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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry