This Account provides an overview of the methods that are currently being used to study the electromagnetics of silver and gold nanoparticles, with an emphasis on the determination of extinction and surface-enhanced Raman scattering (SERS) spectra. These methods have proven to be immensely useful in recent years for interpreting a wide range of nanoscience experiments and providing the capability to describe optical properties of particles up to several hundred nanometers in dimension, including arbitrary particle structures and complex dielectric environments (adsorbed layers of molecules, nearby metal films, and other particles). While some of the methods date back to Mie's celebrated work a century ago, others are still at the forefront of algorithm development in computational electromagnetics. This Account gives a qualitative description of the physical and mathematical basis behind the most commonly used methods, including both analytical and numerical methods, as well as representative results of applications that are relevant to current experiments. The analytical methods that we discuss are either derived from Mie theory for spheres or from the quasistatic (Gans) model as applied to spheres and spheroids. In this discussion, we describe the use of Mie theory to determine electromagnetic contributions to SERS enhancements that include for retarded dipole emission effects, and the use of the quasistatic approximation for spheroidal particles interacting with dye adsorbate layers. The numerical methods include the discrete dipole approximation (DDA), the finite difference time domain (FDTD) method, and the finite element method (FEM) based on Whitney forms. We discuss applications such as using DDA to describe the interaction of two gold disks to define electromagnetic hot spots, FDTD for light interacting with metal wires that go from particle-like plasmonic response to the film-like transmission as wire dimension is varied, and FEM studies of electromagnetic fields near cubic particles.

We report the light-to-heat energy transfer efficiencies of gold nanoparticles with variable sizes by assessing the temperature profiles of laser-activated particle suspensions in water. Gold nanoparticles with sizes ranging from 5 to 50 nm were synthesized by chemical reduction methods using sodium borohydride, sodium citrate, or hydroquinone as reducing agents. As-synthesized gold nanoparticle solution (1 mL) was loaded into a quartz cuvette and exposed to a CW green laser (532 nm). Heat input into the system by energy transfer from nanoparticles equals heat dissipation at thermal equilibrium. The transducing efficiency was then determined by plotting temperature increase as a function of laser power extinction. The efficiency increases from 0.650 ± 0.012 to 0.803 ± 0.008 as the particle size decreases from 50.09 ± 2.34 to 4.98 ± 0.59 nm, respectively. The results indicate that the photothermal properties of gold nanoparticles are size-tunable, and the variation of efficiency can be correlated to the absorption/extinction ratios calculated by Mie theory for different particle sizes. We further expanded our Mie theory calculations of absorption/extinction ratios to a broader range of diameters and wavelengths. These studies are crucial for practical applications of gold nanoparticles in nanotechnology and bioengineering, such as enhancing the treatment efficiency of laser surgery.

Make like a leaf: The synthesis and characterization of a family of “flowerlike” Au/Fe3O4 nanoparticles is described, whereby Fe3O4 “leaves” adhere to a gold core (see image). The size and numbers of iron oxide domains can be adjusted flexibly by changing the proportion of the starting materials and the reaction time.

We study the influence of a substrate on the surface plasmon resonance absorption in silver nanoparticles depending on the distance between the nanoparticles and the substrate. The experimentally observed red shift of the resonant absorption is explained in the frame of the image-induced charges at the interface between the ambient medium and the substrate. The influence of a metallic substrate is negligible when the clusters are at a distance d>2R from the substrate. A dielectric substrate has much less influence on the optical response of silver clusters than a metallic one.

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