1997/05/01 by Marcos M. Alvarez, Joseph T. Khoury, T. Gregory Schaaff +3 · 9 citations
Materials Science · #Gold and Silver Nanoparticles Synthesis and Applications #Nanocluster Synthesis and Applications #Quantum Dots Synthesis And Properties
paper · doi:10.1021/jp962922n
openalex publication_date 1997/05/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/02
The optical absorption spectra of a series of nanocrystal gold molecules larger, crystalline Au clusters that are passivated by a compact monolayer of n -alkylthiol(ate)s have been measured across the electronic range (1.1−4.0 eV) in dilute solution at ordinary temperature. Each of the ∼20 samples, ranging in effective core diameter from 1.4 to 3.2 nm (∼70 to ∼800 Au atoms), has been purified by fractional crystallization and has undergone a separate compositional and structural characterization by mass spectrometry and X-ray diffraction. With decreasing core mass (crystallite size) the spectra uniformly show a systematic evolution, specifically (i) a broadening of the so-called surface-plasmon band until it is essentially unidentifiable for crystallites of less than 2.0 nm effective diameter, (ii) the emergence of a distinct onset for strong absorption near the energy (∼1.7 eV) of the interbandgap (5d → 6sp), and (iii) the appearance in the smallest crystallites of a weak steplike structure above this onset, which is interpreted as arising from a series of transitions from the continuum d-band to the discrete level structure of the conduction band just above the Fermi level. The classical electrodynamic (Mie) theory, based on bulk optical properties, can reproduce this spectral evolution and thereby yield a consistent core-sizing only by making a strong assumption about the surface chemical interaction. Quantitative agreement with the spectral line shape requires a size-dependent offset of the frequency-dependent dielectric function, which may be explained by a transition in electronic structure just below 2.0 nm (∼200 atoms), as proposed earlier.