Journal
ACS NANO
Volume 7, Issue 1, Pages 513-521Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nn3046083
Keywords
ligand-protected metal nanoparticles; chirality; circular dichroism; thiol adsorption; silver nanoparticle; dissymmetric field
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Funding
- DGA-PA-UNAM PAPIIT [IN104212]
- CONACyT [179454]
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The electronic circular dichroism (CD) spectra of a methyl-thiol adsorbed at different sites on an icosahedral silver nanoparticle is studied by using time-perturbed density functional theory. Despite that separately molecule and nanoparticle are achiral and consequently optically inactive, the Ag-55-SCH3 compound emerges with a new symmetry, which may be chiral or not depending on the adsorption site and orientation of the molecule. It is found that chirality Is favored when the thiol is adsorbed between two atoms of different coordination number. Chiral compounds have characteristic CD spectra in the UV-visible region, where Ag-55 shows optical absorption but SCH3 does not; revealing that highly degenerated molecular-like electronic states of Ag-55 are modified by the presence of the molecule Inducing optical activity. It Is concluded that CD line-shapes and magnitude strongly depend on the site where the adsorption takes place, while its intensity is modulated by the molecule orientation.
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