Abstract
Density functional theory (DFT) calculations have been performed to develop a systematic structural analysis of Au13L83+, where L = SCH3, SeCH3, SCH2OCH3 and S(CH2)2NH2, in order to examine the influence of different ligands. Binding energy calculations indicate that the gold core is more stabilized by the ligand in the following sequence S(CH2)2NH2 > SCH2OCH3 > SeCH3 > SCH3. Natural bond orbital (NBO) analysis describes the interaction between the gold and the ligands, showing that the strongest electron donation occurs from a lone pair orbital on the sulfur and selenium atoms to the antibonding acceptor σ* (Au-S) and σ* (Au-Se) orbitals, respectively. The NBO analysis allowed to understand the origin of enhanced stability of the [Au13(S(CH2)2NH2)8]3+. Time-dependent DFT (TDDFT) calculations have been performed to simulate the optical absorption spectra of Au13L83+ in gas phase and under the effect of solvents with different polarities. The absorption spectrum of [Au13(S(CH2)2NH2)8]3+ shows a spectral profile that differs considerably from the others in gas phase and which is strongly affected by the solvent.
Highlights
We employed density functional theory to investigate the effect of different ligands on the structural and optical properties of Au13L8, with L = SCH3, SeCH3, SCH2OCH3 and S(CH2)2NH2
The Natural bond orbital (NBO) analysis show that the secondorder perturbation stabilization energy, E(2), of the dominant donor-acceptor charge transfer interaction
Both results demonstrate that the ligand containing the amine group shows an enhanced capacity to stabilize the Au133+ cluster
Summary
The physical chemical properties of gold clusters and their dependence with atomic arrangement (shape) and size (number of atoms) have driven the interest of researchers for some decades.[1,2,3] Among the properties of the gold clusters, the magnetic,[4] catalytic,[5,6,7] electrochemical,[8,9] optical[10,11,12] and structural[13] ones have been intensively studied, which lead to promising applications in nanoelectronics, chemical sensing, catalysis, biomedicine, etc.[14,15,16] Many of these properties are affected by the strong relativistic effect present on gold atoms.[17,18] This feature explains the trend of gold atoms to generate clusters of different sizes, in contrast with other analogous metals like silver and copper.[19].
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