Optical Sum-frequency Generation Research Articles

On the generation of optical third-harmonic through quasi-phase-matching in quadratic nonlinear crystals

We investigate the simultaneous processes of optical frequency doubling and sum frequency generation in quasi-phase-matched quadratically nonlinear crystals. Specifically, we focus on lattices with domain thicknesses corresponding to the coherence lengths of the two cascaded parametric processes and explore the realistic scenario of a single crystal containing sequential domain segments, each independently satisfying quasi-phase-matching for optical frequency doubling and summing, respectively. We demonstrate that high conversion efficiencies to the third harmonic can be obtained from an arbitrary fundamental wavelength.

Desorption activation energy of hydrogen from the Si (111)1x1: H surface studied by optical sum frequency generation and second harmonic generation

The desorption kinetics of hydrogen from the H-Si (111)1 × 1 surface prepared by molecular hydrogen exposure has been studied by combining optical sum frequency generation (SFG) for higher coverage and second harmonic generation (SHG) for lower coverage at several sample temperatures from 711 K to 770 K. The hydrogen desorption activation energy was found as Ed = 60.1 ± 8.8 kcal/mol (2.60 ± 0.38 eV) for the second order desorption for the coverage above 0.44 ML. For the first order desorption at the coverage below 0.18 ML the desorption activation energy was found as Ed= 32.6 ± 8.1 kcal/mol (1.41±0.35 eV).

Changes in fine structure of amylopectin and internal structures of starch granules in developing endosperms and culms caused by starch branching enzyme mutations of japonica rice.

BEIIb plays a specific role in determining the structure of amylopectin in rice endosperm, whereas BEIIa plays the similar role in the culm where BEIIb is absent. Cereals have three types of starch branching enzymes (BEs), BEI, BEIIa, and BEIIb. It is widely known that BEIIb is specifically expressed in the endosperm and plays a distinct role in the structure of amylopectin because in its absence the amylopectin type changes to the amylose-extender-type (ae-type) or B-type from the wild-type or A-type and this causes the starch crystalline allomorph to the B-type from the wild-type A-type. This study aimed to clarify the role of BEIIa in the culm where BEIIb is not expressed, by using a be2a mutant in comparison with results with be2b and be1 mutants. The results showed that the amylopectin structure exhibited the B-type in the be2a culm compared with the A-type in the wild-type culm. The starch granules from the be2a culm also showed the B-type like allomorph when examined by X-ray diffraction analysis and optical sum frequency generation spectroscopy. Both amylopectin chain-length profile and starch crystalline properties were found to be the A-type at the very early stage of endosperm development at 4-6days after pollination (DAP) even in the be2b mutant. All these results support a view that in the culm as well as in the endosperm at 4-6 DAP, BEIIa can play the role of BEIIb which has been well documented in maturing endosperm. The possible mechanism as to how BEIIa can play its role is discussed.

Effects of BEIIb-Deficiency on the Cluster Structure of Amylopectin and the Internal Structure of Starch Granules in Endosperm and Culm of Japonica-Type Rice.

It is known that one of starch branching enzyme (BE) isoforms, BEIIb, plays a specific role not only in the synthesis of distinct amylopectin cluster structure, but also in the formation of the internal structure of starch granules in rice endosperm because in its absence the starch crystalline polymorph changes to the B-type from the typical A-type found in the wild-type (WT) cereal endosperm starch granules. In the present study, to examine the contribution of BEIIb to the amylopectin cluster structure, the chain-length distributions of amylopectin and its phosphorylase-limit dextrins (Φ-LD) from endosperm and culm of a null be2b mutant called amylose-extender (ae) mutant line, EM10, were compared with those of its WT cultivar, Kinmaze, of japonica rice. The results strongly suggest that BEIIb specifically formed new short chains whose branch points were localized in the basal part of the crystalline lamellae and presumably in the intermediate between the crystalline and amorphous lamellae of amylopectin clusters in the WT endosperm, whereas in its absence branch points which were mainly formed by BEI were only located in the amorphous lamellae of amylopectin. These differences in the cluster structure of amylopectin between Kinmaze and EM10 endosperm were considered to be responsible for the differences in the A-type and B-type crystalline structures of starch granules between Kinmaze and EM10, respectively. The changes in internal structure of starch granules caused by BEIIb were analyzed by wide angle X-ray diffraction, small-angle X-ray scattering, solid state 13C NMR, and optical sum frequency generation spectroscopy. It was noted that the size the amylopectin cluster in ae endosperm (approximately 8.24 nm) was significantly smaller than that in WT endosperm (approximately 8.81 nm). Based on the present results, we proposed a model for the cluster structure of amylopectin in WT and ae mutant of rice endosperm. We also hypothesized the role of BEIIa in amylopectin biosynthesis in culm where BEIIb was not expressed and instead BEIIa was the major BE component in WT of rice.

Dual Resonant Sum Frequency Generations from Two-Dimensional Materials.

We propose dual resonant optical sum frequency generation (SFG), where the two most singular resonances could be selected, and report for the monolayer (1L-) WSe2 when one (ω1) of two excitation pulses is resonant to A exciton and their sum frequency (ω1 + ω2) to D exciton. The dual resonant SFG confirms that, under an irradiation of ω1 and ω2 pulses with the same fluence of ∼1.4 × 1010 W/m2, its signal intensity could be enhanced about 20 times higher than the resonant SHG (i.e., 2ω1 to the D excitonic absorption). Further, the dual resonant SFG intensity of 1L-WSe2 is found to be 1 order of magnitude higher than the single resonant SFG intensity of 1L-WS2 under the same condition of two-pulse irradiation. Finally, observations of the dual resonant SFG are thoroughly examined using real-time time-dependent density functional theory (rt-TDDFT), and the relevant nonlinear optical characteristics are scrutinized using the Greenwood-Kubo formalism.

Understanding Dissolution and Crystallization with Imaging: A Surface Point of View.

The tendency for crystallization during storage and administration is the most considerable hurdle for poorly water-soluble drugs formulated in the amorphous form. There is a need to better detect often subtle and complex surface crystallization phenomena and understand their influence on the critical quality attribute of dissolution. In this study, the interplay between surface crystallization of the amorphous form during storage and dissolution testing, and its influence on dissolution behavior, is analyzed for the first time with multimodal nonlinear optical imaging (coherent anti-Stokes Raman scattering (CARS) and sum frequency generation (SFG)). Complementary analyses are provided with scanning electron microscopy, X-ray diffraction and infrared and Raman spectroscopies. Amorphous indomethacin tablets were prepared and subjected to two different storage conditions (30 °C/23% RH and 30 °C/75% RH) for various durations and then dissolution testing using a channel flow-through device. Trace levels of surface crystallinity previously imaged with nonlinear optics after 1 or 2 days of storage did not significantly decrease dissolution and supersaturation compared to the freshly prepared amorphous tablets while more extensive crystallization after longer storage times did. Multimodal nonlinear optical imaging of the tablet surfaces after 15 min of dissolution revealed complex crystallization behavior that was affected by both storage condition and time, with up to four crystalline polymorphs simultaneously observed. In addition to the well-known α- and γ-forms, the less reported metastable ε- and η-forms were also observed, with the ε-form being widely observed in samples that had retained significant surface amorphousness during storage. This form was also prepared in the pure form and further characterized. Overall, this study demonstrates the potential value of nonlinear optical imaging, together with more established solid-state analysis methods, to understand complex surface crystallization behavior and its influence on drug dissolution during the development of amorphous drugs and dosage forms.

All-Optical Stern-Gerlach Effect.

We introduce a novel formalism in which the paraxial coupled wave equations of the nonlinear optical sum-frequency generation process are shown to be equivalent to the Pauli equation describing the dynamics of a spin-1/2 particle in a spatially varying magnetic field. This interpretation gives rise to a new classical state of paraxial light, described by a mutual beam comprising of two frequencies. As a straightforward application, we propose the existence of an all-optical Stern-Gerlach effect, where an idler beam is deflected by a gradient in the nonlinear coupling, into two mutual beams of the idler and signal waves (equivalent to oppositely oriented spinors), propagating in two discrete directions. The Stern-Gerlach deflection angle and the intensity pattern in the far field are then obtained analytically, in terms of the parameters of the original optical system, laying the grounds for future experimental realizations.

Localised detection of thiophenol with gold nanotriangles highly structured as honeycombs by nonlinear sum frequency generation spectroscopy

Gold nanotriangles structured as honeycombs and fabricated by nanosphere lithography on a gold film are functionalised by thiophenol molecules in order to be used as plasmonic sensors in nonlinear optical sum frequency generation (SFG) spectroscopy. The monitoring and the characterisation of the surface optical properties are performed by UV–visible differential reflectance spectroscopy showing an absorbance maximum located at 540 nm for p- and s-polarisation beams. SFG spectroscopy proves to be effective for thiophenol detection in ssp-polarisation scheme, while the molecular SFG signal disappears in ppp-configuration due to the strong s–d interband contribution of gold. However, in ssp-configuration, the vibration modes of thiophenol molecules at 3050 and 3071 $${\hbox {cm}}^{-1}$$ are yet observed thanks to the excitation of a transversal plasmon mode by the incident visible laser beam, whereas they are usually very difficult to distinguish by surface-enhanced Raman scattering and other vibrational optical probes.

Hydrogen desorption kinetics from H‐Si (111) surfaces studied by optical sum frequency generation and second harmonic generation

We have studied hydrogen desorption from a flat H‐Si (111)1 × 1 surface at 711 K by observing sum frequency generation (SFG) and second harmonic generation (SHG) spectra. Flat H‐Si (111) surfaces were prepared by dosing hydrogen molecules in an ultra‐high vacuum chamber with a base pressure of 〜10−8 Pa. Combining the SFG and SHG methods, the desorption order has been clarified over the whole hydrogen coverage range from 1 monolayer (ML) to 0 ML. The hydrogen desorption was assigned as second order in the high coverage range of 1 ML–0.18 ML by using SFG spectroscopy and as first order in the coverage range of 0.18 ML–0.0 ML by using SHG spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.

Optical Sum Frequency Generation Spectroscopy of Cracked Non-Glutinous Rice (<i>Oryza sativa</i> L.) Kernels

In order to study the correlation between the cracking of rice (Oryza sativa L.) kernels and the molecular structure of the amylopectin in them, we attempted optical sum frequency generation (SFG) spectroscopy in the C-H stretching vibration region for normal and cracked japonica non-glutinous rice kernels. The samples were Koshihikari and Nipponbare. In Nipponbare, the width of the SFG spectrum peak at 2915 cm- 1 of the cracked rice kernels was broader than that of the normal ones, while for Koshihikari there was no clear difference. The width of the 2915 cm- 1 peak is suggested to originate from the variety of the higher-order structure of the saccharide chains in amylopectin. Although this is a tentative result, this method is shown to have a potential of serving for preventing the cracking of the rice kernels.

Wetting effect on optical sum frequency generation (SFG) spectra of d-glucose, d-fructose, and sucrose

We report a sum frequency generation (SFG) spectroscopy study of d-glucose, d-fructose and sucrose in the CH stretching vibration regime. Wetting effect on the SFG spectra was investigated. The SFG spectrum of d-glucose changed from that of α-d-glucose into those of α-d-glucose monohydrate by wetting. The SFG spectra showed evidence of a small change of β-d-fructopyranose into other anomers by wetting. SFG spectra of sucrose did not change by wetting. Assignments of the vibrational peaks in the SFG spectra of the three sugars in the dry and wet states were performed in the CH stretching vibration region near 3000cm−1.

Optical sum-frequency generation in a whispering-gallery-mode resonator

We demonstrate sum-frequency generation between a telecom wavelength and the Rb D2 line, achieved through natural phase matching in a nonlinear whispering gallery mode resonator. Due to the strong optical field confinement and ultra high Q of the cavity, the process saturates already at sub-mW pump peak power, at least two orders of magnitude lower than in existing waveguide-based devices. The experimental data are in agreement with the nonlinear dynamics and phase matching theory based on spherical geometry. Our experimental and theoretical results point toward a new platform for manipulating the color and quantum states of light waves for applications such as atomic memory based quantum networking and logic operations with optical signals.

Optical Sum Frequency Generation Spectra of Water Molecules on a Polycarbonate Film Exposed to O<sub>2 </sub>Plasma

Optical Sum Frequency Generation Spectra of Water Molecules on a Polycarbonate Film Exposed to O<sub>2 </sub>Plasma

Red beam generation based on aperiodically poled lithium niobate

We propose a novel device with a simple architecture for high-power red beam generation. The device is an optical parametric generator based on an aperiodically poled LiNbO3 grating in which both the optical parametric amplification and sum frequency generation processes are simultaneously phase matched. The pump is a quasi-continuous-wave laser operating at 1064nm. Aperiodic gratings which enable simultaneous phase matching of the two processes were designed using a method that gives the flexibility to adjust the relative strength of these two processes. A model that takes the diffraction of the beams into account was developed to characterize the red beam generation performance of the device depending on the parameters: the relative strength of these processes, the length of the crystal, the average pump power, and the pump beam waist radius. If one uses the 2-D Fourier transform in the solution of the coupled-mode equations, the computation power required for performing such a characterization on a personal computer is prohibitively large. Owing to the circular symmetry of the system, we employ the Hankel transform to overcome this bottleneck.

Si[sbnd]H vibrational mode on a H[sbnd]Si(111)1 × 1 surface with hydrogen deficiency

We used a dipole coupling theory to calculate modulations of the SiH vibrational mode on a HSi(111)1×1 surface, and analyzed the observed optical sum frequency generation (SFG) spectra. As the hydrogen coverage decreased, the peak position of the SiH vibrational mode shifted to the red side in the experimental SFG spectra [Hien et al., Surf. Int. Anal., 44 662 (2012)]. The calculated peak shift was quantitatively consistent with the observed redshift, indicating that the peak shift can be attributed to dipole coupling among the SiH oscillators. On the other hand, the experimental peak widths at lower coverages were wider than those of the calculated peaks. This suggests that local structural defects and/or dangling bonds modulated the vibration of the surrounding SiH oscillators.

Feasibility Study for Near-Field Optical Sum-Frequency Generation Spectroscopy Using a Metal-Coated Fiber

Feasibility Study for Near-Field Optical Sum-Frequency Generation Spectroscopy Using a Metal-Coated Fiber

X-ray and optical wave mixing

Light-matter interactions are ubiquitous, and underpin a wide range of basic research fields and applied technologies. Although optical interactions have been intensively studied, their microscopic details are often poorly understood and have so far not been directly measurable. X-ray and optical wave mixing was proposed nearly half a century ago as an atomic-scale probe of optical interactions but has not yet been observed owing to a lack of sufficiently intense X-ray sources. Here we use an X-ray laser to demonstrate X-ray and optical sum-frequency generation. The underlying nonlinearity is a reciprocal-space probe of the optically induced charges and associated microscopic fields that arise in an illuminated material. To within the experimental errors, the measured efficiency is consistent with first-principles calculations of microscopic optical polarization in diamond. The ability to probe optical interactions on the atomic scale offers new opportunities in both basic and applied areas of science.

Basic Theory of Surface Sum-Frequency Generation

A detailed description on the basic theory of optical sum-frequency generation from an interfacial system is presented. Both the interface and the bulk generally contribute to the sum-frequency output. Two seemingly different approaches to specify bulk nonlinearity that includes electric-quadrupole and magnetic-dipole contributions are shown to yield the same sum-frequency output if surface nonlinearity is properly taken into account. The question of whether surface and bulk nonlinearities can be uniquely defined and separately measured is discussed. It is shown that the answer is affirmative. Truly bulk and truly surface nonlinear susceptibilities can be uniquely defined and separately deduced from measurements of transmitted and reflected sum-frequency generation.

Optical Sum Frequency Generation Image of Rice Grains

We observed optical sum frequency generation (SFG) images of cross-sections of glutinous rice grains, in order to test a possibility of the SFG microscopy as a tool for monitoring polysaccharide species in rice grains. The SFG response in the CH vibration range was the most intense in the crush cell layer at the edge of the endosperm adjacent to the embryo probably due to optical reflection and scattering effectby the rugged dielectric structure of the crush cell layer. The SFG spectra as a function of the infrared wavelength depended on the measurement position in the endosperm. The SFG results were compared with those by Raman and infrared spectroscopies for the same samples.

Simultaneously phase-matched parametric processes in a single-pass interaction for efficient visible generation

We demonstrate simultaneously phase-matched cascaded optical parametric amplification (OPA) and sum-frequency generation (SFG) processes in a single-pass interaction in a BBO crystal, where the seed pulse is produced through the self-induced superfluorescence generation. Tunable femtosecond pulses in the blue-green spectral range are produced through the single-pass SFG interaction with a maximum conversion efficiency of about 12%.