered proteins such as bacteriorhodopsin, which can convert light energy into conformational changes for biological functions. Such natural machines are a great source of inspiration for creation of their synthetic analogues. However, synthetic molecular machines typically operate at the nanometre scale or below. Translating controlled operation of individual molecular machines to a larger dimension, for example, to 10-100 nm, which features many practical applications, is highly important but remains challenging. Here we demonstrate a light-driven plasmonic nanosystem that can amplify the molecular motion of azobenzene through the host nanostructure and consequently translate it into reversible chiroptical function with large amplitude modulation. Light is exploited as both energy source and information probe. Our plasmonic nanosystem bears unique features of optical addressability, reversibility and modulability, which are crucial for developing all-optical molecular devices with desired functionalities.

We present a comprehensive review of recent developments in the field of chiral plasmonics. Significant advances have been made recently in understanding the working principles of chiral plasmonic structures. With advances in micro- and nanofabrication techniques, a variety of chiral plasmonic nanostructures have been experimentally realized; these tailored chiroptical properties vastly outperform those of their molecular counterparts. We focus on chiral plasmonic nanostructures created using bottom-up approaches, which not only allow for rational design and fabrication but most intriguingly in many cases also enable dynamic manipulation and tuning of chiroptical responses. We first discuss plasmon-induced chirality, resulting from the interaction of chiral molecules with plasmonic excitations. Subsequently, we discuss intrinsically chiral colloids, which give rise to optical chirality owing to their chiral shapes. Finally, we discuss plasmonic chirality, achieved by arranging achiral plasmonic particles into handed configurations on static or active templates. Chiral plasmonic nanostructures are very promising candidates for real-life applications owing to their significantly larger optical chirality than natural molecules. In addition, chiral plasmonic nanostructures offer engineerable and dynamic chiroptical responses, which are formidable to achieve in molecular systems. We thus anticipate that the field of chiral plasmonics will attract further widespread attention in applications ranging from enantioselective analysis to chiral sensing, structural determination, and in situ ultrasensitive detection of multiple disease biomarkers, as well as optical monitoring of transmembrane transport and intracellular metabolism.

We theoretically study hot electron generation through the emission of a dipole source coupled to a nanoresonator on a metal surface. In our hybrid approach, we solve the time-harmonic Maxwell's equations numerically and apply a quantum model to predict the efficiency of hot electron generation. Strongly confined electromagnetic fields and the strong enhancement of hot electron generation at the metal surface are predicted and are further interpreted with the theory of quasinormal modes. In the investigated nanoresonator setup, both the emitting source and the acceptor resonator are localized in the same volume, and this configuration looks promising to achieve high efficiencies of hot electron generation. By comparing with the efficiency calculated in the absence of the plasmonic nanoresonator, that is, the dipole source is located near a flat, unstructured metal surface, we show that the effective excitation of the modes of the nanoresonator boosts the generation efficiency of energetic charge carriers. The proposed scheme can be used in tip-based spectroscopies and other optoelectronic applications.

Molecular chirality plays a crucial role in innumerable biological processes. The chirality of a molecule can typically be identified by its characteristic optical response, the circular dichroism (CD). CD signals have thus long been used to identify the state of molecules or to follow dynamic protein configurations. In recent years, the focus has moved towards plasmonic nanostructures, as they show potential for applications ranging from pathogen sensing to novel optical materials. The plasmonic coupling of the individual elements of such chiral metallic structures is a crucial prerequisite to obtain sizeable CD signals. We here identified and implemented various coupling entities - chiral and achiral - to obtain chiral transfer over distances close to 100 nm. The coupling is realized by an achiral nanosphere situated between a pair of gold nanorods that are arranged far apart but in a chiral fashion. We synthesized these structures with nanometer precision using DNA origami and obtained sample homogeneity that allowed us to directly demonstrate efficient chiral energy transfer between the distant nanorods. The transmitter particle causes a strong enhancement in amplitude of the CD response, the emergence of an additional chiral feature at the resonance frequency of the nanosphere, and a redshift of the longitudinal plasmonic resonance frequency of the nanorods. Numerical simulations closely match our experimental observations and give insights in the intricate behavior of chiral optical fields and the transfer of plasmons in complex architectures., Comment: Manuscript including SI, 35 pages

We prove #P-completeness results for counting edge colorings on simple graphs. These strengthen the corresponding results on multigraphs from [4]. We prove that for any $\kappa \ge r \ge 3$ counting $\kappa$-edge colorings on $r$-regular simple graphs is #P-complete. Furthermore, we show that for planar $r$-regular simple graphs where $r \in \{3, 4, 5\}$ counting edge colorings with \k{appa} colors for any $\kappa \ge r$ is also #P-complete. As there are no planar $r$-regular simple graphs for any $r > 5$, these statements cover all interesting cases in terms of the parameters $(\kappa, r)$.

The authors of preprint arXiv:2009.00286 and paper Appl. Phys. Lett. 117, 130501 (2020), Y. Sivan and Y. Dubi, made several wrong and inconsistent comments on our papers [J. Phys. Chem. C 117, 16616-16631 (2013), ACS Photonics 4 (11), 2759-2781 (2017)]. Moreover, the authors of arXiv:2009.00286 addressed in their comments features that were not present in our paper [ACS Photonics 4 (11), 2759-2781 (2017)]. In this document we go through the comments made in arXiv:2009.00286, which we found to be wrong and misleading., Comment: 7 pages

The complexity of graph homomorphisms has been a subject of intense study [11, 12, 4, 42, 21, 17, 6, 20]. The partition function $Z_{\mathbf A}(\cdot)$ of graph homomorphism is defined by a symmetric matrix $\mathbf A$ over $\mathbb C$. We prove that the complexity dichotomy of [6] extends to bounded degree graphs. More precisely, we prove that either $G \mapsto Z_{\mathbf A}(G)$ is computable in polynomial-time for every $G$, or for some $\Delta > 0$ it is #P-hard over (simple) graphs $G$ with maximum degree $\Delta(G) \le \Delta$. The tractability criterion on $\mathbf A$ for this dichotomy is explicit, and can be decided in polynomial-time in the size of $\mathbf A$. We also show that the dichotomy is effective in that either a P-time algorithm for, or a reduction from #SAT to, $Z_{\mathbf A}(\cdot)$ can be constructed from $\mathbf A$, in the respective cases.

We consider the complexity of counting weighted graph homomorphisms defined by a symmetric matrix $A$. Each symmetric matrix $A$ defines a graph homomorphism function $Z_A(\cdot)$, also known as the partition function. Dyer and Greenhill [10] established a complexity dichotomy of $Z_A(\cdot)$ for symmetric $\{0, 1\}$-matrices $A$, and they further proved that its #P-hardness part also holds for bounded degree graphs. Bulatov and Grohe [4] extended the Dyer-Greenhill dichotomy to nonnegative symmetric matrices $A$. However, their hardness proof requires graphs of arbitrarily large degree, and whether the bounded degree part of the Dyer-Greenhill dichotomy can be extended has been an open problem for 15 years. We resolve this open problem and prove that for nonnegative symmetric $A$, either $Z_A(G)$ is in polynomial time for all graphs $G$, or it is #P-hard for bounded degree (and simple) graphs $G$. We further extend the complexity dichotomy to include nonnegative vertex weights. Additionally, we prove that the #P-hardness part of the dichotomy by Goldberg et al. [12] for $Z_A(\cdot)$ also holds for simple graphs, where $A$ is any real symmetric matrix.

Elucidating the underlying principles behind band gap engineering is paramount for the successful implementation of semiconductors in photonic and optoelectronic devices. Recently it has been shown that the band gap of a wide and direct band gap semiconductor, such as ZnO, can be modified upon co-crystallization with amino acids, with the role of the biomolecules remaining unclear. Here, by probing and modeling the light emitting properties of ZnO-amino acid co-crystals, we identify the amino acids role on this band gap modulation and demonstrate their effective chirality transfer to the inter-band excitations in ZnO. Our 3D quantum model suggests that the strong band edge emission blue shift in the co-crystals can be explained by a quasi-periodic distribution of amino acid potential barriers within the ZnO crystal lattice. Overall, our findings indicate that biomolecule co-crystallization can be used as a truly bio-inspired means to induce chiral quantum confinement effects in quasi-bulk semiconductors.

Graph homomorphism has been an important research topic since its introduction [17]. Stated in the language of binary relational structures in that paper [17], Lov\'asz proved a fundamental theorem that, for a graph $H$ given by its $0$-$1$ valued adjacency matrix, the graph homomorphism function $G \mapsto \hom(G, H)$ determines the isomorphism type of $H$. In the past 50 years various extensions have been proved by many researchers [18, 12, 1, 23, 21]. These extend the basic $0$-$1$ case to admit vertex and edge weights; but these extensions all have some restrictions such as all vertex weights must be positive. In this paper we prove a general form of this theorem where H can have arbitrary vertex and edge weights. A noteworthy aspect is that we prove this by a surprisingly simple and unified argument. This bypasses various technical obstacles and unifies and extends all previous known versions of this theorem on graphs. The constructive proof of our theorem can be used to make various complexity dichotomy theorems for graph homomorphism effective in the following sense: it provides an algorithm that for any $H$ either outputs a P-time algorithm solving $\hom(\cdot, H)$ or a P-time reduction from a canonical #P-hard problem to $\hom(\cdot, H)$.

We develop a theory of graph algebras over general fields. This is modeled after the theory developed by Freedman, Lov\'asz and Schrijver in [22] for connection matrices, in the study of graph homomorphism functions over real edge weight and positive vertex weight. We introduce connection tensors for graph properties. This notion naturally generalizes the concept of connection matrices. It is shown that counting perfect matchings, and a host of other graph properties naturally defined as Holant problems (edge models), cannot be expressed by graph homomorphism functions with both complex vertex and edge weights (or even from more general fields). Our necessary and sufficient condition in terms of connection tensors is a simple exponential rank bound. It shows that positive semidefiniteness is not needed in the more general setting.

Designing broadband metamaterial perfect absorbers is challenging due to the intrinsically narrow bandwidth of surface plasmon resonances. Here, the paper reports an ultra-broadband metamaterial absorber by using space filling Gosper curve. The optimized result shows an average absorptivity of 95.78% from 2.64 to 9.79 {\mu}m across the entire mid-infrared region. Meanwhile, the absorber shows insensitivity to the polarization angle and the incident angle of the incident light. The underlying physical principles, used in our broadband absorber, involve a fractal geometry with multiple scales and a dissipative plasmonic crystal. The broadband perfect absorption can be attributed to multiple electric resonances at different wavelengths supported by a few segments in the defined Gosper curve.

The authors of preprint arXiv:1810.00565 and paper in Light: Science & Applications (2019), Y. Dubi and Y. Sivan, made several wrong and inconsistent comments on several of our papers. In addition, the paper in Faraday Discuss. 214, 215-233 (2018) by the same authors also contains several wrong statements in relationship with our work. Moreover, the authors address in their comments features that were in fact not present in our work. In what follows we present correction to a number of specific points in which they either misrepresented or erroneously interpreted our published work., Comment: 22 pages, 2 figures, commentary

The chiral state of a molecule plays a crucial role in molecular recognition and biochemical reactions. Because of this and owing to the fact that most modern drugs are chiral, the sensitive and reliable detection of the chirality of molecules is of great interest to drug development. The majority of naturally occurring biomolecules exhibit circular dichroism (CD) in the UV-range. Theoretical studies and several experiments have demonstrated that this UV-CD can be transferred into the plasmonic frequency domain when metal surfaces and chiral biomolecules are in close proximity. Here, we demonstrate that the CD transfer effect can be drastically enhanced by placing chiral molecules, here double-stranded DNA, inside a plasmonic hotspot. By using different particle types (gold, silver, spheres and rods) and by exploiting the versatility of DNA origami we were able to systematically study the impact of varying particle distances on the CD transfer efficiency and to demonstrate CD transfer over the whole optical spectrum down to the near infrared. For this purpose, nanorods were also placed upright on our DNA origami sheets, this way forming strong optical antennas. Theoretical models, demonstrating the intricate relationships between molecular chirality and achiral electric fields, support our experimental findings.