Title: Combined experimental and computational study of the photoabsorption of the monodoped and nondoped nanoclusters Au24Pt(SR)18, Ag24Pt(SR)18, and Ag25(SR)18
Authors: Pierpaolo D’Antoni, Luca Sementa, Sara Bonacchi, Mattia Reato, Flavio Maran, Alessandro Fortunelli, Mauro Stener
DOI: 10.1039/D4CP00789A
Date: 2024-06-07
Working Group: WG3
Grant Period: GP2
Grant Period Goal (number): GPG6
Covered deliverables from the MoU (number): 1.2.1
Countries involved: Italy
Number of female/young/ITC coauthors: 1/2/0
Is the publication open access?: Yes
Is the publication co-lead by a YRI?: No
Abstract: Assessing the accuracy of first-principles computational approaches is instrumental to predict electronic excitations in metal nanoclusters with quantitative confidence. Here we describe a validation study on the optical response of a set of monolayer-protected clusters (MPC). The photoabsorption spectra of Ag25(DMBT)18−, Ag24Pt(DMBT)182− and Au24Pt(SC4H9)18, where DMBT is 2,4-dimethylbenzenethiolate and SC4H9 is n-butylthiolate, have been obtained at low temperature and compared with accurate TDDFT calculations. An excellent match between theory and experiment, with typical deviations of less than 0.1 eV, was obtained, thereby validating the accuracy and reliability of the proposed computational framework. Moreover, an analysis of the TDDFT simulations allowed us to ascribe all relevant spectral features to specific transitions between occupied/virtual orbital pairs. The doping effect of Pt on the optical response of these ultrasmall MPC systems was identified and discussed.
