Modeling the photosensitizing properties of thiolate-protected gold nanoclusters.
نویسندگان
چکیده
An accurate computational strategy for studying the structural, redox and optical properties of thiolated gold nanoclusters (GNCs) using (Time-Dependent) Density Functional Theory is proposed. The influence of the pseudopotential/basis set, solvent description and the choice of the functional has been investigated to model the structural and electronic properties of the Au25(SR)18(-) system, with R being an organic ligand. This study aims to describe with a comparable precision both the GNC and the organic ligands and rationalize the effect of coating on different GNC properties. Two differently coated GNCs have been considered: the system with R = CH2CH2Ph and the GNC coated with 17 alkyl chains (C6H13) and functionalized by one fluorophore pyrene derivative (CH2CH2(NH)(CO)Py). The computational protocol we propose should then be used to design more efficient metal cluster-sensitized solar cells.
منابع مشابه
Investigating the structural evolution of thiolate protected gold clusters from first-principles.
Unlike bulk materials, the physicochemical properties of nano-sized metal clusters can be strongly dependent on their atomic structure and size. Over the past two decades, major progress has been made in both the synthesis and characterization of a special class of ligated metal nanoclusters, namely, the thiolate-protected gold clusters with size less than 2 nm. Nevertheless, the determination ...
متن کاملUnraveling a generic growth pattern in structure evolution of thiolate-protected gold nanoclusters.
Precise control of the growth of thiolate-protected gold nanoclusters is a prerequisite for their applications in catalysis and bioengineering. Here, we bring to bear a new series of thiolate-protected nanoclusters with a unique growth pattern, i.e., Au20(SR)16, Au28(SR)20, Au36(SR)24, Au44(SR)28, and Au52(SR)32. These nanoclusters can be viewed as resulting from the stepwise addition of a comm...
متن کاملOptimization of Thiolate Stabilized Gold Nanoclusters For Near Infrared Emission in Subcellular Imaging
Monothiolate protected gold nanoclusters with near IR luminescence underwent a five-toten fold enhancement of quantum efficiency by heating in the presence of excess thiols. Two monothiolate nanoclusters, mercaptosuccinic acid and tiopronin, were shown to benefit from this procedure. Emission maximum around 700-900 nm is favorable for bioimaging applications due to reduction of background signa...
متن کاملControlled reduction for size selective synthesis of thiolate-protected gold nanoclusters Aun(n = 20, 24, 39, 40)
This work presents a controlled reduction method for the selective synthesis of different sized gold nanoclusters protected by thiolate (SR = SC2H4Ph). Starting with Au(III) salt, all the syntheses of Aun(SR)m nanoclusters with (n, m) = (20, 16), (24, 20), (39, 29), and (40, 30) necessitate experimental conditions of slow stirring and slow reduction of Au(I) intermediate species. By controlling...
متن کاملOn the opto-electronic properties of phosphine and thiolate-protected undecagold nanoclusters.
We present here a detailed time-dependent density-functional theory investigation aimed at systematically dissecting the electronic spectra of two thiolate and phosphine protected undecagold nanoclusters. Calculations performed on the experimental structures of Au11(PPh3)7Cl3 and Au11(PPh3)7(SPyr)3 show that ligands have negligible contributions in the visible region. Metal → ligand charge tran...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Physical chemistry chemical physics : PCCP
دوره 18 11 شماره
صفحات -
تاریخ انتشار 2016