The impact of size and shape distributions on the electron charge transfer properties of silver nanoparticles

Many applications of silver nanoparticles are moderated by the electron charge transfer properties, such as the ionization potential, electron affinity and Fermi energy, which may be tuned by controlling the size and shape of individual particles. However, since producing samples of silver nanoparticles that are perfectly monodispersed in terms of both size and shape can be prohibitive, it is important to understand how these properties are impacted by polydispersivity, and ideally be able to predict the tolerance for variation of different geometric features. In this study, we use straightforward statistical methods, together with electronic structure simulations, to predict the electron charge transfer properties of different types of ensembles of silver nanoparticles and how restricting the structural diversity in different ways can improve or retard performance. In agreement with previous reports, we confirm that restricting the shape distribution will tune the charge transfer properties toward specific reactions, but by including the quality factors for each case we go beyond this assessment and show how targeting specific classes of morphologies and restricting the distribution of size can impact sensitivity.