First-principles investigation on dimerization of metal-encapsulated gold nanoclusters

Abstract

Density functional theory is used to study dimerization of metal-encapsulated gold nanoclusters M@Au₁₂ (M = W, Mo) with I_h or O_h symmetry, and their structural and electronic properties. To determine the most stable dimer structure in each case, various configurations are considered. We find that during dimerization, gold atoms near the interface tend to form inter-cluster triangular bonds, which stabilize two monomer clusters by about 3.3–3.5 eV. The dimerization along a specific axis selected as the z axis causes the symmetry reduction of each M@Au₁₂ cluster resulting in the modification of electronic structures. It is found that all the stable dimers exhibit a much smaller HOMO–LUMO gap than those of their comprising monomers. Such a gap decrease is mainly attributed to the d_z² orbital splitting of the central atoms owing to dimerization. We also calculate the vibrational modes and the corresponding IR-active spectra, which are distinguishable for different dimer configurations. In addition, we find that the IR-active modes of the O_h-based dimer structures appear to be red-shifted in comparison to those of I_h-based ones. Thus, the IR spectra may be utilized experimentally to discriminate dimer configurations with different central metal atoms and/or dissimilar structural symmetries.