Issue 7, 2013
From the journal:

Chemical Science

A theoretical and experimental examination of systematic ligand-induced disorder in Au dendrimer-encapsulated nanoparticles†

David F. Yancey,ab   Samuel T. Chill,ac   Liang Zhang,ac   Anatoly I. Frenkel,*d   Graeme Henkelman*ac  and  Richard M. Crooks*ab  

* Corresponding authors

a Department of Chemistry and Biochemistry, 105 E 24th St. Stop A5300, Austin, TX 78712-0165, USA
E-mail: crooks@cm.utexas.edu, henkelman@cm.utexas.edu
Tel: +1 512-475-8674

b Texas Materials Institute, 105 E 24th St. Stop A5300, Austin, TX 78712-0165, USA

c Institute for Computational and Engineering Sciences, The University of Texas at Austin Department of Chemistry and Biochemistry, 105 E 24th St. Stop A5300, Austin, TX 78712-0165, USA

d Physics Department, Yeshiva University, 245 Lexington Avenue, New York, NY 10016, USA
E-mail: anatoly.frenkel@yu.edu
Tel: +1 212-340-7827

Abstract

In this paper we present a new methodology for the analysis of 1–2 nm nanoparticles using extended X-ray absorption fine structure (EXAFS) spectroscopy. Different numbers of thiols were introduced onto the surfaces of dendrimer-encapsulated Au nanoparticles, consisting of an average of 147 atoms, to systematically tune the nanoparticle disorder. An analogous system was investigated using density functional theory molecular dynamics (DFT-MD) simulations to produce theoretical EXAFS signals that could be directly compared to the experimental results. Validation of the theoretical results by comparing to experiment allows us to infer previously unknown details of structure and dynamics of the nanoparticles. Additionally, the structural information that is learned from theoretical studies can be compared with traditional EXAFS fitting results to identify and rationalize any errors in the experimental fit. This study demonstrates that DFT-MD simulations accurately depict complex experimental systems in which we have control over nanoparticle disorder, and shows the advantages of using a combined experimental/theoretical approach over standard EXAFS fitting methodologies for determining the structural parameters of metallic nanoparticles.

Graphical abstract: A theoretical and experimental examination of systematic ligand-induced disorder in Au dendrimer-encapsulated nanoparticles

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Article information

DOI
https://doi.org/10.1039/C3SC50614B
Article type
Edge Article
Submitted
05 Mar 2013
Accepted
30 Apr 2013
First published
13 May 2013

Chem. Sci., 2013,4, 2912-2921

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A theoretical and experimental examination of systematic ligand-induced disorder in Au dendrimer-encapsulated nanoparticles

D. F. Yancey, S. T. Chill, L. Zhang, A. I. Frenkel, G. Henkelman and R. M. Crooks, Chem. Sci., 2013, 4, 2912 DOI: 10.1039/C3SC50614B

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