Circular dichroism (CD) of materials, difference in absorbance of left- and right-circularly polarized light, is a standard measure of chirality. Detection of the chirality for individual molecules is a frontier in analytical chemistry and optical science. The usage of a superchiral electromagnetic field near metallic structure is one promising way because it boosts the molecular far-field CD signal. However, it is still elusive as to how such a field actually interacts with the molecules. The cause is that the distribution of the electric field vector is unclear in the vicinity of the metal surface. In particular, it is difficult to directly measure the localized field, e.g., using aperture-type scanning near-field optical microscope. Here, we calculate the three-dimensional (3D) electric field vector, including the longitudinal field, and reveal the whole figure of the near-field CD on a two-dimensional (2D) plane just above the metal surface. Moreover, we propose a method to measure the near-field CD of the whole superchiral field by photo-induced force microscopy (PiFM), where the optical force distribution is mapped in a scanning 2D plane. We numerically demonstrate that, although the presence of the metallic probe tip affects the 3D electric field distribution, the PiFM is sufficiently capable to evaluate the superchiral field. Unveiling the whole figure of near-field is significantly beneficial in obtaining rich information of single molecules with multiple orientations and in analyzing the boosted far-field CD signals.
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http://dx.doi.org/10.1063/5.0179189 | DOI Listing |
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