In recent years, the possibility to induce chemical transformations by using tunable plasmonic modes has opened the question of whether we can control or create chemical hot spots in these systems. This can be rationalized as the reactive analogue of the well-established concept of optical hot spots, which have drawn a great deal of attention to plasmonic nanostructures for their ability to circumvent the far-field diffraction limit of conventional optical elements.

Although optical hot spots can be mainly defined by the geometry and permittivity of the nanostructures, the degrees of freedom influencing their photocatalytic properties appear to be much more numerous. In fact, the reactivity of plasmonic systems are deeply influenced by the dynamics and interplay of photons, plasmon-polaritons, carriers, phonons, and molecular states. These degrees of freedom can affect the reaction rates, the product selectivity, or the spatial localization of a chemical reaction. In this Account, we discuss the oportunities to control chemical hot spots by tuning the cascade of events that follows the excitation and decay of plasmonic modes in nanostructures.

We discuss a series of techniques to spatially map and image plasmonic nanoscale reactivity at the single photocatalyst level. We show how to optimize the reactivity of carriers by manipulating their excitation and decay mechanisms in plasmonic nanoparticles. In addition, the tailored generation of non-thermal phonons in metallic nanostructures and their dissipation is shown as a promise to understand and exploit thermal photocatalysis at the nanoscale. Understanding and controlling these processes is essential for the rational design of solar nanometric photocatalysts.

Nevertheless, the ultimate capability of a plasmonic photocatalyst to trigger a chemical reaction is correlated to its ability to navigate through, or even modify, the potential energy surface of a given chemical reaction. Here we reunite both worlds, the plasmonic photocatalysts and the molecular ones, identifying different energy transfer pathways and their influence on selectivity and efficiency of chemical reactions. We foresee that the migration from optical to chemical hot spots will greatly assist the understanding of ongoing plasmonic chemistry.