The remarkable relationship between the size, shape, and optical properties of silver nanoparticles is proving to be very useful in a range of high performance applications. Considerable effort and investment are focused on delivering silver nanoparticles with precise morphologies. However, the reliability of these particles is contingent upon the morphological stability, particularly against variations in the thermodynamic environment, such as changes in temperature. Using a combination of computational and theoretical approaches, we have constructed a size-and shape-dependent phase diagram of nanoscale silver and projected the optical emission spectrum to produce a detailed structure/property map at thermal equilibrium. This map demonstrates that faceted near-spherical shapes and spheres are the predominant morphologies in a Ag NPs colloidal sample at low and high temperatures, showing a light yellow color. However, samples with more faceted shapes such as cubes or tetrahedrons, which gain stability at sizes smaller than 8 nm at intermediate temperatures, will present brighter yellow hues and dark red colors, respectively.

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.

The importance of anisotropy in the optical response of metal nanoparticles of different end shapes is studied theoretically. The number, behavior, and localization of the plasmon modes in terms of the shape and elongation is revised in detail for silver, gold, and copper nanoparticles. It is found that the position of longitudinal and transversal modes depends not only on the aspect ratio but also on the nanoparticle end shape. Besides, the relation between nanoparticles' anisotropy and optical macroscopic birefringence is also analyzed for different shapes and materials.

The influence of morphology on the optical properties of silver nanoparticles is studied. A general relationship between the surface plasmon resonances and the morphology of each nanoparticle is established. The optical response is investigated for cubes and decahedrons with different truncations. We found that polyhedral nanoparticles composed with less faces show more surface plasmon resonances than spherical-like ones. It is also observed that the vertices of the nanoparticles play an important role in the optical response, because the sharpener they become, the greater the number of resonances. For all the nanoparticles, a main resonance with a dipolar character was identified as well as other secondary resonances of less intensity. It is also found that as the nanoparticle becomes more symmetric, the main resonance is always blue shifted.

The cover picture of this issue of physica status solidi (c) has been taken from the article [1].