Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au 30 (SR) 18

Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar; De Vetta, Martina; Dass, Amala; Aprà, Edoardo; Stener, Mauro; Fortunelli, Alessandro

doi:10.1021/acs.jpcc.6b12029

Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au ₃₀ (SR) ₁₈

Journal Article · Tue Jan 24 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b12029· OSTI ID:1343948

Sementa, Luca ^[1]; Barcaro, Giovanni ^[1]; Baseggio, Oscar ^[2]; De Vetta, Martina ^[2]; ^[3]; ^[4]; ^[2]; ^[1]

Consiglio Nazionale delle Ricerche (CNR), Pisa (Italy)
Univ. of Trieste (Italy). Dept. of Chemical Science and Pharmacy
Univ. of Mississippi, Oxford, MS (United States). Dept. of Chemistry and Biochemistry
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.

We investigate via first-principles simulations the optical absorption spectra of three different Au₃₀(SR)₁₈ monolayer-protected clusters (MPC): Au₃₀(StBu)₁₈, Au₃₀(SPh)₁₈, and Au₃₀(SPh-pNO₂)₁₈. Au₃₀(StBu)₁₈ is known in the literature, and its crystal structure is available. In contrast, Au₃₀(SPh)₁₈ and Au₃₀(SPh-pNO₂)₁₈ are two species that have been designed by replacing the tert-butyl organic residues of Au₃₀(StBu)₁₈ with aromatic ones so as to investigate the effects of ligand replacement on the optical response of Au nanomolecules. By analogy to a previously studied Au₂₃(SR)16– anionic species, despite distinct differences in charge and chemical composition, a substantial ligand enhancement of the absorption intensity in the optical region is also obtained for the Au₃₀(SPh-pNO₂)₁₈ MPC. Furthermore, the use of conjugated aromatic ligands with properly chosen electron-withdrawing substituents and exhibiting steric hindrance so as to also achieve charge decompression at the surface is therefore demonstrated as a general approach to enhancing the MPC photoabsorption intensity in the optical region. In addition, we here subject the ligand-enhancement phenomenon to a detailed analysis based on the fragment projection of electronic excited states and on induced transition densities, leading to a better understanding of the physical origin of this phenomenon, thus opening avenues to its more precise control and exploitation.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1343948

Alternate ID(s):: OSTI ID: 1364002

Report Number(s):: PNNL-SA--123164

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 2 Vol. 8; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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