Helicity-Preserving Optical Cavity Modes for Enhanced Sensing of Chiral Molecules.

Researchers routinely sense molecules by their infrared vibrational "fingerprint" absorption resonances. In addition, the dominant handedness of chiral molecules can be detected by circular dichroism (CD), the normalized difference between their optical response to incident left- and right- handed circularly polarized light. Here, we introduce a cavity composed of two parallel arrays of helicity-preserving silicon disks that allows one to enhance the CD signal by more than 2 orders of magnitude for a given molecule concentration and given thickness of the cell containing the molecules. The underlying principle is first-order diffraction into helicity-preserving modes with large transverse momentum and long lifetimes. In sharp contrast, in a conventional Fabry-Perot cavity, each reflection flips the handedness of light, leading to large intensity enhancements inside the cavity, yet to smaller CD signals than without the cavity.

Computation of Electromagnetic Properties of Molecular Ensembles.

We outline a methodology for efficiently computing the electromagnetic response of molecular ensembles. The methodology is based on the link that we establish between quantum-chemical simulations and the transfer matrix (T-matrix) approach, a common tool in physics and engineering. We exemplify and analyze the accuracy of the methodology by using the time-dependent Hartree-Fock theory simulation data of a single chiral molecule to compute the T-matrix of a cross-like arrangement of four copies of the molecule, and then computing the circular dichroism of the cross. The results are in very good agreement with full quantum-mechanical calculations on the cross. Importantly, the choice of computing circular dichroism is arbitrary: Any kind of electromagnetic response of an object can be computed from its T-matrix. We also show, by means of another example, how the methodology can be used to predict experimental measurements on a molecular material of macroscopic dimensions. This is possible because, once the T-matrices of the individual components of an ensemble are known, the electromagnetic response of the ensemble can be efficiently computed. This holds for arbitrary arrangements of a large number of molecules, as well as for periodic or aperiodic molecular arrays. We identify areas of research for further improving the accuracy of the method, as well as new fundamental and technological research avenues based on the use of the T-matrices of molecules and molecular ensembles for quantifying their degrees of symmetry breaking. We provide T-matrix-based formulas for computing traditional chiro-optical properties like (oriented) circular dichroism, and also for quantifying electromagnetic duality and electromagnetic chirality. The formulas are valid for light-matter interactions of arbitrarily-high multipolar orders.

Manipulation of Magnetic Dipole Emission from Eu3+ with Mie-Resonant Dielectric Metasurfaces.

Mie-resonant high-index dielectric nanoparticles and metasurfaces have been suggested as a viable platform for enhancing both electric and magnetic dipole transitions of fluorescent emitters. While the enhancement of the electric dipole transitions by such dielectric nanoparticles has been demonstrated experimentally, the case of magnetic-dipole transitions remains largely unexplored. Here, we study the enhancement of spontaneous emission of Eu3+ ions, featuring both electric and magnetic-dominated dipole transitions, by dielectric metasurfaces composed of Mie-resonant silicon nanocylinders. By coating the metasurfaces with a layer of an Eu3+ doped polymer, we observe an enhancement of the Eu3+ emission associated with the electric (at 610 nm) and magnetic-dominated (at 590 nm) dipole transitions. The enhancement factor depends systematically on the spectral proximity of the atomic transitions to the Mie resonances as well as their multipolar order, both controlled by the nanocylinder size. Importantly, the branching ratio of emission via the electric or magnetic transition channel can be modified by carefully designing the metasurface, where the magnetic dipole transition is enhanced more than the electric transition for cylinders with radii of about 130 nm. We confirm our observations by numerical simulations based on the reciprocity principle. Our results open new opportunities for bright nanoscale light sources based on magnetic transitions.

Exact dipolar moments of a localized electric current distribution.

The multipolar decomposition of current distributions is used in many branches of physics. Here, we obtain new exact expressions for the dipolar moments of a localized electric current distribution. The typical integrals for the dipole moments of electromagnetically small sources are recovered as the lowest order terms of the new expressions in a series expansion with respect to the size of the source. All the higher order terms can be easily obtained. We also provide exact and approximated expressions for dipoles that radiate a definite polarization handedness (helicity). Formally, the new exact expressions are only marginally more complex than their lowest order approximations.

A Multi-Scale Approach to Simulate the Nonlinear Optical Response of Molecular Nanomaterials.

Nonlinear optics is essential for many recent photonic technologies. Here, a novel multi-scale approach is introduced to simulate the nonlinear optical response of molecular nanomaterials combining ab initio quantum-chemical and classical Maxwell-scattering computations. In this approach, the first hyperpolarizability tensor is computed with time-dependent density-functional theory and incorporated into a multi-scattering formalism that considers the optical interaction between neighboring molecules. Such incorporation is achieved by a novel object: the Hyper-Transition(T)-matrix. With this object at hand, the nonlinear optical response from single molecules and also from entire photonic devices can be computed, including the full tensorial and dispersive nature of the optical response of the molecules, as well as the optical interaction between different molecules as, for example, in the lattice of a molecular crystal. To demonstrate the applicability of the novel approach, the generation of a second-harmonic signal from a thin film of an Urea molecular crystal is computed and compared to more traditional simulations. Furthermore, an optical cavity is designed, which enhances the second-harmonic response of the molecular film up to more than two orders of magnitude. This approach is highly versatile and accurate and can be the working horse for the future exploration of nonlinear photonic molecular materials in structured photonic environments.

Circular dichroism of relativistically-moving chiral molecules.

Understanding the impact of the relativistic motion of a chiral molecule on its optical response is a prime challenge for fundamental science, but it also has a direct practical relevance in our search for extraterrestrial life. To contribute to these significant developments, we describe a multi-scale computational framework that combines quantum chemistry calculations and full-wave optical simulations to predict the chiral optical response from molecules moving at relativistic speeds. Specifically, the effect of a relativistic motion on the transmission circular dichroism (TCD) of three life-essential biomolecules, namely, B-DNA, chlorophyll a, and chlorophyll b, is investigated. Inspired by previous experiments to detect interstellar chiral molecules, we assume that the molecules move between a stationary observer and a light source, and we study the rotationally averaged TCD as a function of the speed of the molecule.We find that the TCD spectrum that contains the signatures of the molecules shifts with increasing speed to shorter wavelengths, with the effects already being visible for moderate velocities.

Forward and backward helicity scattering coefficients for systems with discrete rotational symmetry.

The forward and backward scattering off linear systems with discrete rotational symmetries R(z)(2π/n) with n ≥ 3 are shown to be restricted by symmetry reasons. Along the symmetry axis, forward scattering can only be helicity preserving and backward scattering can only be helicity flipping. These restrictions do not exist for n < 3. If, in addition to the n ≥ 3 discrete rotational symmetry, the system has duality symmetry (obeys the helicity conservation law), it will exhibit zero backscattering. The results pinpoint the underlying symmetry reasons for some notable scattering properties of R(z)(2π/4) symmetric systems that have been reported in the metamaterials and radar literature. Applications to planar metamaterials and solar cells are briefly discussed.

Electromagnetic duality symmetry and helicity conservation for the macroscopic Maxwell's equations.

In this Letter, we show that the electromagnetic duality symmetry, broken in the microscopic Maxwell's equations by the presence of charges, can be restored for the macroscopic Maxwell's equations. The restoration of this symmetry is shown to be independent of the geometry of the problem. These results provide a tool for the study of light-matter interactions within the framework of symmetries and conservation laws. We illustrate its use by determining the helicity content of the natural modes of structures possessing spatial inversion symmetries and by elucidating the root causes for some surprising effects in the scattering off magnetic spheres.

Necessary symmetry conditions for the rotation of light.

Two conditions on symmetries are identified as necessary for a linear scattering system to be able to rotate the linear polarization of light: Lack of at least one mirror plane of symmetry and electromagnetic duality symmetry. Duality symmetry is equivalent to the conservation of the helicity of light in the same way that rotational symmetry is equivalent to the conservation of angular momentum. When the system is a solution of a single species of particles, the lack of at least one mirror plane of symmetry leads to the familiar requirement of chirality of the individual particle. With respect to helicity preservation, according to the analytical and numerical evidence presented in this paper, the solution preserves helicity if and only if the individual particle itself preserves helicity. However, only in the particular case of forward scattering the helicity preservation condition on the particle is relaxed: We show that the random orientation of the molecules endows the solution with an effective rotational symmetry; at its turn, this leads to helicity preservation in the forward scattering direction independently of any property of the particle. This is not the case for a general scattering direction. These results advance the current understanding of the phenomena of molecular optical activity and provide insight for the design of polarization control devices at the nanoscale.

A Multi-Scale Approach for Modeling the Optical Response of Molecular Materials Inside Cavities.

The recent fabrication advances in nanoscience and molecular materials point toward a new era where material properties are tailored in silico for target applications. To fully realize this potential, accurate and computationally efficient theoretical models are needed for: a) the computer-aided design and optimization of new materials before their fabrication; and b) the accurate interpretation of experiments. The development of such theoretical models is a challenging multi-disciplinary problem where physics, chemistry, and material science are intertwined across spatial scales ranging from the molecular to the device level, that is, from ångströms to millimeters. In photonic applications, molecular materials are often placed inside optical cavities. Together with the sought-after enhancement of light-molecule interactions, the cavities bring additional complexity to the modeling of such devices. Here, a multi-scale approach that, starting from ab initio quantum mechanical molecular simulations, can compute the electromagnetic response of macroscopic devices such as cavities containing molecular materials is presented. Molecular time-dependent density-functional theory calculations are combined with the efficient transition matrix based solution of Maxwell's equations. Some of the capabilities of the approach are demonstrated by simulating surface metal-organic frameworks -in-cavity and J-aggregates-in-cavity systems that have been recently investigated experimentally, and providing a refined understanding of the experimental results.

Effects of symmetry-breaking on electromagnetic backscattering.

Systems with a discrete rotational symmetry [Formula: see text] where [Formula: see text] that also have electromagnetic duality symmetry exhibit zero backscattering. The impact of breaking one of the two symmetries on the emerging backscattering has not yet been systematically studied. Here, we investigate the effect that perturbatively breaking each of the two symmetries has on the backscattering off individual objects and 2D arrays. We find that the backscattering off electromagnetically-small prisms increases with the parameters that determine the symmetry breaking, and that the increase of the backscattering due to the progressive breaking of one of the symmetries can be related to the other symmetry. Further exploration of the interplay between the two symmetries reveals that, in systems lacking enough rotational symmetry, the backscattering can be almost-entirely suppressed for a given linear polarization by deliberately breaking the duality symmetry. This duality breaking can be interpreted as an effective increase of the electromagnetic degree of rotational symmetry for that linear polarization.

Interaction of atomic systems with quantum vacuum beyond electric dipole approximation.

The photonic environment can significantly influence emission properties and interactions among atomic systems. In such scenarios, frequently the electric dipole approximation is assumed that is justified as long as the spatial extent of the atomic system is negligible compared to the spatial variations of the field. While this holds true for many canonical systems, it ceases to be applicable for more contemporary nanophotonic structures. To go beyond the electric dipole approximation, we propose and develop in this article an analytical framework to describe the impact of the photonic environment on emission and interaction properties of atomic systems beyond the electric dipole approximation. Particularly, we retain explicitly magnetic dipolar and electric quadrupolar contributions to the light-matter interactions. We exploit a field quantization scheme based on electromagnetic Green's tensors, suited for dispersive materials. We obtain expressions for spontaneous emission rate, Lamb shift, multipole-multipole shift and superradiance rate, all being modified with dispersive environment. The considered influence could be substantial for suitably tailored nanostructured photonic environments, as demonstrated exemplarily.

Correction: Computing the T-matrix of a scattering object with multiple plane wave illuminations.

[This corrects the article DOI: 10.3762/bjnano.8.66.].

On the dynamic toroidal multipoles from localized electric current distributions.

We analyze the dynamic toroidal multipoles and prove that they do not have an independent physical meaning with respect to their interaction with electromagnetic waves. We analytically show how the split into electric and toroidal parts causes the appearance of non-radiative components in each of the two parts. These non-radiative components, which cancel each other when both parts are summed, preclude the separate determination of each part by means of measurements of the radiation from the source or of its coupling to external electromagnetic waves. In other words, there is no toroidal radiation or independent toroidal electromagnetic coupling. The formal meaning of the toroidal multipoles is clear in our derivations. They are the higher order terms of an expansion of the multipolar coefficients of electric parity with respect to the electromagnetic size of the source.

Computing the T-matrix of a scattering object with multiple plane wave illuminations.

Given an arbitrarily complicated object, it is often difficult to say immediately how it interacts with a specific illumination. Optically small objects, e.g., spheres, can often be modeled as electric dipoles, but which multipole moments are excited for larger particles possessing a much more complicated shape? The T-matrix answers this question, as it contains the entire information about how an object interacts with any electromagnetic illumination. Moreover, a multitude of interesting properties can be derived from the T-matrix such as the scattering cross section for a specific illumination and information about symmetries of the object. Here, we present a method to calculate the T-matrix of an arbitrary object numerically, solely by illuminating it with multiple plane waves and analyzing the scattered fields. Calculating these fields is readily done by widely available tools. The finite element method is particularly advantageous, because it is fast and efficient. We demonstrate the T-matrix calculation at four examples of relevant optical nanostructures currently at the focus of research interest. We show the advantages of the method to obtain useful information, which is hard to access when relying solely on full wave solvers.

Far-field measurements of vortex beams interacting with nanoholes.

We measure the far-field intensity of vortex beams going through nanoholes. The process is analyzed in terms of helicity and total angular momentum. It is seen that the total angular momentum is preserved in the process, and helicity is not. We compute the ratio between the two transmitted helicity components, γm,p. We observe that this ratio is highly dependent on the helicity (p) and the angular momentum (m) of the incident vortex beam in consideration. Due to the mirror symmetry of the nanoholes, we are able to relate the transmission properties of vortex beams with a certain helicity and angular momentum, with the ones with opposite helicity and angular momentum. Interestingly, vortex beams enhance the γm,p ratio as compared to those obtained by Gaussian beams.

Quantum Emulation of Gravitational Waves.

Gravitational waves, as predicted by Einstein's general relativity theory, appear as ripples in the fabric of spacetime traveling at the speed of light. We prove that the propagation of small amplitude gravitational waves in a curved spacetime is equivalent to the propagation of a subspace of electromagnetic states. We use this result to propose the use of entangled photons to emulate the evolution of gravitational waves in curved spacetimes by means of experimental electromagnetic setups featuring metamaterials.