Long-wavelength Properties Research Articles

Helicity-Sensitive Terahertz Detection in Monolayer 1T'-WTe2.

Valleytronics, identified as electronic properties of the energy band extrema in momentum space, has been intensively revived following the emergence of two-dimensional transition metal dichalcogenides (TMDCs) as their valley information can be controlled and probed through the spin angular momentum of light. Previous optical investigations of valleytronics have been limited to the visible/near-infrared spectral regime through which the carriers of most TMDCs can be excited. Monolayer 1T'-WTe2 with broken time-reversal symmetry provides a fertile platform to study the long-wavelength photonic properties in different valleys. Here, we employed a circularly polarized terahertz (THz) laser to selectively excite the valley of monolayer 1T'-WTe2 and demonstrate that the helicity-dependent photoresponse is generated via the photogalvanic effect (PGE). We also observed that the photocurrent is controlled by circular polarization and the external electric field. Because of the tunable Berry curvature dipole derived from the nontrivial wave functions near the inverted gap edge in monolayer WTe2, the bandgap can be tuned efficiently. Our results provide a versatile venue for controlling, detecting, and processing valleytronics and applications in on-chip THz imaging and quantum information processing.

Access to 2,4-Disubstituted Pyrrole-Based Polymer with Long-Wavelength and Stimuli-Responsive Properties via Copper-Catalyzed [3+2] Polycycloaddition.

Pyrrole-based polymers (PBPs), a type of fascinating functional polymers, play a crucial role in materials science. However, efficient synthetic strategies of PBPs with diverse structures are mainly focused on conjugated polypyrroles and still remain challenging. Herein, an atom and step economy protocol is described to access various 2,4-disubstituted PBPs by in situ formation of pyrrole core structure via copper-catalyzed [3+2] polycycloaddition of dialkynones and diisocyanoacetates. A series of PBPs is prepared with high molecular weight (Mw up to 18 200 Da) and moderate to good yield (up to 87%), which possesses a fluorescent emission located in the green to yellow light region. Blending the PBPs with polyvinyl alcohol, the stretchable composite films exhibit a significant strengthening of the mechanical properties (tensile stress up to 59 MPa, elongation at break >400%) and an unprecedented stress-responsive luminescence enhancement that over fourfold fluorescent emission intensity is maintained upon stretching up to 100%. On the basis of computational studies, the unique photophysical and mechanical properties are attributed to the substitution of carbonyl chromophores on the pyrrole unit.

Enhancing Near-Infrared Absorption in Terpyridyl Ru/Os Complexes with Ancillary Ligands to Activate Spin-Forbidden Transitions in Dye-Sensitized Solar Cells: A TDDFT Investigation.

Dye sensitizers with wideband absorption covering the near-IR region have long been of interest because they potentially harvest a wide range of solar energies essential to promote photocurrent power conversion efficiencies. In this study, we used time-dependent density functional theory with spin-orbit (SO) interactions to theoretically explore the long-wavelength absorptions and spin-forbidden triplet transitions activated by SO interactions for terpyridyl ruthenium/osmium complex dyes. These dyes feature a Ru(II) sensitizer coordinated with a phosphine ligand and are exemplified by DX1, denoted as [trans-dichloro-(phenyldimethoxyphosphine)(2,2';6',2″-terpyridyl-4,4',4″-tricarboxylic)Ru]. We found that ancillary ligands significantly affected the longest wavelength spin-allowed absorption, with NCS- ligands yielding longer wavelength S1 transitions than halides. High atomic number halide ligands caused blue shifts in the S1 transition. Os complexes consistently exhibited longer wavelength S1 transitions than Ru complexes with identical ligands. In Ru/Os complexes, ancillary ligands with higher atomic numbers have a more pronounced effect in activating spin-forbidden triplet transitions through spin-orbit coupling (SOC) than those with lower atomic numbers. The absorption wavelength of the SOC-activated transition primarily depended on the energy of lower lying triplet states. Some complexes exhibited T1 states activated by SOC, leading to longer wavelength absorption than that of SOC-activated T2 states. Our study revealed the significance of ancillary ligands and SOC interactions in Ru/Os complexes, offering insights for optimizing materials with enhanced long-wavelength absorption properties, particularly in the near-IR range, for photovoltaic and optoelectronic applications.

Active XY model on a substrate: Density fluctuations and phase ordering.

We explore the generic long-wavelength properties of an active XY model on a substrate, consisting of a collection of nearly phase-ordered active XY spins in contact with a diffusing, conserved species, as a representative system of active spinners with a conservation law. The spins rotate actively in response to the local density fluctuations and local phase differences, on a solid substrate. We investigate this system by Monte Carlo simulations of an agent-based model, which we set up, complemented by the hydrodynamic theory for the system. We demonstrate that this system can phase-synchronize without any hydrodynamic interactions. Our combined numerical and analytical studies show that this model, when stable, displays hitherto unstudied scaling behavior: As a consequence of the interplay between the mobility, active rotation, and number conservation, such a system can be stable over a wide range of the model parameters characterized by a novel correspondence between the phase and density fluctuations. In different regions of the phase space where the phase-ordered system is stable, it displays generalized quasi-long-range order (QLRO): It shows phase ordering which is generically either logarithmically stronger than the conventional QLRO found in its equilibrium limit, together with "miniscule number fluctuations," or logarithmically weaker than QLRO along with "giant number fluctuations," showing a novel one-to-one correspondence between phase ordering and density fluctuations in the ordered states. Intriguingly, these scaling exponents are found to depend explicitly on the model parameters. We further show that in other parameter regimes there are no stable, ordered phases. Instead, two distinct types of disordered states with short-range phase order are found, characterized by the presence or absence of stable clusters of finite sizes. In a surprising connection, the hydrodynamic theory for this model also describes the fluctuations in a Kardar-Parisi-Zhang (KPZ) surface with a conserved species on it, or an active fluid membrane with a finite tension, without momentum conservation and a conserved species living on it. This implies the existence of stable fluctuating surfaces that are only logarithmically smoother or rougher than the Edward-Wilkinson surface at two dimensions (2D) can exist, in contrast to the 2D pure KPZ-like "rough" surfaces.

Newton optimization and the Hessian matrix in scale-separation waveform inversion problems with reflected and transmitted waves

Summary Full waveform inversion (FWI) is often utilized for determining the medium parameters of the Earth by minimizing the misfit between observed and modelled waves. The conventional formulation of FWI is well suited to utilize transmitted waves to determine long-to-intermediate wavelength properties of the medium. Hovewer, the penetration depth of transmitted waves may be limited for a given acquisition. As a remedy, reflection waveform inversion (RWI) exploits the kinematic information in reflected waves to retrieve these long-wavelength properties, particularly below the maximum illumination depth of transmitted waves. Previous works have demonstrated the benefits of utilizing both transmitted and reflected waves, thereby considering a reconciliation of conventional FWI and RWI. One such formulation is known as joint full waveform inversion (JFWI), where reflected and transmitted waves are separately compared in the misfit functional. A disadvantage of gradient-based optimization schemes in RWI and JFWI is the presence of strong crosstalk due to mapping of reflected data residuals along the entire reflection wavepaths. Because RWI and JFWI require frequent least-squares migration, we are incentivized to determine well-focused search directions that allow large movements between the migration steps. Thus, we propose an improvement to RWI and JFWI by utilizing Newton methods to directly account for crosstalk between parameters. The crosstalk effects are described by the second-order sensitivities of the misfit functional, i.e. the Hessian matrix. We adopt the adjoint-state method to compute the first- and second order sensitivities of the misfit functional for any of these waveform inversion procedures in a unified framework and for arbitrary misfit functionals. Furthermore, we conceptually study the Hessian matrix in least-squares based full-, reflection- and joint full waveform inversion from a data-domain point of view. Synthetic examples and a three-dimensional field data example demonstrate that the truncated Gauss-Newton method is effective in attenuating artefacts due to crosstalk between spatially separated variables, thus substantially improving the spatial focusing of the search directions.

Critical dynamics of the antiferromagnetic O(3) nonlinear sigma model with conserved magnetization.

We study the near-equilibrium critical dynamics of the O(3) nonlinear sigma model describing isotropic antiferromagnets with a nonconserved order parameter reversibly coupled to the conserved total magnetization. To calculate response and correlation functions, we set up a description in terms of Langevin stochastic equationsof motion, and their corresponding Janssen-De Dominicis response functional. We find that in equilibrium, the dynamics is well-separated from the statics, at least to one-loop order in a perturbative treatment with respect to the static and dynamical nonlinearities. Since the static nonlinear sigma model must be analyzed in a dimensional d=2+ɛ expansion about its lower critical dimension d_{lc}=2, whereas the dynamical mode-coupling terms are governed by the upper critical dimension d_{c}=4, a simultaneous perturbative dimensional expansion is not feasible, and the reversible critical dynamics for this model cannot be accessed at the static critical renormalization group fixed point. However, in the coexistence limit addressing the long-wavelength properties of the low-temperature ordered phase, we can perform an ε=4-d expansion near d_{c}. This yields anomalous scaling features induced by the massless Goldstone modes, namely subdiffusive relaxation for the conserved magnetization density with asymptotic scaling exponent z_{Γ}=d-2, which may be observable in neutron scattering experiments. Intriguingly, if initialized near the critical point, the renormalization group flow for the effective dynamical exponents recovers their universal critical values z_{c}=d/2 in an intermediate crossover region.

Long-wavelength optical properties of the Ca0.33Sr0.33Ba0.33F2 solid solution single crystals

The optical characteristics of Ca0.33Sr0.33Ba0.33F2 (CSBF) single crystal of a ternary solid solution of calcium, strontium and barium fluorides were studied in order to create disordered optical media. Characteristics of the single crystals of individual fluorides CaF2, SrF2, BaF2 and binary solid solutions Ca0.6Sr0.4F2 and Ba0.67Sr0.33F2 were obtained. Broadband reflection and transmission spectra of the said crystals were recorded in the frequency range of 3–5000 cm−1, and the values of the complex refractive indexes and dielectric constants were calculated. The generalized four parameter model were used for calculation of absorption band parameters. For the CSBF crystal, a significant broadening of the band was observed in the absorption region at optical phonon modes along with an increased absorption in the region below the optical phonon frequencies, which is typical for disordered dielectric media.

Long-wavelength dielectric properties and infrared active optical phonon modes of molecular beam epitaxy ScxAl1−xN determined by infrared spectroscopic ellipsometry

Tuning the optical, electronic, and long-wavelength properties of group-III nitride alloys can be achieved by alloying AlN with ScN. We report here on the infrared dielectric functions determined from spectroscopic ellipsometry of (0001) wurtzite ScxAl1−xN with compositions of 0≤x≤0.20 grown by molecular beam epitaxy on c-plane sapphire substrates. We also report the optical phonons and their parameters determined in our analysis and compare with those in the previous literature. We find that all phonons shift to a lower wavenumber as a function of scandium incorporation, and we also see evidence of a decrease in crystal quality. Further, we report the high frequency and static dielectric constants and the Born effective charge as well as their evolution with the scandium content.

Comparison of static and dynamic characteristics of 1550 nm quantum dash and quantum well lasers.

Compared to quantum well (QW) lasers, lower dimensional quantum dot (QD) or quantum dash (QDash) devices demonstrate superior performances, owing to their quantized energy levels and increased carrier confinement. Here, we report the systematic comparison of static and dynamic properties of long wavelength (1550 nm) QDash and QW lasers. For the QDash lasers, a higher maximum operating temperature and lower temperature dependence was achieved for long cavities, although the threshold current densities were larger than the QW reference devices. The lasing characteristics for QDashes are significantly improved following the application of a high reflectance (HR) coating on the rear facets. The QDash lasers also exhibit three orders lower dark current, of 45 µA/cm2 under -1 V reverse bias. Small signal modulation on the 4 × 550 µm2 Fabry-Perot cavities yields a modulation efficiency of 0.48 GHz/√mA and a maximum 3-dB bandwidth of 7.4 GHz for QDashes, slightly larger than that for the QW devices. Meanwhile, a stronger damping effect was observed for the QDash lasers due to their lower differential gain.

Spectroscopic and Theoretical Investigation of Color Tuning in Deep-Red Luminescent Iridium(III) Complexes.

A series of heteroleptic, neutral iridium(III) complexes of the form [Ir(L)2(N^O)] (where L = cyclometalated 2,3-disubstituted quinoxaline and N^O = ancillary picolinate or pyrazinoate) are described in terms of their synthesis and spectroscopic properties, with supporting computational analyses providing additional insight into the electronic properties. The 10 [Ir(L)2(N^O)] complexes were characterized using a range of analytical techniques (including 1H, 13C, and 19F NMR and IR spectroscopies and mass spectrometry). One of the examples was structurally characterized using X-ray diffraction. The redox properties were determined using cyclic voltammetry, and the electronic properties were investigated using UV–vis, time-resolved luminescence, and transient absorption spectroscopies. The complexes are phosphorescent in the red region of the visible spectrum (λem = 633–680 nm), with lifetimes typically of hundreds of nanoseconds and quantum yields ca. 5% in aerated chloroform. A combination of spectroscopic and computational analyses suggests that the long-wavelength absorption and emission properties of these complexes are strongly characterized by a combination of spin-forbidden metal-to-ligand charge-transfer and quinoxaline-centered transitions. The emission wavelength in these complexes can thus be controlled in two ways: first, substitution of the cyclometalating quinoxaline ligand can perturb both the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital levels (LUMO, Cl atoms on the ligand induce the largest bathochromic shift), and second, the choice of the ancillary ligand can influence the HOMO energy (pyrazinoate stabilizes the HOMO, inducing hypsochromic shifts).

Analytical modeling of dissipative silencers.

This paper applies ideas originally developed in the field of acoustics of multiscale porous media to the analytical modeling of dissipative silencers. Analytical models for the long-wavelength acoustical properties of different types of dissipative silencers, such as pod silencers, lined ducts, splitters, and bar silencers, are introduced in this work. Some of these models account for the possibility of using different porous materials in a given silencer. For instance, a model for a splitter silencer comprising baffles made of different porous materials is derived. Examples of the sound transmission behavior of the said types of silencers are presented to evidence that the dissipation of sound energy is largely influenced by pressure diffusion occurring in the porous constituents. The predictions of the analytical models are in good agreement with finite element calculations.

Analytic ground state wave functions of mean-field px+ipy superconductors with vortices and boundaries

We study Read and Green's mean-field model of the spinless $p_x+ip_y$ superconductor [N.Read and D.Green, Phys. Rev. B 61, 10267 (2000)] at a special set of parameters where we find the analytic expressions for the topologically degenerate ground states and the Majorana modes, including in finite systems with edges and in the presence of an arbitrary number of vortices. The wavefunctions of these ground states are similar (but not always identical) to the Moore-Read Pfaffian states proposed for the $\nu=5/2$ fractional quantum Hall system, which are interpreted as the p-wave superconducting states of composite fermions. The similarity in the long-wavelength universal properties is expected from previous work, but at the special point studied herein the wavefunctions are exact even for short-range, non-universal properties. As an application of these results, we show how to obtain the non-Abelian statistics of the vortex Majorana modes by explicitly calculating the analytic continuation of the ground state wavefunctions when vortices are adiabatically exchanged, an approach different from the previous one based on universal arguments. Our results are also useful for constructing particle number-conserving (and interacting) Hamiltonians with exact projected mean-field states.

Synthesis and photophysical properties of long wavelength absorbing BODIPY/aza-BODIPY bearing a five-membered ring

Five-membered-ring fused BODIPYs and aza-BODIPY were herein prepared. X-ray crystallographic analysis revealed that the core skeleton of six-membered-ring fused BODIPY is nonplanar but twisted. Such five-membered-ring fused BODIPY/aza-BODIPY dyes have long wavelength absorptions/emissions, high extinction coefficients, peak fluorescence and narrow excitations/emissions. MO calculations well supported and explained the same absorption maxima between BODIPY bearing the five-membered ring and BODIPY bearing the six-membered ring.

HERSCHEL OBSERVATIONS OF DUSTY DEBRIS DISKS

ABSTRACT We present results from two Herschel observing programs using the Photodetector Array Camera and Spectrometer. During three separate campaigns, we obtained Herschel data for 24 stars at 70, 100, and 160 μm. We chose stars that were already known or suspected to have circumstellar dust based on excess infrared (IR) emission previously measured with the InfraRed Astronomical Satellite (IRAS) or Spitzer and used Herschel to examine long-wavelength properties of the dust. Fifteen stars were found to be uncontaminated by background sources and possess IR emission most likely due to a circumstellar debris disk. We analyzed the properties of these debris disks to better understand the physical mechanisms responsible for dust production and removal. Seven targets were spatially resolved in the Herschel images. Based on fits to their spectral energy distributions, nine disks appear to have two temperature components. Of these nine, in three cases, the warmer dust component is likely the result of a transient process rather than a steady-state collisional cascade. The dust belts at four stars are likely stirred by an unseen planet and merit further investigation.

Long-wavelength properties of phase-field-crystal models with second-order dynamics.

The phase-field-crystal (PFC) approach extends the notion of phase-field models by describing the topology of the microscopic structure of a crystalline material. One of the consequences is that local variation of the interatomic distance creates an elastic excitation. The dynamics of these excitations poses a challenge: pure diffusive dynamics cannot describe relaxation of elastic stresses that happen through phonon emission. To this end, several different models with fast dynamics have been proposed. In this article we use the amplitude expansion of the PFC model to compare the recently proposed hydrodynamic PFC amplitude model with two simpler models with fast dynamics. We compare these different models analytically and numerically. The results suggest that in order to have proper relaxation of elastic excitations, the full hydrodynamical description of the PFC amplitudes is required.

Interaction of chiral rafts in self-assembled colloidal membranes.

Colloidal membranes are monolayer assemblies of rodlike particles that capture the long-wavelength properties of lipid bilayer membranes on the colloidal scale. Recent experiments on colloidal membranes formed by chiral rodlike viruses showed that introducing a second species of virus with different length and opposite chirality leads to the formation of rafts--micron-sized domains of one virus species floating in a background of the other viruses [Sharma et al., Nature (London) 513, 77 (2014)]. In this article we study the interaction of such rafts using liquid crystal elasticity theory. By numerically minimizing the director elastic free energy, we predict the tilt angle profile for both a single raft and two rafts in a background membrane, and the interaction between two rafts as a function of their separation. We find that the chiral penetration depth in the background membrane sets the scale for the range of the interaction. We compare our results with the experimental data and find good agreement for the strength and range of the interaction. Unlike the experiments, however, we do not observe a complete collapse of the data when rescaled by the tilt angle at the raft edge.

Synthesis of conjugated polymers possessing diketopyrrolopyrrole units bearing phenyl, pyridyl, and thiazolyl groups by direct arylation polycondensation: Effects of aromatic groups in DPP on physical properties

Conjugated polymers containing phenyl-, pyridyl-, and thiazolyl-flanked diketopyrrolopyrrole (DPP) were synthesized by direct arylation polycondensation of 3,4-ethylenedioxythiophene derivatives and dibrominated DPP-based monomers, in order to probe the effects of the aromatic groups in the DPP units on the absorption property, energy level, and crystallinity. A polymer possessing thiazolyl-flanked DPP units was found to display long-wavelength absorption properties and higher crystallinity than the polymers bearing phenyl- and pyridyl-flanked DPP units. These features of the thiazolyl-based polymer were afforded by its coplanar structure of the main chain. The synthesized polymers showed semiconducting properties in organic field effect transistors and organic photovoltaics. Direct arylation polycondensation is an efficient synthetic method that affords a series of DPP-based polymers in a simple fashion and, thus, helping in a comprehensive understanding on the relationship between the aromatic groups in DPP units and their physical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2337–2345

Emergence of cooperative dynamics in fully packed classical dimers.

The classical dimer model on the square lattice is a paradigmatic example of a system subject to strong local constraints. We study its behavior under local stochastic dynamics, by means of Monte Carlo simulations and theoretical arguments. We observe clear signatures of correlated dynamics in both global and local observables and over a broad range of time scales, indicating a breakdown of the simple continuum description that approximates well the statics. We show that this collective dynamics can be understood in terms of one-dimensional "strings" of high mobility, which govern both local and long-wavelength dynamical properties. We introduce a coarse-grained description of the strings, based on the Edwards-Wilkinson model, which leads to exact results in the limit of low string density and provides a detailed qualitative understanding of the dynamics in all flux sectors. We discuss the implications of our results for the dynamics of constrained systems more generally.

Predicting energies of small clusters from the inhomogeneous unitary Fermi gas

We investigate the inhomogeneous unitary Fermi gas and use the long-wavelength properties to predict the energies of small clusters of unitary fermions trapped in harmonic potentials. The large pairing gap and scale invariance place severe restrictions on the form of the density functional. We determine the relevant universal constants needed to constrain the functional from calculations of the bulk in oscillating external potentials. Comparing with exact Quantum Monte Carlo calculations, we find that the same functional correctly predicts the lack of shell closures for small clusters of fermions trapped in harmonic wells as well as their absolute energies. A rapid convergence to the bulk limit in three dimensions, where the surface to volume ratio is quite large, is demonstrated. The resulting functional can be tested experimentally, and is a key ingredient in predicting possible polarized superfluid phases and the properties of the unitary Fermi gas in optical lattices.

Metal based acoustic metamaterials

Two apparently distinct types of acoustic metamaterial are considered: a metallic phononic lattice structure and an array of metal shells in water. The unifying feature is that metal acts primarily as a stiffness, and by adding material one arrives at a desired effective density. The metal provides a reservoir of stiffness in the sense that a little bit goes a long way toward the effective stiffness of water, or properties close to water. We first describe the Metal Water structure proposed as a generic metamaterial for transformation acoustics, in both 2D and 3D. The structures have isotropic elastic properties with low shear modulus, hence mimicking water. While designed for long-wavelength effective properties the structures also display interesting finite frequency effects, such as negative index properties. The thin shell metamaterial elements achieve the bulk modulus of water at a specific thickness/radius ratio. Simultaneous matching of effective bulk modulus and density is obtained using an internal mass. By design, both types of metamaterials separate stiffness and density, allowing for simple lumped parameters modeling. The use of metal also has implications for optimal cloaking properties, which result from the fact the metallic structure is non-causal. [Work supported by ONR.]