密度泛函理论研究MN@H_2O (M=Ga,Ge, In,Sn, Sb; N=M,Al)团簇的特性

采用密度泛函理论的B3LYP, B3P86, B1B95, P3PW91和PBE1PBE方法结合SDD, LANL2DZ和CEP-121G基组计算了d~(10)组态二聚物MN(M=Ga, Ge, In, Sn和Sb; N=M和Al)的几何结构.采用B3P86/SDD进一步研究了MN@H_2O团簇的几何结构及吸附能.结果表明,水分子结合在二聚物M_2上时,对二聚物影响较大,对水分子自身影响较小.将M_2中Ga, Ge, In, Sn或Sb替换一个原子为Al时,水分子在GeAl和SnAl上的吸附能变化较大,而在GaAl, InAl和SbAl上吸附能变化较小.另外, H_2O吸附在Ga, Ge, In, Sn和Sb上时,与吸附在Al上时,吸附能的变化不大.     

Frequency-dependent acoustic energy focusing in hexagonal ceramic micro-scaffolds

Acoustic properties of an additive-manufactured SiC scaffold with hexagonal symmetry fabricated by the robocasting method are studied both numerically and experimentally. The numerical analysis is based on the finite element method (FEM) using Bloch boundary conditions. The calculations show both angular and frequency dispersion of the acoustic waves with wavelengths comparable to the spacing between the rods, i.e., on a millimeter scale, indicating interesting acoustic properties in the MHz range. The dispersion character leads to focusing of the energy propagation into the directions of the rods of the hexagonal structure. This is illustrated by modal-based calculations of the propagation of longitudinal and out-of-plane shear wave packets with a dominant wavelength. The experimental analysis consists of two steps, the measurement of the resonant spectrum and shear wave propagation character. The measured resonant spectrum is in good agreement with the one calculated using numerically obtained low-frequency properties of the structure, also showing the quality of the overall manufactured structure. The time-domain measurement shows significant changes in the energy propagation between low and high frequencies, as predicted by FEM calculations.     

Capturing the experimental behaviour of a point-absorber WEC by simplified numerical models

The paper presents a wave basin experiment of a direct-driven point-absorber wave energy converter moving in six degrees of freedom. The goal of the work is to study the dynamics and energy absorption of the wave energy converter, and to verify under which conditions numerical models restricted to heave can capture the behaviour of a point-absorber moving in six degrees of freedom. Several regular and irregular long-crested waves and different damping values of the power take-off system have been tested. We collected data in terms of power output, device motion in six degrees of freedom and wave elevation at different points of the wave basin. A single-body numerical model in the frequency domain and a two-body model in the time domain are used in the study. Motion instabilities due to parametric resonance observed during the experiments are discussed and analysis of the buoy motion in terms of the Mathieu instability is also presented. Our results show that the simplified models can reproduce the body dynamics of the studied converter as long as the transverse non-linear instabilities are not excited, which typically is the case in irregular waves. The performance of the more complex time domain model is able to reproduce both the buoy and PTO dynamics, while the simpler frequency domain model can only reproduce the PTO dynamics for specific cases. Finally, we show that the two-body dynamics of the studied wave energy converter affects the power absorption significantly, and that common assumptions in the numerical models, such as stiff mooring line or that the float moves only in heave, may lead to incorrect predictions for certain sea states.     

Suppressing Strong Exciton–Phonon Coupling in Blue Perovskite Nanoplatelet Solids by Binary Systems

Quasi-two-dimensional (2D) perovskites are promising candidates for light generation owing to their high radiative rates. However, strong exciton–phonon interactions caused by mechanical softening of the surface act as a bottleneck in improving their suitability for a wide range of lighting and display applications. Moreover, it is not easily available to tune the phonon interactions in bulk films. Here, we adopt bottom-up fabricated blue emissive perovskite nanoplatelets (NPLs) as model systems to elucidate and as well as tune the phonon interactions via engineering of binary NPL solids. By optimizing component domains, the phonon coupling strength can be reduced by a factor of 2 driven by the delocalization of 2D excitons in out-of-plane orientations. It shows the picosecond energy transfer originated from the Förster resonance energy transfer (FRET) efficiently competes with the exciton–phonon interactions in the binary system.     

Manipulating Light-Induced Dynamic Macro-Movement and Static Photonic Properties within 1D Isostructural Hydrogen-Bonded Molecular Cocrystals

Smart molecular crystals with light-driven mechanical responses have received interest owing to their potential uses in molecular machines, artificial muscles, and biomimetics. However, challenges remain in control over both the dynamic photo-mechanical behaviors and static photonic properties of molecular crystals based on the same molecule. Herein, we show the construction of isostructural co-crystals allows their light-induced cracking and jumping behaviors (photosalient effect) to be controlled. Hydrogen-bonded co-crystals from 4-(1-naphthylvinyl)pyridine ( NVP ) with co-formers (tetrafluoro-4-hydroxybenzoic acid ( THA ) and tetrafluorobenzoic acid ( TA )) crystallize as isostructural crystals, but have different static and dynamic photo-mechanical behaviors. These differences are due to alternations in the orientation of NVP and hydrogen-bonding modes of the co-formers. After light activation, the 1D NVP-TA crystal splits and shears off within 1 s. For NVP-THA , its photostability and high quantum yield give novel photonic properties, including low optical waveguide loss, highly polarized anisotropy, and efficient up-conversion fluorescence.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Pattern formation in a variable diffusion predator–prey model with additive Allee effect

This paper deals with a variable diffusion predator–prey model with additive Allee effect. A good understanding of the existence of steady states is gained for the case  $\sigma =0$. The result shows that the reduce problem has multiple solutions. Moreover, by applying the singular perturbation method, we give a proof of existence of large amplitude solutions when  $\sigma$ is sufficiently small.     

Sharper uncertainty principles associated with Lp-norm

Motivated by the well-established phase derivative embedded technique, this study devotes to sharper uncertainty principles related to the L^p-norm type of uncertainty product, giving rise to two kinds of uncertainty inequalities that improve the classical result through providing tighter lower bounds. The conditions that truly reach these better estimates are obtained. Examples and simulations are carried out to verify the correctness of the derived results, and finally, possible applications in time-frequency analysis are also given.