Whispering‐gallery microcavities with unidirectional laser emission

Optical whispering‐gallery mode (WGM) microcavities featuring ultrahigh Q factors and small mode volumes enhance significantly the interaction between light and matter, becoming an excellent platform for achieving ultralow‐threshold microlasers. However, the emission of traditional WGMs is isotropic due to the rotational symmetry of cavity geometries, which hinders the potential photonics applications. In this review, the progress in WGM microcavities towards unidirectional laser emission is summarized. When a subwavelength scatterer is placed on the boundary of the microcavity, the unidirectional emission occurs due to the collimation effect of the microcavity‐enhanced scattering field. Furthermore, microcavities deformed from the circular shapes can not only produce the chaos‐assisted unidirectional emission, but also maintain high Q factors by special design and fabrication processes. Finally, gratings along the circumference of the WGM microdisk or microring can scatter the WGMs in the vertical direction. The review also lists several important applications of these types of microcavities, such as wide‐band laser illumination source, free‐space coupling, evanescent‐field enhancement, optical energy storage, and sensing.

     

Whispering gallery modes in intrinsic TiO2 microspheres coupling to the defect‐related photoluminescence after visible excitation

Defect‐caused visible photoluminescence after visible excitation in anatase TiO₂ microresonators couples to whispering gallery modes (WGMs). Spherical anatase TiO₂ of a radius between 1.5 µm and 4 µm have been prepared by a sol–gel technique based on hydrolysis of titanium tetrabutoxide. The observation of WGMs in intrinsic anatase TiO₂ without additional dopant offers new perspectives for the localisation of light at TiO₂ surfaces for the design of photocatalysts.

WGMs show up as narrow peaks in the photoluminescence spectra of TiO₂ microparticles after visible excitation.     

Scattering Invisibility With Free‐Space Field Enhancement of All‐Dielectric Nanoparticles

Simultaneous scattering invisibility and free‐space field enhancement have been achieved based on multipolar interferences among all‐dielectric nanoparticles. The scattering properties of all‐dielectric nanowire quadrumers are investigated and two sorts of scattering invisibilities have been identified: the trivial invisibility where the individual nanowires are not effectively excited; and the nontrivial invisibility with strong multipolar excitations within each nanowire, which results in free‐space field enhancement outside the particles. It is revealed that such nontrivial invisibility originates from not only the simultaneous excitations of both electric and magnetic resonances, but also their significant magnetoelectric cross‐interactions. We further show that the invisibility obtained is both polarization and direction selective, which can probably play a significant role in various applications including non‐invasive detection, sensing, and non‐disturbing medical diagnosis with high sensitivity and precision.     

Polarization‐free directional coupling of surface plasmon polaritons

Surface plasmon polaritons (SPPs) have sparked enormous interest on nanophotonics beyond the diffraction limit for their remarkable capabilities of subwavelength confinements and strong enhancements. Due to the inherent polarization sensitivity of the SPPs [transverse‐magnetic (TM) polarization], it is a great challenge to couple the s‐polarized free‐space light to the SPPs. Here, an ultrasmall defect aperture (<λ²/2) is designed to directionally couple both the p‐ and s‐polarized incident beams to the single SPP mode in a broad bandwidth, which is guided by a subwavelength plasmonic waveguide. Simulations show that hot spots emerge at the sharp corners of the defect aperture when the incident beams illuminate it from the back side. The strong radiative fields from the hot spots are directionally coupled to the SPP mode because of the symmetry breaking of the defect aperture. By adjusting the structural parameters, both the unidirectional and bidirectional SPP coupling from the two orthogonal linear‐polarization incident beams are experimentally demonstrated. The polarization‐free coupling of the SPPs is of importance in circuits for fully optical processing of information with a deep‐subwavelength footprint.

     

Coulomb‐enhanced spin–orbit coupling and semiconductor to half‐metal transition under pressure in Sr2CrReO6

Ordered Sr₂CrReO₆ has been synthesized recently. It is measured to be ferrimagnetic semiconductor, in contrary to the previous reports of metallic properties. To solve the discrepancy, we have investigated the compound by using the density functional theory. The semiconducting behavior is reproduced by including the electron correlation and spin–orbit coupling simultaneously. The calculated band gap is 0.22 eV, close to the experimental value of 0.21 eV. A large orbital moment of 0.69µ_B is found for Re, which is caused by the Coulomb‐enhanced spin–orbit coupling. By applying pressure, a semiconductor to half‐metal transition is observed through 5% volume compression.

     

Single‐shot CARS thermometry of high‐pressure hydrocarbon flames using simultaneous intensity and linewidth measurements

We demonstrate the feasibility of single laser shot coherent anti‐Stokes Raman scattering thermometry with simultaneous measurement of intensities of hydrogen Q‐branch lines and their linewidths in a pulsed CH₄/O₂ combustion chamber operating at 20 MPa pressure and 3000 K temperature—parameters that are typical for full‐scale rocket engines. The measurements were done by means of a spectrograph combined with an interferometer having orthogonal directions of dispersions. This approach allows correct temperature evaluation that takes into account the directly measured linewidths. Copyright © 2010 John Wiley & Sons, Ltd.     

Excited‐state structural dynamics and vibronic coupling of 1,3‐dithiole‐2‐thione—resonance Raman spectroscopy and density functional theory calculation study

1,3‐Dithiole‐2‐thione (DTT) was synthesized and characterized using NMR, FT‐Raman, FT‐IR, UV spectroscopies. Resonance Raman spectra (RRs) were obtained with 341.5, 354.7 and 368.9 nm excitation wavelengths and density functional calculations were done to elucidate the electronic transitions and the RRs of DTT in cyclohexane solution. The RRs indicate that the Franck‐Condon region photodynamics is predominantly along the CS stretch+ H‐CC‐H scissor υ₄, accompanied by the H‐CC‐H scissor υ₃, S‐C‐S symmetric stretch υ₆, CC stretch υ₂, and overtone of the non‐totally symmetric SC‐S2 out‐of‐plane deformation 2υ₁₁. The excited‐state dynamics and the force constant of CS stretch calculated by the RRs were discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Online coupling of high‐performance liquid chromatography with surface‐enhanced Raman spectroscopy for the identification of historical dyes

High‐performance liquid chromatography (HPLC) is still, today, the technique of choice for the analysis of natural dyes in artistic objects and historical textiles, particularly in association with photodiode array (PDA) detection. In the last two decades, surface‐enhanced Raman spectroscopy (SERS) gained also increasing importance for these investigations thanks to its sensitivity and limited requirements in terms of sample quantity. In favor of SERS, its high specificity in molecular recognition typical of vibrational spectroscopy should be mentioned, whereas this non‐separative technique is obviously disadvantaged in the analyses of mixed chromophores, as is often the case of many natural dyes and also of tints obtained by the combined use of different colorants. An optimized experimental setup combining the two techniques, HPLC‐PDA and SERS, is proposed in the present work, allowing online SERS detection of different dyeing compounds eluted from the HPLC column. Examples are presented concerning some of the colorants most widely used in history, such as morin and luteolin for yellow dyes, alizarin, purpurin, laccaic, kermesic, and carminic acids for red ones, and indigotin for blue tints. Copyright © 2016 John Wiley & Sons, Ltd.     

Design of plasmonic bowtie nanoring array with high sensitivity and reproducibility for surface‐enhanced Raman scattering spectroscopy

A metallic bowtie nanoring array is designed to gain high sensitive and reproducible substrate for surface‐enhanced Raman scattering (SERS) spectroscopy. The localized surface plasmon resonance (LSPR), the electric field enhancement factors (EFs) and the electric field distribution of the bowtie and bowtie nanoring array are numerically investigated by means of the finite‐difference time domain (FDTD) method. After the optimization of the particle size and the array period, the maximum electromagnetic field EF approaches 153, and the corresponding SERS electromagnetic enhancement factor (EMEF) reaches 5.4 × 10⁸. This highly sensitive and reproducible substrate can be a good candidate for SERS applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Palladium‐catalyzed cyclization of 2‐alkynyl‐N‐ethanoyl anilines to indoles: synthesis,structural, spectroscopic,and mechanistic study

This study reports a facial regio‐selective synthesis of 2‐alkyl‐N‐ethanoyl indoles from substituted‐N‐ethanoyl anilines employing palladium (II) chloride, which acts as a cyclization catalyst. The mechanistic trait of palladium‐based cyclization is also explored by employing density functional theory. In a two‐step mechanism, the palladium, which attaches to the ethylene carbons, promotes the proton transfer and cyclization. The gas‐phase barrier height of the first transition state is 37 kcal/mol, indicating the rate‐determining step of this reaction. Incorporating acetonitrile through the solvation model on density solvation model reduces the barrier height to 31 kcal/mol. In the presence of solvent, the electron‐releasing (–CH₃) group has a greater influence on the reduction of the barrier height compared with the electron‐withdrawing group (–Cl). These results further confirm that solvent plays an important role on palladium‐catalyzed proton transfer and cyclization. For unveiling structural, spectroscopic, and photophysical properties, experimental and computational studies are also performed. Thermodynamic analysis discloses that these reactions are exothermic. The highest occupied molecular orbital?lowest unoccupied molecular orbital gap (4.9–5.0 eV) confirms that these compounds are more chemically reactive than indole. The calculated UV–Vis spectra by time‐dependent density functional theory exhibit strong peaks at 290, 246, and 232 nm, in good agreement with the experimental results. Moreover, experimental and computed ¹H and ¹³C NMR chemical shifts of the indole derivatives are well correlated. Copyright © 2015 John Wiley & Sons, Ltd.     

Quantum uncertainties of the confined Harmonic Oscillator in position,momentum and phase‐space

Quantum uncertainties in position, momentum and phase‐space are studied in the confined Harmonic Oscillator. Standard deviations and Shannon entropies are used to quantify these uncertainties and their behaviors are compared and contrasted. We observe a minimum in the momentum space Shannon entropy as the box length is increased, a feature that is not present in the momentum space standard deviation. The behaviors of the standard deviation product and the Shannon entropy sum, which form the basis of uncertainty relationships, are also analyzed. Maxima are observed in the product as the box length increases in sharp contrast to the entropy sum. The relationship between these behaviors and that of the Shannon entropy of the phase‐space Wigner function is analyzed and discussed. An analysis of the energetic components is also performed. The results reinforce the idea that the confined Harmonic Oscillator can be considered as an intermediate model which interpolates between the Particle in a Box Model and the Harmonic Oscillator and thus contains characteristics of both models.

     

Radiation coupling with two‐dimensional electron systems in the low limit of the microwave band: magnetoresistance response

We report on a theoretical study of radiation‐induced resistance oscillations and zero‐resistance states in two‐dimensional electron systems when the irradiation frequency is very low. In this situation the photon energy is much smaller than the spacing between the Landau levels and therefore interlevel transitions are excluded. Experiments show that when these frequencies are used, resistance oscillations disappear and, instead, a strong suppression of magnetoresistance response is obtained. We apply the radiation‐driven electron orbit model concluding that the resistance suppression is a manifestation of an oscillation of very large wavelength. Under this regime we study the connection with larger frequencies and the dependence on radiation power and temperature. For high enough radiation intensity, we predict that a regime of zero‐resistance states can be reached at these low frequencies, too. The calculated results are in good agreement with experiments. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vibrational spectral studies on charge transfer and ionic hydrogen‐bonding interactions of nonlinear optical material L‐arginine nitrate hemihydrate

The near infrared Fourier‐transform (NIR FT)‐Raman and Fourier‐transform infrared (FT‐IR) spectroscopies supported by HF/6‐31G(d) computations have been employed to derive equilibrium geometry, vibrational wavenumbers and the first hyperpolarizability of the nonlinear optical (NLO) material, L ‐arginine nitrate (LAN) hemihydrate. The reasonable NLO efficiency, predicted for the first time in this novel compound, has been confirmed by Kurtz–Perry powder second harmonic generation (SHG) experiments. The changes in the atomic charge distribution among different groups due to the presence of strong electronegative atoms and the shrinking of N O bonds of nitrate anion and C N bonds of guanidyl group have been analyzed. The splitting of the carboxylate stretching modes, blue shifting of methine vibrations and the electronic effects such as backdonation and induction on the methylene hydrogen atoms have also been examined in detail. The intense low wavenumber H‐bond Raman vibrations due to electron–phonon coupling and nonbonded interactions in making the LAN molecule NLO active have been discussed based on the vibrational spectral features. The natural bond orbital (NBO) analysis and HF computations confirm the occurrence of strong intra‐ and intermolecular N H·O and O H·O ionic hydrogen bonding between charged species providing the noncentrosymmetric structure in the LAN crystal. Copyright © 2008 John Wiley & Sons, Ltd.     

1H NMR study of through‐bond and through‐space effects in the hetero‐association of pyridine with alkane diols

The ¹H NMR titration method is used to investigate through‐space and through‐bond effects on the association of diols with pyridine in benzene. Alkan‐1,n‐diols (n goes from 2 to 10), DL and meso isomers of butan‐2,3‐, pentan‐2,4‐ and hexan‐2,5‐diols, two adamantane diols and a bicyclo[2.2.2]octane diol are compared with alkanols. The –CH₂OH groups of the tri‐ and bicyclic compounds behave as if they were independent, with limiting OH proton shifts (at very low concentration) and both the first and the second association constants similar to those of a primary alcohol. In contrast, the alkane diols, with n = 2–4, display unusually high limiting shifts, ranging from 1.0 to 1.5 ppm (2.1 ppm for one methyl‐substituted diol). For these diols the first dissociation constant and the sum of the OH proton shifts in the 1:1 pyridine: diol complex are enhanced. This may be attributed to small cooperative effects, implying intramolecular hydrogen bonding, for n = 3 and 4, but for n = 2 a through‐bond effect accounts for most of the increase. Substituent interaction falls off sharply for n = 5 and is practically negligible for n = 10, for which the second association constant is close to the first. A sterically hindered BiEDOT diol, 2,2′‐bis{(3,4‐ethylenedioxythienyl)‐5‐[3‐(2,2,4,4‐tetramethylpentan‐3‐ol)]} behaves like the polycyclic compounds, with the two ? C(t‐Bu)₂OH groups independent. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrogen‐bonded nucleophile effects in ANS: the reactions of 1‐chloro and 1‐fluoro‐2,4‐dinitrobenzene with 2‐guanidinobenzimidazole, 1‐(2‐aminoethyl)piperidine and N‐(3‐aminopropyl)morpholine in aprotic solvents

The kinetics of the reactions of 2,4‐dinitrofluorobenzene (DNFB) and 2,4‐dinitrochlorobenzene (DNClB) with 2‐guanidinobenzimidazole (2‐GB) at 40 ± 0.2 °C in dimethylsulphoxide (DMSO), toluene, and in toluene–DMSO mixtures, and with 1‐(2‐aminoethyl)piperidine (2‐AEPip) and N‐(3‐aminopropyl)morpholine (3‐APMo) in toluene at 25 ± 0.2 °C were studied under pseudo first‐order conditions. For the reactions of 2‐GB carried out in pure DMSO, the second‐order rate coefficients were independent of the amine concentration. In contrast, the reactions of 2‐GB with DNFB in toluene, showed a kinetic behaviour consistent with a base‐catalysed decomposition of the zwitterionic intermediate. These results suggest an intramolecular H‐bonding of 2‐GB in toluene, which is not present in DMSO. To confirm this interpretation the reactions were studied in DMSO–toluene mixtures. Small amounts of DMSO produce significant increase in rate that is not expected on the basis of the classical effect of a dipolar aprotic medium; the effect is consistent with the formation of a nucleophile/co‐solvent mixed aggregate. For the reactions of 3‐APMo with both substrates in toluene, the second‐order rate coefficients, k_A, show a linear dependence on the [amine]. 3‐APMo is able to form a six‐membered ring by an intramolecular H‐bond which prevents the formation of self‐aggregates. In contrast, a third order was observed in the reactions with 2‐AEPip: these results can be interpreted as a H‐bonded homo‐aggregate of the amine acting as a better nucleophile than the monomer. Most of these results can be well explained within the frame of the ‘dimer nucleophile’ mechanism. Copyright © 2010 John Wiley & Sons, Ltd.     

Absorption and resonance Raman spectroscopy of the 1Bu state of trans‐1,3,5‐hexatriene including vibronic coupling

The vibronic coupling between the first excited S₁ (2¹A_g) and the second excited S₂ (1¹B_u) singlet electronic states in spectroscopy of trans‐1,3,5‐hexatriene molecule is investigated on the basis of a model consisting of two electronic states coupled by two vibrational modes. Employing a perturbation theory that treats the intramolecular couplings in a perturbative manner, the absorption and resonance Raman cross sections and excitation profiles of this molecule are calculated using the time‐correlation function formalism. The non‐Condon corrections are included in evaluation of cross sections. The multidimensional time‐domain integrals that arise in these calculations have been evaluated for the case in which S₀ (1¹A_g) S₂ (1¹B_u) electronic transition takes place between displaced and distorted harmonic potential energy surfaces. The calculated spectra are in good agreement with the experimental ones. Copyright © 2011 John Wiley & Sons, Ltd.     

Growth and properties of Li,Ta modified (K,Na)NbO3 lead‐free piezoelectric single crystals

Li, Ta modified (K,Na)NbO₃ single crystals with the size of 18 mm × 18 mm × 10 mm were successfully grown by top‐seeded solution growth method, with orthorhombic–tetra‐gonal phase transition temperature ～79 °C and Curie temperature ～276 °C. The electromechanical coupling factors k₃₃ and k_t were found to be ～88% and ～65%, respectively. The piezoelectric coefficient d₃₃ for the [001]_c poled crystals reached 255 pC/N. In addition, the electromechanical coupling factor exhibited high stability over the temperature range of –50 °C to 70 °C, making these lead free crystals good candidates for electromechanical applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Plasmon‐enhanced Raman scattering of coaxial hybrid nanowires made with light‐emitting polymer and gold

We report on the plasmon‐enhanced Raman scattering of coaxial hybrid nanowires (NWs) made with light emitting poly(3‐methylthiophene) (P3MT) and gold (Au) core or coating. Absorption spectra of coaxial hybrid NWs showed the absorption peaks because of localized surface plasmon (SP) excitation at ~ 567 and ~ 610 nm, in addition to the π–π* transition peaks of P3MT. Raman spectra of a single strand of coaxial hybrid NW and plain P3MT NW was obtained by using three different wavelengths of laser excitation of 514, 633, and 785 nm. We found that Raman intensities of hybrid coaxial NWs were enhanced by 4 to 15 times over those of plain P3MT NWs with the Raman excitation wavelengths close to the observed SP energies of coaxial NWs. We attributed the observed enhancement of the Raman signal to the resonance of the incident laser with the matching SP energies, rather than the possible doping level change, in hybrid coaxial NWs. Copyright © 2012 John Wiley & Sons, Ltd.     

Electron–phonon coupling and vibrational modes contributing to linear electro‐optic effect of the efficient NLO chromophore 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST) from their vibrational spectra

The optimized geometry and structural features of the most prospective electro‐optic crystal 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST), and the vibrational spectral investigations have been comprehensively described with the near infrared Fourier transform (NIR FT) Raman and Fourier transform infrared (FT‐IR) spectra supported by the density functional theoretical (DFT) computations to elucidate the contribution of vibrational modes to the linear electro‐optic (LEO) effect. Mulliken population analysis and natural bond orbital (NBO) analysis have also been carried out to analyze the effects of intramolecular charge transfer (ICT), intramolecular hydrogen bonding and hyperconjugative interactions on the geometries. The influence of CT interaction between the phenyl ring and the dimethylamino group of the nonlinear optical (NLO) chromophore on the endocyclic and exocyclic angles, and the electronic effects such as hyperconjugation and back‐donation on the methyl hydrogen atoms have been examined. The concurrent intense activation of Raman and IR activities of the effective conjugation vibrational coordinate, which significantly contributes to the LEO effect resulting from the strong electron–phonon (e/ph) coupling, has been analyzed in detail. The effects of frontier orbitals, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), transition of electron density (ED) transfer and the influence of planarity in the stilbazolium ring on the first hyperpolarizability are also discussed. Copyright © 2008 John Wiley & Sons, Ltd.