TY - JOUR
T1 - Probing ligand-induced modulation of metallic states in small gold nanoparticles using conduction electron spin resonance
AU - Cirri, Anthony
AU - Silakov, Alexey
AU - Jensen, Lasse
AU - Lear, Benjamin J.
N1 - Publisher Copyright:
© 2016 the Owner Societies.
PY - 2016
Y1 - 2016
N2 - Thiolate-protected gold nanoparticles have a rich history as model systems for understanding the physical and chemical properties of metallic nanoscale materials that, in turn, form the basis for applications in areas such as molecular electronics, photocatalytic systems, and plasmonic solar cells. It is well known that the electronic properties of gold nanoparticles can be tuned by modifying the geometry, size and dielectric surrounding of the particle. However, much less is known of how modifications to the surface chemistry modulates the electronic properties of gold nanoparticles. In part, this stems from the fact that there are few good tools for measuring the electronic properties with the sensitivity required for following the response to subtle changes in surface chemistry. In this work, we demonstrate conduction spin electron resonance (CESR) to be a sensitive and selective probe to determine how changes in surface chemistry of gold nanoparticles affect the metallic states near the Fermi energy. Using a series of para-substituted aromatic thiolate ligands, we find that the g-factor, as measured using CESR, correlates well with experimental and computational parameters often used to understand ligand effects in classical inorganic complexes. This suggests classical inorganic reasoning can function as a framework for understanding how to control the electronic properties of gold nanoparticles using their surface chemistry.
AB - Thiolate-protected gold nanoparticles have a rich history as model systems for understanding the physical and chemical properties of metallic nanoscale materials that, in turn, form the basis for applications in areas such as molecular electronics, photocatalytic systems, and plasmonic solar cells. It is well known that the electronic properties of gold nanoparticles can be tuned by modifying the geometry, size and dielectric surrounding of the particle. However, much less is known of how modifications to the surface chemistry modulates the electronic properties of gold nanoparticles. In part, this stems from the fact that there are few good tools for measuring the electronic properties with the sensitivity required for following the response to subtle changes in surface chemistry. In this work, we demonstrate conduction spin electron resonance (CESR) to be a sensitive and selective probe to determine how changes in surface chemistry of gold nanoparticles affect the metallic states near the Fermi energy. Using a series of para-substituted aromatic thiolate ligands, we find that the g-factor, as measured using CESR, correlates well with experimental and computational parameters often used to understand ligand effects in classical inorganic complexes. This suggests classical inorganic reasoning can function as a framework for understanding how to control the electronic properties of gold nanoparticles using their surface chemistry.
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U2 - 10.1039/c6cp02205g
DO - 10.1039/c6cp02205g
M3 - Article
C2 - 27711383
AN - SCOPUS:84988430990
SN - 1463-9076
VL - 18
SP - 25443
EP - 25451
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 36
ER -