Photoinduced intramolecular charge transfer and S2 fluorescence in thiophene-pi-conjugated donor-acceptor systems: experimental and TDDFT studies

Experimental and theoretical methods were used to study newly synthesized thiophene-pi-conjugated donor-acceptor compounds, which were found to exhibit efficient intramolecular charge-transfer emission in polar solvents with relatively large Stokes shifts and strong solvatochromism. To gain insight into the solvatochromic behavior of these compounds, the dependence of the spectra on solvent polarity was studied on the basis of Lippert-Mataga models. We found that intramolecular charge transfer in these donor-acceptor systems is significantly dependent on the electron-withdrawing substituents at the thienyl 2-position. The dependence of the absorption and emission spectra of these compounds in methanol on the concentration of trifluoroacetic acid was used to confirm intramolecular charge-transfer emission. Moreover, the calculated absorption and emission energies, which are in accordance with the experimental values, suggested that fluorescence can be emitted from different geometric conformations. In addition, a novel S(2) fluorescence phenomenon for some of these compounds was also be observed. The fluorescence excitation spectra were used to confirm the S(2) fluorescence. We demonstrate that S(2) fluorescence can be explained by the calculated energy gap between the S(2) and S(1) states of these molecules. Furthermore, nonlinear optical behavior of the thiophene-pi-conjugated compound with diethylcyanomethylphosphonate substituents was predicted in theory.     

Electronic and vibronic contributions to two-photon absorption in donor-acceptor-donor squaraine chromophores

Many squaraines have been observed to exhibit two-photon absorption at transition energies close to those of the lowest energy one-photon electronic transitions. Here, the electronic and vibronic contributions to these low-energy two-photon absorptions are elucidated by performing correlated quantum-chemical calculations on model chromophores that differ in their terminal donor groups (diarylaminothienyl, indolenylidenemethyl, dimethylaminopolyenyl, or 4-(dimethylamino)phenylpolyenyl). For squaraines with diarylaminothienyl and dimethylaminopolyenyl donors and for the longer examples of 4-(dimethylamino)phenylpolyenyl donors, the calculated energies of the lowest two-photon active states approach those of the lowest energy one-photon active (1B(u)) states. This is consistent with the existence of purely electronic channels for low-energy two-photon absorption (TPA) in these types of chromophores. On the other hand, for all squaraines containing indolinylidenemethyl donors, the calculations indicate that there are no low-lying electronic states of appropriate symmetry for TPA. Actually, we find that the lowest energy TPA transitions can be explained through coupling of the one-photon absorption (OPA) active 1B(u) state with b(u) vibrational modes. Through implementation of Herzberg-Teller theory, we are able to identify the vibrational modes responsible for the low-energy TPA peak and to reproduce, at least qualitatively, the experimental TPA spectra of several squaraines of this type.     

Second-harmonic properties of dendritic polymers skeleton-constructed with azobenzene moiety used for nonlinear optical materials

A series of dendrons and dendrimers skeleton-constructed with azobenzene moiety were synthesized and doped in a high T_g polycarbonate (PC) as a host for nonlinear optical (NLO) materials. The optimal loading density and poling conditions were investigated using UV-vis spectral and second-harmonic generation (SHG) measurements. The results showed that the dendrons and dendrimers have good solubility in PC host, which increased with the generation increased. Moreover, the SHG measurements indicated that the dendrons possess higher nonlinearity than the dendrimers. The chromophores of lower generation dendrons were easier to orient along the poling electric field and gave a cone shape with the azobenzene branching units, which coherently contributed to the molecular hyperpolarizability and resulted in the higher SHG intensity. The temporal stability of the dendrons with 15% loading density was also investigated, and showed that the decaying in nonlinearity was slower for higher generation dendrons.     

Cavity QED based tuneable,delayed-choice quantum eraser

We propose an experimentally feasible idea for the delayed-choice quantum eraser, having adjustable path distinguishability/fringe visibility. The schematics are based on resonant, dispersive and Ramsey interactions of atoms under cavity QED scenario. The option for tuneability of the fringes in a delayed-choice setup stringently marks the conception of the time in the quantum theory, operational meanings of the state vector reduction and raises questions about Ψ$\Psi$-ontic models while helping to shed out the controversies surrounding the quantum eraser theme. The proposal can be efficiently executed experimentally within the prevailing cavity QED experimental research scenario with good overall success probability and fidelity.     

Nonlinear optical characteristics of monolayer MoSe2

In this study, we utilized picosecond pulses from an Nd:YAG laser to investigate the nonlinear optical characteristics of monolayer MoSe₂. Two‐step growth involving the selenization of pulsed‐laser‐deposited MoO₃ film was employed to yield the MoSe₂ monolayer on a SiO₂/Si substrate. Raman scattering, photoluminescence (PL) spectroscopy, and atomic force microscopy verified the high optical quality of the monolayer. The second‐order susceptibility χ⁽²⁾ was calculated to be ～50 pm V^?1 at the second harmonic wavelength ～810 nm, which is near the optical gap of the monolayer. Interestingly, our wavelength‐dependent second harmonic scan can identify the bound excitonic states including negatively charged excitons much more efficiently, compared with the PL method at room temperature. Additionally, the MoSe₂ monolayer exhibits a strong laser‐induced damage threshold ～16 GW cm^?2 under picosecond‐pulse excitation_. Our findings suggest that monolayer MoSe₂ can be considered as a promising candidate for high‐power, thin‐film‐based nonlinear optical devices and applications.     

Beam delivery system with a non-digitized diffractive beam splitter for laser-drilling of silicon

We report a beam-delivery system consisting of a non-digitized diffractive beam splitter and a Fourier transform lens. The system is applied to the deep-drilling of silicon using a nanosecond pulse laser in the manufacture of inkjet printer heads. In this process, a circularly polarized pulse beam is divided into an array of uniform beams, which are then delivered precisely to the process points. To meet these requirements, the splitter was designed to be polarization-independent with an efficiency>95%. The optical elements were assembled so as to allow the fine tuning of the effective overall focal length by adjusting the wavefront curvature of the beam. Using the system, a beam alignment accuracy of<5 μm was achieved for a 12-mm-wide beam array and the throughput was substantially improved (10,000 points on a silicon wafer drilled in ~1 min). This beam-delivery scheme works for a variety of laser applications that require parallel processing.     

Remarkable ability of spiral orthogonal zone plate in generating various focused optical vortices

We propose an amplitude spiral orthogonal zone plate (ASOZP) as a Cartesian-based spiral zone plate for generating variety of optical vortices. The presented model is made by overlapping closely a vertical spiral one-dimensional zone plate and a horizontal one. We demonstrate that the element produces diversity of focused vortices, in a way that the vorticity and number of the produced vortices could be easily manipulated. In addition, the generated vortices show rotation features in the vicinity of the focal plane. Furthermore, it is demonstrated that diffraction efficiency of the model is much more higher than the previously introduced Cartesian-based elements. We finally verify numerical results by experimental studies.     

超强激光功率密度对等离子体中自生磁场和电子热传导的影响

应用多光子非线性康普顿散射模型、3维粒子模拟模型和数值计算方法,研究了超强激光与等离子体作用中自生磁场产生和电子热传导过程,提出了将非线性康普顿散射光作为改变等离子体自生磁场和电子热传导的新机制,给出了自生磁场最大饱和值和超热电子热传导的修正方程和数值计算结果。研究发现在时间为100~160范围内,自生磁场能量随入射激光功率密度增大而迅速增大,之后处于较高饱和阶段。增大的初始时刻较散射前提前了20,增大阶段的时间延长了30,饱和阶段增幅为40。入射激光功率密度为1019~1020W/cm2时,自生磁场强度最大模拟值为1.47104~3.75104T,单电子能谱峰值出现在3.3MeV和6.6MeV附近,能谱曲线在4~15 MeV和11~14.3MeV范围迅速衰减,在6.7MeV和13.2MeV以上时,超热电子有效温度为2.6MeV和4.5MeV,比无散射的理论值和拟合值均有一定增大。随入射激光强度增大,热流随激光脉冲一起向等离子体内流动的时间缩短,自生磁场限制热流的时间延长。并对所得结果给出了初步物理解释。     

New figuring model based on surface slope profile for grazing‐incidence reflective optics

Surface slope profile is widely used in the metrology of grazing‐incidence reflective optics instead of surface height profile. Nevertheless, the theoretical and experimental model currently used in deterministic optical figuring processes is based on surface height, not on surface slope. This means that the raw slope profile data from metrology need to be converted to height profile to perform the current height‐based figuring processes. The inevitable measurement noise in the raw slope data will introduce significant cumulative error in the resultant height profiles. As a consequence, this conversion will degrade the determinism of the figuring processes, and will have an impact on the ultimate surface figuring results. To overcome this problem, an innovative figuring model is proposed, which directly uses the raw slope profile data instead of the usual height data as input for the deterministic process. In this paper, first the influence of the measurement noise on the resultant height profile is analyzed, and then a new model is presented; finally a demonstration experiment is carried out using a one‐dimensional ion beam figuring process to demonstrate the validity of our approach.     

Collimating Montel mirror as part of a multi‐crystal analyzer system for resonant inelastic X‐ray scattering

Advances in resonant inelastic X‐ray scattering (RIXS) have come in lockstep with improvements in energy resolution. Currently, the best energy resolution at the Ir L₃‐edge stands at ～25 meV, which is achieved using a diced Si(844) spherical crystal analyzer. However, spherical analyzers are limited by their intrinsic reflection width. A novel analyzer system using multiple flat crystals provides a promising way to overcome this limitation. For the present design, an energy resolution at or below 10 meV was selected. Recognizing that the angular acceptance of flat crystals is severely limited, a collimating element is essential to achieve the necessary solid‐angle acceptance. For this purpose, a laterally graded, parabolic, multilayer Montel mirror was designed for use at the Ir L₃‐absorption edge. It provides an acceptance larger than 10 mrad, collimating the reflected X‐ray beam to smaller than 100 µrad, in both vertical and horizontal directions. The performance of this mirror was studied at beamline 27‐ID at the Advanced Photon Source. X‐rays from a diamond (111) monochromator illuminated a scattering source of diameter 5 µm, generating an incident beam on the mirror with a well determined divergence of 40 mrad. A flat Si(111) crystal after the mirror served as the divergence analyzer. From X‐ray measurements, ray‐tracing simulations and optical metrology results, it was established that the Montel mirror satisfied the specifications of angular acceptance and collimation quality necessary for a high‐resolution RIXS multi‐crystal analyzer system.