Mapping electric field components of superchiral field with photo-induced force.

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.

Rotational dynamics of indirect optical bound particle assembly under a single tightly focused laser.

The optical binding of many particles has the potential to achieve the wide-area formation of a "crystal" of small materials. Unlike conventional optical binding, where the entire assembly of targeted particles is directly irradiated with light, if remote particles can be indirectly manipulated using a single trapped particle through optical binding, the degrees of freedom to create ordered structures can be enhanced. In this study, we theoretically investigate the dynamics of the assembly of gold nanoparticles that are manipulated using a single trapped particle by a focused laser. We demonstrate the rotational motion of particles through an indirect optical force and analyze it in terms of spin-orbit coupling and the angular momentum generation of light. The rotational direction of bound particles can be switched by the numerical aperture. These results pave the way for creating and manipulating ordered structures with a wide area and controlling local properties using scanning laser beams.

Enantioselective optical trapping of single chiral molecules in the superchiral field vicinity of metal nanostructures.

In this study, we theoretically analyzed the optical force acting on single chiral molecules in the plasmon field induced by metallic nanostructures. Using the extended discrete dipole approximation, we quantitatively examined the optical response of single chiral molecules in the localized plasmon by numerically analyzing the internal polarization structure of the molecules obtained from quantum chemical calculations, without phenomenological treatment. We evaluated the chiral gradient force due to the optical chirality gradient of the superchiral field near the metallic nanostructures for chiral molecules. Our calculation method can be used to evaluate the molecular-orientation dependence and rotational torque by considering the chiral spatial structure inside the molecules. We theoretically showed that the superchiral field induced by chiral plasmonic nanostructures can be used to selectively optically capture the enantiomers of a single chiral molecule.

Near-field circular dichroism of single molecules.

Near-field images of molecules provide information about their excited orbitals, giving rise to photonic and chemical functions. Such information is crucial to the elucidation of the full potential of molecules as components in functional materials and devices at the nanoscale. However, direct imaging inside single molecules with a complex structure in the near-field is still challenging because it requires in situ observation at a higher resolution than the molecular scale. Here, using a proven theoretical method that has demonstrated sub-nanoscale resolution based on photoinduced force microscopy (PiFM) experiment [Nat. Commun.12, 3865 (2021)10.1038/s41467-021-24136-2], we propose an approach to obtaining the near-field imaging with spatial patterns of electronic transitions of single molecules. We use an extended discrete dipole approximation method that incorporates microscopic nonlocal optical response of molecules and demonstrate that PiFM can visualize circular-dichroism signal patterns at sub-nanometer scale for both optically allowed and forbidden transitions. The result will open the possibility for the direct observation of complex spatial patterns of electronic transitions in a single molecule, providing insight into the optical function of single molecules and helping realize new functional materials and devices.

Optical force spectroscopy for measurement of nonlinear optical coefficient of single nanoparticles through optical manipulation.

Compared with manipulation of microparticles with optical tweezers and control of atomic motion with atom cooling, the manipulation of nanoscale objects is challenging because light exerts a significantly weaker force on nanoparticles than on microparticles. The complex interaction of nanoparticles with the environmental solvent media adds to this challenge. In recent years, optical manipulation using electronic resonance effects has garnered interest because it has enabled researchers to enhance the force as well as sort nanoparticles by their quantum mechanical properties. Especially, a precise observation of the motion of nanoparticles irradiated by resonant light enables the precise measurement of the material parameters of single nanoparticles. Conventional spectroscopic methods of measurement are based on indirect processes involving energy dissipation, such as thermal dissipation and light scattering. This study proposes a theoretical method to measure the nonlinear optical constant based on the optical force. The nonlinear susceptibility of single nanoparticles can be directly measured by evaluating the transportation distance of particles through pure momentum exchange. We extrapolate an experimentally verified method of measuring the linear absorption coefficient of single nanoparticles by the optical force to determine the nonlinear absorption coefficient. To this end, we simulate the third-order nonlinear susceptibility of the target particles with the kinetic analysis of nanoparticles at the solid-liquid interface incorporating the Brownian motion. The results show that optical manipulation can be used as nonlinear optical spectroscopy utilizing direct exchange of momentum. To the best of our knowledge, this is currently the only way to measure the nonlinear coefficient of individual single nanoparticles.

Formulation of resonant optical force based on the microscopic structure of chiral molecules.

Optical manipulation, exemplified by Ashkin's optical tweezers, is a promising technique in the fields of bioscience and chemistry, as it enables the non-destructive and non-contact selective transport or manipulation of small particles. To realize the separation of chiral molecules, several researchers have reported on the use of light and discussed feasibility of selection. Although the separation of micrometer-sized chiral molecules has been experimentally demonstrated, the separation of nanometer-sized chiral molecules, which are considerably smaller than the wavelength of light, remains challenging. Therefore, we formulated an optical force under electronic resonance to enhance the optical force and enable selective manipulation. In particular, we incorporated the microscopic structures of molecular dipoles into the nonlocal optical response theory. The analytical expression of optical force could clarify the mechanism of selection exertion of the resonant optical force on chiral molecules. Furthermore, we quantitatively evaluated the light intensity and light exposure time required to separate a single molecule in a solvent. The results can facilitate the design of future schemes for the selective optical manipulation of chiral molecules.

Nanoscale rotational optical manipulation.

Light has momentum, and hence, it can move small particles. The optical tweezer, invented by Ashkin et al. [Opt. Lett. 11, 288 (1986)] is a representative application. It traps and manipulates microparticles and has led to great successes in the biosciences. Currently, optical manipulation of "nano-objects" is attracting growing attention, and new techniques have been proposed and realized. For flexible manipulation, push-pull switching [Phys. Rev. Lett. 109, 087402 (2012)] and super-resolution trapping by using the electronic resonance of nano-objects have been proposed [ACS Photonics 5, 318 (2017)]. However, regarding the "rotational operation" of nano-objects, the full potential of optical manipulation remains unknown. This study proposes mechanisms to realize rotation and direction switching of nano-objects in macroscopic and nanoscopic areas. By controlling the balance between the dissipative force and the gradient force by using optical nonlinearity, the direction of the macroscopic rotational motion of nano-objects is switched. Further, conversion between the spin angular momentum and orbital angular momentum by light scattering through localized surface plasmon resonance in metallic nano-complexes induces optical force for rotational motion in the nanoscale area. This study pieces out fundamental operations of the nanoscale optical manipulation of nanoparticles.

Theoretical analysis of optically selective imaging in photoinduced force microscopy.

We present a theoretical study on the measurement of photoinduced force microscopy (PiFM) for composite molecular systems. Using discrete dipole approximation, we calculate the self-consistent response electric field of the entire system, including the PiFM tip, substrate, and composite molecules. We demonstrate a higher sensitivity for PiFM measurement on resonant molecules than the previously obtained tip-sample distance dependency, z-4, owing to multifold enhancement of the localized electric field induced at the tip-substrate nanogap and molecular polarization. The enhanced localized electric field in PiFM allows high-resolution observation of forbidden optical electronic transitions in dimer molecules. We investigate the wavelength dependence of PiFM for dimer molecules, obtaining images at incident light wavelengths corresponding to the allowed and forbidden transitions. We reveal that these PiFM images drastically change with the frequency-dependent spatial structures of the localized electric field vectors and resolve different types of nanoparticles beyond the resolution for the optically allowed transitions. This study demonstrates that PiFM yields multifaceted information based on microscopic interactions between nanomaterials and light.

Synergetic Enhancement of Light-Matter Interaction by Nonlocality and Band Degeneracy in ZnO Thin Films.

This study aims to reveal the full potential of ZnO as an ultrafast photofunctional material. Based on nonlocal response theory to incorporate the spatially inhomogeneous quality of the samples coupled with experimental observations of linear and nonlinear optical responses, we establish the ultrafast radiative decay of excitons in ZnO thin films that reaches the speed of excitonic dephasing at room temperature in typical semiconductors at a couple tens of femtoseconds. The consistency between the observed delay-time dependence of the transient-grating signals and the theoretical prediction reveals that the ultrafast radiative decay is due to the synergetic effects of the giant light-exciton interaction volume and the radiative coupling between multicomponent excitons.

Up-conversion superfluorescence induced by abrupt truncation of coherent field and plasmonic nanocavity.

We theoretically propose a new method for generating up-converted coherent light from two-level systems (TLSs) coupled with a plasmonic nanocavity. The emission spectrum of a TLS excited by a strong laser exhibits a triplet structure called the Mollow triplet. If the lower Mollow sideband is tuned to the cavity mode energy, population inversion of a TLS occurs. When the driving laser is abruptly truncated under this condition, an up-converted photon is emitted from the TLSs. We also predict the up-converted superfluorescence from an ensemble of TLSs as a correlation effect among the excited states of the TLSs.

Resonance optical trapping of individual dye-doped polystyrene particles with blue- and red-detuned lasers.

We demonstrate resonance optical trapping of individual dye-doped polystyrene particles with blue- and red-detuned lasers whose energy are higher and lower compared to electronic transition of the dye molecules, respectively. Through the measurement on how long individual particles are trapped at the focus, we here show that immobilization time of dye-doped particles becomes longer than that of bare ones. We directly confirm that the immobilization time of dye-doped particles trapped by the blue-detuned laser becomes longer than that by the red-detuned one. These findings are well interpreted by our previous theoretical proposal based on nonlinear optical response under intense laser field. It is discussed that the present result is an important step toward efficient and selective manipulation of molecules, quantum dots, nanoparticles, and various nanomaterials based on their quantum mechanical properties.

Synchronization Dynamics in a Designed Open System.

We theoretically propose a unifying expression for synchronization dynamics between two-level constituents. Although synchronization phenomena require some substantial mediators, the distinct repercussions of their propagation delays remain obscure, especially in open systems. Our scheme directly incorporates the details of the constituents and mediators in an arbitrary environment. As one example, we demonstrate the synchronization dynamics of optical emitters on a dielectric microsphere. We reveal that the whispering gallery modes (WGMs) bridge the well-separated emitters and accelerate the synchronized fluorescence, known as superfluorescence. The emitters are found to overcome the significant and nonuniform retardation, and to build up their pronounced coherence by the WGMs, striking a balance between the roles of resonator and intermediary. Our work directly illustrates the dynamical aspects of many-body synchronizations and contributes to the exploration of research paradigms that consider designed open systems.

Enhanced up-conversion of entangled photons and quantum interference under a localized field in nanostructures.

We theoretically investigate the up-conversion process of two entangled photons on a molecule, which is coupled by a cavity or nanoscale metallic structure. Within one-dimensional input-output theory, the propagators of the photons are derived analytically and the up-conversion probability is calculated numerically. It is shown that the coupling with the nanostructure clearly enhances the process. We also find that the enhancement becomes further pronounced for some balanced system parameters, such as the quantum correlation between photons, radiation decay, and coupling between the nanostructure and molecule. The nonmonotonic dependencies are reasonably explained in view of quantum interference between the coupled modes of the whole system. This result indicates that controlling quantum interference and correlation is crucial for few-photon nonlinearity, and provides a new guidance to wide variety of fields, e.g., quantum electronics and photochemistry.

Description of a Remarkable New Skate Species of Leucoraja Malm, 1877 (Rajiformes, Rajidae) from the Southwestern Indian Ocean: Introducing 3D Modeling as an Innovative Tool for the Visualization of Clasper Characters.

A remarkable new deep-water skate, Leucoraja longirostris n. sp., is described based on eight specimens caught during different expeditions to the southern Madagascar Ridge in the southwestern Indian Ocean. The new species differs from all congeners by its remarkably long and acutely angled snout (horizontal preorbital length 17.2-22.6% TL vs. 8.5-11.9% TL and 4.2-6.1 vs. 1.7-3.5 times orbit length, snout angle 65-85° vs. 90-150°). Furthermore, it is apparently endemic to the Madagascar Ridge, distant from the known distribution areas of all congeners. In addition to L. fullonica and L. pristispina, L. longirostris n. sp. is also the only species with plain dorsal coloration. Furthermore, the new species is the only Leucoraja species with an external clasper component dike and, besides L. wallacei, the only one with four dorsal terminal (dt) cartilages. The shape of the accessory terminal 1 (at1) cartilage with four tips is also unique within the genus. A new approach for the visualization of the clasper characters is introduced based on 3D models of all skeletal and external features. This enables a much easier and much more precise interpretation of every single clasper component, of the entire structure, and, in particular, the relationship between external features and skeletal cartilages. A new English translation of the first diagnosis of Leucoraja is provided, along with a revised generic diagnosis and a key to the species of Leucoraja in the Indian Ocean.

Optical Imaging of a Single Molecule with Subnanometer Resolution by Photoinduced Force Microscopy.

Visualizing the optical response of individual molecules is a long-standing goal in catalysis, molecular nanotechnology, and biotechnology. The molecular response is dominated not only by the electronic states in their isolated environment but also by neighboring molecules and the substrate. Information about the transfer of energy and charge in real environments is essential for the design of the desired molecular functions. However, visualizing these factors with spatial resolution beyond the molecular scale has been challenging. Here, by combining photoinduced force microscopy and Kelvin probe force microscopy, we have mapped the photoinduced force in a pentacene bilayer with a spatial resolution of 0.6 nm and observed its "multipole excitation". We identified the excitation as the result of energy and charge transfer between the molecules and to the Ag substrate. These findings can be achieved only by combining microscopy techniques to simultaneously visualize the optical response of the molecules and the charge transfer between the neighboring environments. Our approach and findings provide insights into designing molecular functions by considering the optical response at each step of layering molecules.

Fishing for oil and meat drives irreversible defaunation of deepwater sharks and rays.

The deep ocean is the last natural biodiversity refuge from the reach of human activities. Deepwater sharks and rays are among the most sensitive marine vertebrates to overexploitation. One-third of threatened deepwater sharks are targeted, and half the species targeted for the international liver-oil trade are threatened with extinction. Steep population declines cannot be easily reversed owing to long generation lengths, low recovery potentials, and the near absence of management. Depth and spatial limits to fishing activity could improve conservation when implemented alongside catch regulations, bycatch mitigation, and international trade regulation. Deepwater sharks and rays require immediate trade and fishing regulations to prevent irreversible defaunation and promote recovery of this threatened megafauna group.

Permanent fixing or reversible trapping and release of DNA micropatterns on a gold nanostructure using continuous-wave or femtosecond-pulsed near-infrared laser light.

The use of localized surface plasmons (LSPs) for highly sensitive biosensors has already been investigated, and they are currently being applied for the optical manipulation of small nanoparticles. The objective of this work was the optical trapping of λ-DNA on a metallic nanostructure with femtosecond-pulsed (fs) laser irradiation. Continuous-wave laser irradiation, which is generally used for plasmon excitation, not only increased the electromagnetic field intensity but also generated heat around the nanostructure, causing the DNA to become permanently fixed on the plasmonic substrate. Using fs laser irradiation, on the other hand, the reversible trapping and release of the DNA was achieved by switching the fs laser irradiation on and off. This trap-and-release behavior was clearly observed using a fluorescence microscope. This technique can also be used to manipulate other biomolecules such as nucleic acids, proteins, and polysaccharides and will prove to be a useful tool in the fabrication of biosensors.

Model of finite-momentum excitons driven by surface plasmons in photoexcited carbon nanotubes covered by gold metal films.

Optical spectra of finite-momentum excitons in carbon nanotubes with gold nanostructures are theoretically studied. A Green function method is developed for self-consistently solving Maxwell equations including the quantum-mechanical nonlocal response of the nanotubes and the local response of the nanostructures. Excitons with finite momenta in the axis direction in the nanotubes are effectively excited by localized electric fields due to surface plasmons in the gold nanostructures and counteract the surface plasmons through depolarization fields, showing the crucial self-consistency of these effects.

Resonance optical manipulation of nano-objects based on nonlinear optical response.

Optical manipulation is a technique to control the mechanical motion of small objects by using electromagnetic radiation force. Optical tweezers are the most popular tool to trap and move microparticles suspended in a medium. Recent interest has been shifting to manipulating nano-objects considerably smaller than the wavelength of light. Since the radiation force exerted on nano-objects is extremely small, an innovative method is necessary to make this concept feasible. Utilizing the resonant optical response of the objects to electronic transitions is one of the promising ways to approach nanoscale optical manipulation, and several advances in this direction have been made recently. Despite experimental studies on resonance optical tweezers showing favorable results, conventional theories have been unable to explain the results though demonstrations of resonant manipulations for traveling and standing waves have shown favorable results. In the present article, we provide a perspective view of resonance optical manipulation based on nonlinear optical response that we have recently proposed. This idea coherently elucidates recently reported puzzling phenomena appearing in studies concerning resonance optical tweezers that contradict the conventional understanding of resonance optical trapping. Further, this concept opens up the possibility to develop potentially powerful manipulation techniques because the nonlinear optical response involves processes with considerably greater degrees of freedom than those of the linear optical response. As examples, we propose a method for trapping single organic molecules that is more effective than ever before, selectively pulling the molecules with a particular transition energy, and our proposed method allows for high-spatial-resolution optical manipulation beyond the diffraction limit.

Model of the photoexcitation processes of a two-level molecule coherently coupled to an optical antenna.

We theoretically investigate photoexcitation processes of a two-level molecular system coherently coupled with an antenna system having a significant dissipation. The auxiliary antenna enables the whole system to exhibit anomalous optical effects by controlling the coupling with the molecule. For example, in the weak excitation regime, the quantum interference yields a distinctive energy transparency through the antenna, which drastically reduces the energy dissipation. On the other hand, in the strong excitation regime, a population inversion of the two-level molecule appears due to the nonlinear effect. Both phenomena can be explained by regarding the antenna and molecule as one quantum-mechanically coupled system. Such an approach drives further research to exploit the full potential of the coupled systems.