Abstract
Determining the composition of plasmonic nanoparticles is challenging due to a deficiency in tools capable of accurately evaluating the number of atoms. Mass spectrometry plays a significant role in determining nanoparticle composition at the atomic level. Significant progress has been made in understanding ultra-small gold nanoparticles, like Au25(SR)18 and Au38(SR)24, with a Au core diameter of 0.97 and 1.3 nm, respectively. However, progress in small plasmonic nanoparticles (2 - 5 nm) is currently challenging, due in part to limitations in synthesizing monodisperse nanoparticles. Here, we report a plasmonic nanocrystal that is highly monodisperse, with an unprecedented variation of less than 20 gold atoms. The composition of the super-stable plasmonic nanocrystals at 115 kDa was determined to contain Au500±10SR120±3. The Au~500 system, named Faraduarate-500, is the largest size to be characterized using high resolution ESI mass spectrometry. Atomic pair distribution function (PDF) data shows that the local atomic structure is consistent with a face-centered cubic (fcc) or Marks decahedral arrangement. High resolution scanning transmission electron microscopy images show that the diameter is 2.4 ± 0.1 nm. The radius of gyration measured by small angle X-ray scattering (SAXS), is 1.05 ± 0.05 nm, and the size and the shape of SAXS molecular envelope are in agreement with TEM and PDF measurements.
