Measuring optical activity in the far-field from a racemic nanomaterial: diffraction spectroscopy from plasmonic nanogratings

Christian Kuppe, Xuezhi Zheng, Calum Williams, Alexander Murphy, Joel Collins, Sergey Gordeev, Guy A E Vandenbosch, Ventsislav Valev

Research output: Contribution to journalArticle

Abstract

Recent progress in nanofabrication has redrawn the boundaries of the applicability of chiroptical (chiral optical) effects. Chirality, often expressed as a twist in biomolecules, is crucial for pharmaceuticals, where it can result in extremely different chemical properties. Because chiroptical effects are typically very weak in molecules, plasmonic nanomaterials are often proposed as a promising platform to significantly enhance these effects. Unfortunately, the ideal plasmonic nanomaterial has conflicting requirements: its chirality should enhance that of the chiral molecules and yet it should have no chiroptical response on its own. Here, we propose a unique reconciliation to satisfy the requirements: a racemic plasmonic nanomaterial, consisting of equal amounts of opposite chiral unit cells. We show how diffraction spectroscopy can be used to unveil the presence of chirality in such racemic nanogratings in the far-field. Our experiments are supported by numerical simulations and yield a circular intensity difference of up to 15%. The physical origin is demonstrated by full wave simulations in combination with a Green’s function – group-theory-based analysis. Contributions from Circular Dichroism in the Angular Distribution of Photoelectrons (CDAD) and pseudo/extrinsic chirality are ruled out. Our findings enable the far-field measurement and tuning of racemic nanomaterials, which is crucial for hyper-sensitive chiral molecular characterization.
LanguageEnglish
JournalNanoscale Horizons
Early online date10 May 2019
DOIs
StatusE-pub ahead of print - 10 May 2019

Cite this

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title = "Measuring optical activity in the far-field from a racemic nanomaterial: diffraction spectroscopy from plasmonic nanogratings",
abstract = "Recent progress in nanofabrication has redrawn the boundaries of the applicability of chiroptical (chiral optical) effects. Chirality, often expressed as a twist in biomolecules, is crucial for pharmaceuticals, where it can result in extremely different chemical properties. Because chiroptical effects are typically very weak in molecules, plasmonic nanomaterials are often proposed as a promising platform to significantly enhance these effects. Unfortunately, the ideal plasmonic nanomaterial has conflicting requirements: its chirality should enhance that of the chiral molecules and yet it should have no chiroptical response on its own. Here, we propose a unique reconciliation to satisfy the requirements: a racemic plasmonic nanomaterial, consisting of equal amounts of opposite chiral unit cells. We show how diffraction spectroscopy can be used to unveil the presence of chirality in such racemic nanogratings in the far-field. Our experiments are supported by numerical simulations and yield a circular intensity difference of up to 15{\%}. The physical origin is demonstrated by full wave simulations in combination with a Green’s function – group-theory-based analysis. Contributions from Circular Dichroism in the Angular Distribution of Photoelectrons (CDAD) and pseudo/extrinsic chirality are ruled out. Our findings enable the far-field measurement and tuning of racemic nanomaterials, which is crucial for hyper-sensitive chiral molecular characterization.",
author = "Christian Kuppe and Xuezhi Zheng and Calum Williams and Alexander Murphy and Joel Collins and Sergey Gordeev and Vandenbosch, {Guy A E} and Ventsislav Valev",
year = "2019",
month = "5",
day = "10",
doi = "10.1039/C9NH00067D",
language = "English",
journal = "Nanoscale Horizons",
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publisher = "Royal Society of Chemistry",

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T1 - Measuring optical activity in the far-field from a racemic nanomaterial: diffraction spectroscopy from plasmonic nanogratings

AU - Kuppe, Christian

AU - Zheng, Xuezhi

AU - Williams, Calum

AU - Murphy, Alexander

AU - Collins, Joel

AU - Gordeev, Sergey

AU - Vandenbosch, Guy A E

AU - Valev, Ventsislav

PY - 2019/5/10

Y1 - 2019/5/10

N2 - Recent progress in nanofabrication has redrawn the boundaries of the applicability of chiroptical (chiral optical) effects. Chirality, often expressed as a twist in biomolecules, is crucial for pharmaceuticals, where it can result in extremely different chemical properties. Because chiroptical effects are typically very weak in molecules, plasmonic nanomaterials are often proposed as a promising platform to significantly enhance these effects. Unfortunately, the ideal plasmonic nanomaterial has conflicting requirements: its chirality should enhance that of the chiral molecules and yet it should have no chiroptical response on its own. Here, we propose a unique reconciliation to satisfy the requirements: a racemic plasmonic nanomaterial, consisting of equal amounts of opposite chiral unit cells. We show how diffraction spectroscopy can be used to unveil the presence of chirality in such racemic nanogratings in the far-field. Our experiments are supported by numerical simulations and yield a circular intensity difference of up to 15%. The physical origin is demonstrated by full wave simulations in combination with a Green’s function – group-theory-based analysis. Contributions from Circular Dichroism in the Angular Distribution of Photoelectrons (CDAD) and pseudo/extrinsic chirality are ruled out. Our findings enable the far-field measurement and tuning of racemic nanomaterials, which is crucial for hyper-sensitive chiral molecular characterization.

AB - Recent progress in nanofabrication has redrawn the boundaries of the applicability of chiroptical (chiral optical) effects. Chirality, often expressed as a twist in biomolecules, is crucial for pharmaceuticals, where it can result in extremely different chemical properties. Because chiroptical effects are typically very weak in molecules, plasmonic nanomaterials are often proposed as a promising platform to significantly enhance these effects. Unfortunately, the ideal plasmonic nanomaterial has conflicting requirements: its chirality should enhance that of the chiral molecules and yet it should have no chiroptical response on its own. Here, we propose a unique reconciliation to satisfy the requirements: a racemic plasmonic nanomaterial, consisting of equal amounts of opposite chiral unit cells. We show how diffraction spectroscopy can be used to unveil the presence of chirality in such racemic nanogratings in the far-field. Our experiments are supported by numerical simulations and yield a circular intensity difference of up to 15%. The physical origin is demonstrated by full wave simulations in combination with a Green’s function – group-theory-based analysis. Contributions from Circular Dichroism in the Angular Distribution of Photoelectrons (CDAD) and pseudo/extrinsic chirality are ruled out. Our findings enable the far-field measurement and tuning of racemic nanomaterials, which is crucial for hyper-sensitive chiral molecular characterization.

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