Broadband Single-Particle Absorption Circular Dichroism Reveals Chiroptical Heterogeneity in Gold Helicoids
Abstract
Quantitative measurements of absorption circular dichroism (CD) at the single-particle level are essential for understanding how individual chiral nanostructures dissipate optical energy, yet broadband absorptance measurements remain experimentally challenging. Here, we introduce a wavelength-tunable integrating-sphere microscope that determines the absorptance of individual nanoparticles under right- and left-circularly polarized illumination through direct optical energy balance, enabling broadband measurement of the absorption dissymmetry factor, gabs. Measurements of achiral gold nanospheres and strongly anisotropic gold nanorods establish the apparent absorption CD baseline and demonstrate minimal detectable linear-dichroism-to-circular-dichroism (LD-to-CD) leakage under the experimental conditions. Applying this approach to 87 chiral gold helicoids synthesized using L-glutathione (L-helicoids) and 96 synthesized using D-glutathione (D-helicoids) reveals mean particle-level gabs values of opposite sign, with a statistically significant difference between the two populations. Individual particles nevertheless exhibit pronounced heterogeneity in response sign, magnitude, spectral position, and line shape. More than one-third of the particles in each population display opposite-sign absorption CD responses relative to their population-average tendency. Correlative SEM analysis of the L-helicoid population further shows that opposite-sign responses persist among isolated particles exhibiting the characteristic projected helicoid morphology, indicating that aggregation and gross differences in projected morphology are insufficient to explain the observed heterogeneity. These results establish broadband single-particle absorption CD spectroscopy as a direct probe of absorptive chiroptical heterogeneity and reveal particle-specific responses obscured by ensemble averaging.
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BibTeX
@misc{raj2026broadband,
title = {{Broadband Single-Particle Absorption Circular Dichroism Reveals Chiroptical Heterogeneity in Gold Helicoids}},
author = {Rohit B. Raj and Susanna Bertuletti and Jeong Hyun Han and Sepin Cho and Debapriya Pal and Nick Feldman and Ki Tae Nam and Willem L. Noorduin and A. Femius Koenderink and Erik C. Garnett},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.24772},
eprint = {2609.24772},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.24772},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - UNPB
TI - Broadband Single-Particle Absorption Circular Dichroism Reveals Chiroptical Heterogeneity in Gold Helicoids
AU - Rohit B. Raj
AU - Susanna Bertuletti
AU - Jeong Hyun Han
AU - Sepin Cho
AU - Debapriya Pal
AU - Nick Feldman
AU - Ki Tae Nam
AU - Willem L. Noorduin
AU - A. Femius Koenderink
AU - Erik C. Garnett
PY - 2026
DA - 2026/09/21
PB - arXiv
DO - 10.48550/arxiv.2609.24772
UR - https://arxiv.org/abs/2609.24772
AB - Quantitative measurements of absorption circular dichroism (CD) at the single-particle level are essential for understanding how individual chiral nanostructures dissipate optical energy, yet broadband absorptance measurements remain experimentally challenging. Here, we introduce a wavelength-tunable integrating-sphere microscope that determines the absorptance of individual nanoparticles under right- and left-circularly polarized illumination through direct optical energy balance, enabling broadband measurement of the absorption dissymmetry factor, gabs. Measurements of achiral gold nanospheres and strongly anisotropic gold nanorods establish the apparent absorption CD baseline and demonstrate minimal detectable linear-dichroism-to-circular-dichroism (LD-to-CD) leakage under the experimental conditions. Applying this approach to 87 chiral gold helicoids synthesized using L-glutathione (L-helicoids) and 96 synthesized using D-glutathione (D-helicoids) reveals mean particle-level gabs values of opposite sign, with a statistically significant difference between the two populations. Individual particles nevertheless exhibit pronounced heterogeneity in response sign, magnitude, spectral position, and line shape. More than one-third of the particles in each population display opposite-sign absorption CD responses relative to their population-average tendency. Correlative SEM analysis of the L-helicoid population further shows that opposite-sign responses persist among isolated particles exhibiting the characteristic projected helicoid morphology, indicating that aggregation and gross differences in projected morphology are insufficient to explain the observed heterogeneity. These results establish broadband single-particle absorption CD spectroscopy as a direct probe of absorptive chiroptical heterogeneity and reveal particle-specific responses obscured by ensemble averaging.
ER -