Giant circular dichroism of a molecule in a region of strong plasmon resonances between two neighboring gold nanocrystals

We report on giant circular dichroism (CD) of a molecule inserted into a plasmonic hot spot. Naturally occurring molecules and biomolecules have typically CD signals in the UV range, whereas plasmonic nanocrystals exhibit strong plasmon resonances in the visible spectral interval. Therefore, excitations of chiral molecules and plasmon resonances are typically off-resonant. Nevertheless, we demonstrate theoretically that it is possible to create strongly-enhanced molecular CD utilizing the plasmons. This task is doubly challenging since it requires both creation and enhancement of the molecular CD in the visible region. We demonstrate this effect within the model which incorporates a chiral molecule and a plasmonic dimer. The associated mechanism of plasmonic CD comes from the Coulomb interaction which is greatly amplified in a plasmonic hot spot.Comment: Manuscript: 4+pages, 4 figures; Supplemental_Material: 10 pages, 7 figure

Chiral discrimination in optical binding

The laser-induced intermolecular force that exists between two or more particles in the presence of an electromagnetic field is commonly termed “optical binding.” Distinct from the single-particle forces that are at play in optical trapping at the molecular level, the phenomenon of optical binding is a manifestation of the coupling between optically induced dipole moments in neutral particles. In other, more widely known areas of optics, there are many examples of chiral discrimination—signifying the different response a chiral material has to the handedness of an optical input. In the present analysis, extending previous work on chiral discrimination in optical binding, a mechanism is identified using a quantum electrodynamical approach. It is shown that the optical binding force between a pair of chiral molecules can be significantly discriminatory in nature, depending upon both the handedness of the interacting particles and the polarization of the incident light, and it is typically several orders of magnitude larger than previously reported

Magnetic circular dichroism spectra from resonant and damped coupled cluster response theory

A computational expression for the Faraday A term of magnetic circular dichroism (MCD) is derived within coupled cluster response theory and alternative computational expressions for the B term are discussed. Moreover, an approach to compute the (temperature-independent) MCD ellipticity in the context of coupled cluster damped response is presented, and its equivalence with the stick-spectrum approach in the limit of infinite lifetimes is demonstrated. The damped response approach has advantages for molecular systems or spectral ranges with a high density of states. Illustrative results are reported at the coupled cluster singles and doubles level and compared to time-dependent density functional theory results.Comment: Submitted to J. Chem. Phys. on May 10, 202