Issue 40, 2019

Elucidating the optical spectra of [Au25(SR)18]q nanoclusters

Abstract

Ligand-protected Au nanoclusters have attracted tremendous interest due to their atomically precise structural determination and controllable optical properties. However, the origin of their optical features is not well understood. Herein, we address the effects of charge state and type of ligands on the structural, electronic, and optical properties of the Au25(SR)18 nanocluster, using first principles calculations. In particular, we analyze in detail the optical absorption spectra of phenylethanethiol-capped [Au25(SCH2CH2Ph)18]q nanocluster (q = −1, 0, and 1) and demonstrate that the nanocluster undergoes geometric changes when increasing its charge state, yielding the development of additional photoabsorption features. Moreover, by comparing the properties of the anionic [Au25(SR)18]1− nanoclusters (with SR = –SCH2CH2Ph, –SCH3 and –SH) we demonstrate that accounting for full (–SCH2CH2Ph) compared to simplified (–SCH3 and –SH) ligands leads to significant modifications in the shape of the main absorption features, such as the emergence of step-like absorption shoulders. In addition, we show that the energy of the main absorption peaks of the [Au25(SR)18]1− significantly blue-shifts when using –SH as model ligands. Overall, our computational work aids the experimental characterization of optical properties of ligand-protected nanoclusters and highlights the importance of accounting for full ligands in optical spectra calculations.

Graphical abstract: Elucidating the optical spectra of [Au25(SR)18]q nanoclusters

Supplementary files

Article information

Article type
Paper
Submitted
16 জুলাই 2019
Accepted
29 সেপ্টে. 2019
First published
30 সেপ্টে. 2019

Phys. Chem. Chem. Phys., 2019,21, 22272-22282

Author version available

Elucidating the optical spectra of [Au25(SR)18]q nanoclusters

R. Juarez-Mosqueda and G. Mpourmpakis, Phys. Chem. Chem. Phys., 2019, 21, 22272 DOI: 10.1039/C9CP03982A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements