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This paper reports an investigation of the electronic structure and photophysical properties of two "diblock" π-conjugated oligomers (T4-TBT and T8-TBT) that feature electron rich tetra(thiophene) (T4) or octa(thiophene) (T8) segments linked to an electron poor 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) moiety. Electrochemistry and UV-visible absorption spectroscopy reveals that the diblock oligomers display redox and absorption features that can be attributed to the Tn and TBT units. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations support the experimental electrochemistry and optical spectroscopy results, suggesting that the frontier orbitals on the diblock oligomers retain characteristics of the individual π-conjugated segments. However, low energy optical transitions are anticipated to arise from Tn to TBT charge transfer. Fluorescence spectroscopy on the diblock oligomers reveals that the oligomers feature strongly solvent dependent fluorescence. In non-polar solvents (hexane, toluene), the emission is structured with a moderate Stokes shift; however, in more polar solvents the emission becomes broader, and red-shifts significantly. Transient absorption spectroscopy on timescales from femtoseconds (fs) to microseconds (μs) reveals that in non-polar solvents excitation produces a singlet excited state (LE) that decays uniformly to the ground state in parallel with intersystem crossing to a triplet state. By contrast, in more polar solvents, excitation produces a very short-lived excited state (1–3 ps) which evolves rapidly into a second excited state that is attributed to the charge transfer (CT) state. The fast dynamics are associated with crossing from the LE state, which is populated initially by photoexcitation, into the CT state, which then decays to the ground state. The photophysical properties and dynamics of the LE and CT excited states are very similar for T4-TBT and T8-TBT, suggesting that the length of the oligo(thiophene) segment does not have a strong influence on the energy, structure or dynamics of the LE and CT excited states. [ABSTRACT FROM AUTHOR]

In this paper, a TM polarization multi-band absorber is achieved in a graphene–Ag asymmetrical grating structure. The proposed absorber can achieve perfect absorption at 1108 nm, 1254 nm, and 1712 nm (the absorption exceeds 98.4% at the three peaks). Results show that the perfect absorption effect originates from the excitation of magnetic polaritons (MPs) in the silver ridge grating; a LC equivalent circuit model is utilized to confirm the finite-difference-time-domain (FDTD) simulation. The influences of the incident angle, polarization angle, and geometrical size on the absorption spectrum are investigated. Moreover, a quadruple band absorber and a quintuple band absorber are also designed by introducing more silver grating ridges in one period. The proposed graphene–Ag asymmetrical structure has some advantages compared with other absorbers such as the ability to be independently tuned and a simple structure. Thus, the proposed structure can be applied in the areas of multiple absorption switches, near-infrared modulators, and sensors. [ABSTRACT FROM AUTHOR]

The electronic structure and magnetic properties of Li(ZnMn)As with antisite defects have been investigated by using first-principles calculations within the Perdew–Burke–Ernzerhof generalized gradient approximation. The cation antisite defect induced by Zn substitution for As was considered. Mn-3d, As-4p, Zn-4s, and Zn-4p were involved in the formation of d-sp hybrid orbitals, which enhanced the non-localized properties of Mn-3d electrons and provided a channel of Mn(↑)–As(↓)–ZnAs(↓)–Mn(↑) for indirect exchange of electrons between the magnetic ions. The antisite defect of Zn-substituted As belonged to the acceptor doping, rendering the compound p-type characteristics. The existence of the extra free hole carriers regulated the magnetic ordering transition. The ferromagnetic coupling between the Mn magnetic dopants was more favorable in the system with an antisite defect. In this paper, a novel type of dilute magnetic semiconductor with controllable carriers was designed and the mechanism of ferromagnetic coupling was revealed, which provided a theoretical reference for the subsequent studies. [ABSTRACT FROM AUTHOR]

This study addresses the challenges of sustainable and efficient agricultural practices in the face of climate change and the destruction of agricultural lands by presenting the development of a novel plant growth LED based on Sm3+ and Tm3+ co-doped luminescent glasses with color-converting properties that emit blue and red light, resulting in an increased rate of photosynthesis and density of photosynthetically active radiation reaching the harvesting pigments. The developed LED exhibits photoluminescence (PL) peak positions ranging from 454 to 648 nm, with a spectral coverage of 50% and 39% of the absorption regions of chlorophyll a and chlorophyll b, respectively, resulting in an impressive 56% photoluminescence quantum yield (PLQY). Furthermore, the developed plant growth LED demonstrates robust performance, remaining unaffected by temperature cycles and extended operation periods. Using Romaine lettuce cultivated under identical conditions, a comparative study between the developed LED and commercially available plant growth LED is conducted, with the designed LED showing significant improvements in plant growth characteristics, including increased plant height, weight, number of leaves, and enhanced levels of chlorophyll a, chlorophyll b, and carotenoid content, while the root diameter is reduced, and the shoot-to-root ratio is diminished in comparison to the commercially available plant growth LED. The paper also compares the performance of Sm3+ and Tm3+ co-doped luminescent glass-based plant growth LED with other reported plant growth LED designs using different luminescent materials, exploring the impact of PLQY, PL position, and plant growing conditions. The results suggest that the developed LED system offers a more efficient and sustainable way of lighting for indoor horticulture and has significant implications for meeting the increasing food demands of the growing world population. [ABSTRACT FROM AUTHOR]

Refractive index is an optical property explored in the light scattering measurement of micro- and nano-particles as well as in label-free imaging of cells and tissues. Because the refractive index value is a major input to the characterization and quantification of the analyzed specimens, various methods have been developed targeting at different sample types. In this paper, we demonstrate a technique for the refractive index measurement of homogeneous microspheres and liquids in the short-wave infrared (SWIR) range. We use synthetic phase microscopy (SPM), which records a scattering-corrected projection of the 3D refractive index distribution, in combination with a least-squares fitting to a theoretical model of a sphere. Using the method, we determine the refractive index dispersion of two polymer microspheres (polymethyl methacrylate and polystyrene), two glass microspheres (silica and soda lime), and three microscopy mounting media (glycerol, FluorSave, and Eukitt) in the SWIR range of 1100–1650 nm. [ABSTRACT FROM AUTHOR]

Natural gas hydrates have garnered significant attention as a potential new source of alternative energy, and understanding their formation mechanism is of paramount importance for efficient utilization and pipeline transportation. However, there is no consensus among academics on the formation mechanism of natural gas hydrates. In this paper, we propose a method for promoting the rapid formation of natural gas hydrates based on the rupture of methane nanobubbles, which creates local high temperature and pressure to facilitate the mixing of methane and water. The rapid decrease in system temperature and pressure during the process further enhances the formation of gas hydrates. Using molecular dynamics simulations, we theoretically verify the formation of natural gas hydrates. Our results indicate that the instantaneous rupture of methane nanobubbles induced by shock waves leads to a dramatic increase in the local molecular motion velocity around the bubbles. This results in extreme local high temperature and high pressure, leading to complete mixing of methane and water and rapid formation of gas hydrates during the cooling and pressure drop of the mixture. We confirm our findings by analyzing F3-order parameters, F4-order parameters, and water cage statistics. [ABSTRACT FROM AUTHOR]

Vinyl alcohol (VyA) and cyanide (CN) radicals are relatively abundant in the interstellar medium (ISM). VyA is the enolic tautomer of acetaldehyde and has two low-lying conformers, characterized by the syn or anti placement of hydroxyl hydrogen with respect to the double bond. In this paper, we present a gas-phase model of the barrierless reactions of both VyA's conformers with CN employing accurate quantum chemical computations in the framework of a master equation approach based on the transition state theory. Our results indicate that both VyA conformers feature a similar reactivity with CN, starting with a barrierless addition to the double bond and followed by different isomerization, dissociation, and/or hydrogen elimination steps. The rate constants computed for temperatures up to 600 K show that several reaction channels are open even under the harsh conditions of the ISM, with the favoured one providing the first feasible formation route of a prebiotic molecule not yet detected in the ISM, namely cyanoacetaldehyde. This finding suggests looking for cyanoacetaldehyde in regions where both VyA and CN have already been detected, like, e.g., Sagittarius B2N or G+0.693-0.027. [ABSTRACT FROM AUTHOR]

In this paper, a benzyltriethylammonium/urea DES was investigated as a new green and eco-friendly medium for the progress of organic chemical reactions, particularly the dissolution and the functionalization of cellulose. In this regard, the viscosity–average molecular weight of cellulose (M¯w) during the dissolution/regeneration process was investigated, showing no significant degradation of the polymer chains. Moreover, X-ray diffraction patterns indicated that the cellulose dissolution process in the BTEAB/urea DES decreased the crystallinity index from 87% to 75%, and there was no effect on type I cellulose polymorphism. However, a drastic impact of the cosolvents (water and DMSO) on the melting point of the DES was observed. Besides, to understand the evolution of cellulose–DES interactions, the formation mechanism of the system was studied in terms of H-bond density and radial distribution function (RDF) using molecular dynamics modeling. Furthermore, density functional theory (DFT) was used to evaluate the topological characteristics of the polymeric system such as potential energy density (PED), laplacian electron density (LED), energy density, and kinetic energy density (KED) at bond critical points (BCPs) between the cellulose and the DES. The quantum theory of atoms in molecules (AIM), Bader's quantum theory (BQT), and reduced density gradient (RDG) scatter plots have been exploited to estimate and locate non-covalent interactions (NCIs). The results revealed that the dissolution process is attributed to the physical interactions, mainly the strong H-bond interactions. [ABSTRACT FROM AUTHOR]

Coriolis coupling plays a crucial role in reactive scattering, but dynamics calculations including the complete Coriolis coupling significantly increase the difficulty of numerical evolution due to the corresponding expensive matrix processing. The coupled state approximation that completely ignores the off-diagonal Coriolis coupling saves computational cost significantly but its error is usually unacceptable. In this paper, an improved coupled state approximation inspired by recently published results [D. Yang, X. Hu, D. H. Zhang and D. Xie, J. Chem. Phys., 2018, 148, 084101.] of the inelastic scattering problem is extended to deal with the reactive scattering. The calculations using the time-dependent wave packet method reveal that the new method can accurately reproduce the rigorous results of the H + HD (j0 < 3) → D + H2 reaction and immensely improve the computational efficiency. Additionally, we extend the new method to the non-adiabatic Li(2p) + H2 (v0 = 0, j0 = 0, 1) → H + LiH reaction, showcasing its advantages of low computational cost and high accuracy. [ABSTRACT FROM AUTHOR]

Bistable cholesteric liquid crystals have promising application prospects in various fields, such as smart windows and displays. However, the long-term stability of two individual states is not easy to achieve, hindering their practical use. In this research, the bistable feature was enhanced by constructing a microsphere-type polymer with a liquid-crystalline epoxy/thiol monomer in negative dielectric anisotropic cholesteric liquid crystals. Spectroscopic and optical examinations revealed that either the transparent planar state or the opaque focal conic state can be maintained without the aid of an external field. Moreover, they can be switched to each other by applying a high- or low-frequency electric field. Further, factors such as the chemical structure of thiol compounds, curing temperature and curing time were investigated to explore their influences on the micro morphology of the polymer and thereby the electro-optical properties. In addition, the frequency-dependent driving scheme was analysed. Finally, bistable switching was demonstrated using an optimized sample. This energy-efficient bistable film shines light on future applications in smart windows, photonic paper and other electro-optical devices. [ABSTRACT FROM AUTHOR]

In many recent papers devoted to first row transition metal fluorides and oxides, not much attention is devoted to the spin density, a crucial quantity for the determination of the superexchange mechanism, and then for the ferro-antiferromagnetic energy difference. Usually, only the eigenvalues of the system are represented, in the form of band structures or, more frequently, of density of states (DOS). When discussing the orbital ordering and the Jahn-Teller effect, simple schemes with cubes and lobes are used to illustrate the shape of the d occupancy. But the eigenvectors, and the resulting spin density function, as obtained from the calculations, are rarely shown. When represented, only a fuzzy shape that recalls the d orbital shape can be observed. On the basis of these considerations, spin density maps for 5 compounds of the KMF3 (M from Mn to Cu) family have been produced, which clearly illustrate which d orbital is singly or doubly occupied. At variance with respect to the near totality of the papers devoted to these systems, we use an all electron scheme, a Gaussian type basis set, and the Hartree-Fock Hamiltonian or the B3LYP hybrid functional (the resulting maps turn out to be very similar, in the scale used for our figures). The spin density in the five cases can easily be interpreted in terms of the shape of the d orbitals as appearing in textbooks. [ABSTRACT FROM AUTHOR]

In this research, we explore the impact of edge passivation using halogen atoms on armchair stanene nanoribbon (ASNR) for the early detection of lung cancer biomarkers. We employ non-equilibrium green function (NEGF) and density functional theory (DFT) methods to evaluate sensing characteristics. The edges of ASNR are passivated with fluorine, chlorine, bromine, and iodine atoms. Our findings indicate a significant enhancement in sensing performance upon halogenation of ASNR. Notable changes in adsorption energy and current for edge-halogenated ASNR configurations demonstrate improved sensing behavior. Moreover, current curves exhibit greater distinctiveness of halogenated ASNR in comparison to hydrogenated ASNR. The calculations indicate a change in adsorption energy (Eads) of -7.59 eV, -7.6 eV, -8.3 eV, and -8.6 eV for the adsorption by styrene on I-ASnNR, Br-ASnNR, toluene on Cl-ASnNR, and styrene on F-ASnNR, respectively. The corresponding sensitivity improves up to 37.33%, 38.09%, 38.35%, and 45.5%, respectively. These findings highlight that the most significant change occurs with the edge fluorination of ASnNR. Our findings underscore the effectiveness of halogen atom edge passivation in ASNR for heightened sensing performance, making it a promising choice for the development of early-detection lung cancer sensors. [ABSTRACT FROM AUTHOR]

Recently, hydrogen boride (HB) with a pseudo-two-dimensional sheet structure was successfully synthesized, and it is theoretically predicted to have high potential as a negative electrode material for alkali metal ion batteries, making it a promising new candidate. This study represents the first experimental examination of the negative electrode properties of HB. HB was synthesized via cation exchange from MgB2. The confirmation of HB synthesis was achieved through various spectroscopic experiments, including synchrotron radiation X-ray diffraction and X-ray photoelectron spectroscopy, in addition to direct observation using transmission electron microscopy. The HB electrode was prepared by mixing the HB powder sample with conductive additive carbon black and a polymer binder. A test cell was assembled with the HB electrode as the working electrode, and lithium metal as the counter and reference electrodes, and its battery electrode properties were evaluated. Although reversible charge–discharge curves with good reversibility were observed, the reversible capacity was 100 ± 20 mA h g−1 which is significantly smaller than the theoretical predictions. Nitrogen gas adsorption experiments were performed on the HB powder sample to determine the specific surface area indicating that the HB sheets were stacked together. It is plausible to consider that this stacking structure led to a reduced lithium-ion storage capacity compared to the theoretical predictions. [ABSTRACT FROM AUTHOR]

We explore the simulation of conical intersections (CIs) on quantum devices, setting the groundwork for potential applications in nonadiabatic quantum dynamics within molecular systems. The intersecting potential energy surfaces of H3+ are computed from a variance-based contracted quantum eigensolver. We show how the CIs can be correctly described on quantum devices using wavefunctions generated by the anti-Hermitian contracted Schrödinger equation ansatz, which is a unitary transformation of wavefunctions that preserves the topography of CIs. A hybrid quantum-classical procedure is used to locate the seam of CIs. Additionally, we discuss the quantum implementation of the adiabatic to diabatic transformation and its relation to the geometric phase effect. Results on noisy intermediate-scale quantum devices showcase the potential of quantum computers in dealing with problems in nonadiabatic chemistry. [ABSTRACT FROM AUTHOR]

Atomic force microscopy (AFM or SPM) imaging is one of the best matches with machine learning (ML) analysis among microscopy techniques. The digital format of AFM images allows for direct utilization in ML algorithms without the need for additional processing. Additionally, AFM enables the simultaneous imaging of distributions of over a dozen different physicochemical properties of sample surfaces, a process known as multidimensional imaging. While this wealth of information can be challenging to analyze using traditional methods, ML provides a seamless approach to this task. However, the relatively slow speed of AFM imaging poses a challenge in applying deep learning methods broadly used in image recognition. This prospective is focused on ML recognition/classification when using a relatively small number of AFM images, aka small database. We discuss ML methods other than popular deep-learning neural networks. The described approach has already been successfully used to analyze and classify the surfaces of biological cells. It can be applied to recognize medical images, specific material processing, in forensic studies, even to identify the authenticity of arts. A general template for ML analysis specific to AFM is suggested, with a specific example of the identification of cell phenotype. Special attention is given to the analysis of the statistical significance of the obtained results, an important feature that is often overlooked in papers dealing with machine learning. A simple method for finding statistical significance is also described. [ABSTRACT FROM AUTHOR]

Photocatalytic technology is a novel approach that harnesses solar energy for efficient energy conversion and effective pollution abatement, representing a rapidly advancing field in recent years. The development and synthesis of high-performance semiconductor photocatalysts constitute the pivotal focal point. Oxygen vacancies, being intrinsic defects commonly found in metal oxides, are extensively present within the lattice of semiconductor photocatalytic materials exhibiting non-stoichiometric ratios. Consequently, they have garnered significant attention in the field of photocatalysis as an exceptionally effective means for modulating the performance of photocatalysts. This paper provides a comprehensive review on the concept, preparation, and characterization methods of oxygen vacancies, along with their diverse applications in nitrogen fixation, solar water splitting, CO2 photoreduction, pollutant degradation, and biomedicine. Currently, remarkable progress has been made in the synthesis of high-performance oxygen vacancy photocatalysts and the regulation of their catalytic performance. In the future, it will be imperative to develop more advanced in situ characterization techniques, conduct further investigations into the regulation and stabilization of oxygen vacancies in photocatalysts, and comprehensively comprehend the mechanism underlying the influence of oxygen vacancies on photocatalysis. The engineering of oxygen vacancies will assume a pivotal role in the realm of semiconductor photocatalysis. [ABSTRACT FROM AUTHOR]

As one of the most promising energy storage devices, supercapacitors exhibit a higher power density than batteries. However, its low energy density usually requires high-performance electrode materials. Although the RuO2 material shows desirable properties, its high cost and toxicity significantly limit its application in supercapacitors. Recent developments demonstrated that Co-based materials have emerged as a promising alternative to RuO2 for supercapacitors due to their low cost, favorable redox reversibility and environmental friendliness. In this paper, the morphological control and performance engineering of Co-based materials are systematically reviewed. Firstly, the principle of supercapacitors is briefly introduced, and the characteristics and advantages of pseudocapacitors are emphasized. The special forms of cobalt-based materials are introduced, including 1D, 2D and 3D nanomaterials. After that, the ways to enhance the properties of cobalt-based materials are discussed, including adding conductive materials, constructing heterostructures and doping heteroatoms. Particularly, the influence of morphological control and modification methods on the electrochemical performances of materials is highlighted. Finally, the application prospect and development direction of Co-based materials are proposed. [ABSTRACT FROM AUTHOR]

We investigate the thermodiffusive properties of aqueous solutions of lithium chloride, using thermal diffusion forced Rayleigh scattering in a concentration range of 0.5–2 mole per kg of solvent and a temperature range of 5 to 45 °C. All solutions exhibit non-monotonic variations of the Soret coefficient ST with a concentration exhibiting a minimum at about one mole per kg of solvent. The depth of the minimum decreases with increasing temperature and shifts slightly towards higher concentrations. We compare the experimental data with published data and apply a recent model based on overlapping hydration shells. Additionally, we calculate the ratio of the phenomenological Onsager coefficients using our experimental results and published data to calculate the thermodynamic factor. Simple linear, quadratic and exponential functions can be used to describe this ratio accurately, and together with the thermodynamic factors, the experimental Soret coefficients can be reproduced. The main conclusion from this analysis is that the minimum of the Soret coefficients results from a maximum in the thermodynamic factor, which appears itself at concentrations far below the experimental concentrations. Only after multiplication by the (negative) monotonous Onsager ratio does the minimum move into the experimental concentration window. [ABSTRACT FROM AUTHOR]

We are happy to receive the attention of Prof. Lambrecht regarding our paper and we appreciate his comments. However, it is hard to agree with his judgement about the "incorrect application", "incorrect interpretation", and the work being "misleading". Therefore, we would like to provide a defense and further discussion in this reply. [ABSTRACT FROM AUTHOR]

Chemical reaction neural network (CRNN), a recently developed tool for autonomous discovery of reaction models, has been successfully demonstrated on a variety of chemical engineering and biochemical systems. It leverages the extraordinary data-fitting capacity of modern deep neural networks (DNNs) while preserving high interpretability and robustness by embedding widely applicable physical laws such as the law of mass action and the Arrhenius law. In this paper, we further developed Bayesian CRNN to not only reconstruct but also quantify the uncertainty of chemical kinetic models from data. Two methods, the Markov chain Monte Carlo algorithm and variational inference, were used to perform the Bayesian CRNN, with the latter mainly adopted for its speed. We demonstrated the capability of Bayesian CRNN in the kinetic uncertainty quantification of different types of chemical systems and discussed the importance of embedding physical laws in data-driven modeling. Finally, we discussed the adaptation of Bayesian CRNN for incomplete measurements and model mixing for global uncertainty quantification. [ABSTRACT FROM AUTHOR]

Environmental pollution and the shortage of drinking water are the challenges that mankind is facing. Solar interface evaporation technology has been demonstrated as an important method for producing clean water, but its application to sewage still faces problems, mainly manifested in solubility and oily pollutants. Therefore, an evaporator device contains a superhydrophobic Bi2WO6 felt floating layer, a filter paper hydrophilic layer, and a copper foam/CuO photothermal layer, of which the water contact angle of the superhydrophobic felt can reach 159°. The floating layer not only has the ability to adsorb n-hexane but the Rh B degradation can also be realized under indoor/outdoor light conditions. The carrier life of Bi2WO6 is 28.8 ns. A copper foam/CuO photothermal layer prepared through a low-temperature treatment is combined with the floating and hydrophilic layer to obtain an evaporation rate of 1.53 kg m−2 h−1. [ABSTRACT FROM AUTHOR]

Employing nanostructures has been experimentally demonstrated to be an effective way of enhancing the phonon thermal transport across solid–solid interfaces, whereas the strengthening mechanism by large-size nanostructures is still unclear. In this paper, a novel theoretical method for simulating the heat transfer characteristics of the solid–solid contact interface containing large-size nanostructures is developed by combining the lattice Boltzmann method and molecular dynamics. The phonon transport features of the planar interface and the nanostructured ones are compared. The effects of the nanostructure shape and size on the interfacial phonon thermal transport are investigated, and mechanisms for enhancing interfacial phonon thermal transport by large-size nanostructures are revealed. The results show that the phonon transport at the large-size nanostructured interface is distributed regionally and has a pronounced directionality. The thermal transport enhancement of the large-size nanostructured interface is primarily achieved by increasing the interfacial contact area with respect to the planar interface, which increases the probability of phonon scattering at the interface and forms a thermal conduction pathway. The interfacial thermal transfer enhancement of large-size nanostructures is also influenced by the interfacial shape and the ballistic transport effect. There exist the optimal shape and size of the nanostructures to maximize the thermal transport across the solid–solid contact interface. [ABSTRACT FROM AUTHOR]

This paper focuses on the development of a quantum mechanics/molecular mechanics method using the ABEEM polarizable force field (QM/MM(ABEEM) method) to investigate the excision reaction mechanism of damaged thymine. This method does not simply combine the QM method with the polarizable force field. A valence electronegativity piecewise function with the distance between atoms as a variable is introduced to describe the atomic partial charges, and changes greatly during the reaction process. At the same time, the charge transfer effect is treated using the condition of local charge conservation. Compared with the traditional QM/MM method, the QM/MM(ABEEM) method can more accurately simulate the polarization effect and charge transfer effect in the reaction process. Focusing on the controversial problems of the excision of damaged bases, six reaction pathways were designed for monofunctional and difunctional deglycosylation of neutral bases and protonated bases. The results show that the QM/MM(ABEEM) method accurately simulates the polarization effect, charge transfer effect, activation energy and other properties of the reaction process. The process in which the active residue Asp activates the nucleophile H2O to attack the protonated base is the preferred path. The average activation energy and free activation energy of the protonated base are 7.00–14.00 kcal mol−1 lower than that of the neutral base. The study in this paper is helpful to understand the mechanism of repair enzymes in repairing bases. [ABSTRACT FROM AUTHOR]

Some smart hydrogels, like poly(N-isopropylacrylamide) (PNIPA) hydrogels, are sensitive to both stimulus hydrostatic pressure and temperature. The model for thermal-sensitive only hydrogels has been well established in the past two decades. In this work, by combining Flory's mean-field theory and Poisson–Nernst–Planck nonlinear equations, we develop a multiphysics model coupling chemo-electro-thermal-mechanical fields which can quantitatively calculate both hydrostatic pressure and thermal sensitivity of hydrogels in an electrolyte bathing solution. Considering PNIPA hydrogels as an example, the proposed model is validated by comparing the numerical results with experimental results reported in the literature. We investigate the influences of initial fixed-charge density, temperature, hydrostatic pressure, and bathing solution concentration on the volume expansion ratio of the hydrogels. Moreover, the concentration of mobile ions and distribution of electric potential within the hydrogel body and bathing solution are quantitatively predicted. The model and results obtained in this paper can be used to better understand the response of smart hydrogels sensitive to both hydrostatic pressure and temperature. [ABSTRACT FROM AUTHOR]

This work has been motivated by the recent paper by the author [M. Toutounji, Phys. Chem. Chem. Phys., 2021, 23, 21981] whereby a mixed quantum-classical Liouville equation was used to probe the spectroscopy and dynamics of a spin-boson system. A mixed quantum-classical Liouville equation treats the system of interest quantum mechanically, the bath classically, and the coupling term mixed quantum-classical mechanically. This paper offers a two-fold advantage: correcting the treatment of the electronic transition decay (width in frequency domain) and assessing the local heterogeneous vibrational structure. The homogeneous linear absorption spectrum of a chromophore embedded in a mixed quantum-classical environment at low temperature is composed of a sharp peak called a zero-phonon line (ZPL) and a broad phonon sideband (PSB), whereby the ZPL and the PSB are assimilated by a Lorentzian function and Voigt profiles, respectively. The PSB, in this case, is characterized by a local heterogeneous structure due to a dispersive medium of vibrations, modeled by vibrational Gaussian distributions to represent the arising inhomogeneous broadening and Lorentzians to model the homogeneous vibrations. This description seems to model proteins and amorphous solids exhibiting a local heterogeneous structure as both electronic and vibrational inhomogeneous broadening seems to be large in these media. This work provides a derivation of linear absorption lineshape and vibronic transition dipole moment time correlation functions, both of which account for pure electronic dephasing (ZPL width) the Voigt profile description of the phonon profiles (PSB) in dispersive media. [ABSTRACT FROM AUTHOR]

All-organic polymer dielectric films have been widely used for different electrical devices in recent years. However, their development is impeded by low Ue and large device volume. In the present paper, polyvinylidene fluoride (PVDF) composite dielectric materials, with high energy density (Ue) and energy efficiency (η), were prepared through the synergistic effect of a new MMA-co-GMA (MG) copolymer and cyanoethylated cellulose. MG was miscible with PVDF, which reduced the dielectric loss (tan δ) and improved the η of PVDF due to the linear structure and the hydrogen bonding interaction with the epoxy groups for MG. To further enhance the Ue of the dielectric films, cyanoethylated cellulose (CR-C) was added as a third component into the PVDF composite matrix to improve the Ue. The deep trap effect of hydrogen bonds between PVDF/MG and CR-C improved the electric breakdown strength (Eb) of the three-phase composite films from 440 MV m−1 to 640 MV m−1. Moreover, the high polarization of cyanoethylated cellulose can significantly improve the Ue (24.43 J cm−3) of the three-phase composite dielectric film, and the efficiency can be maintained above 75% at 640 MV m−1. This research provides a new idea for the manufacturing of homogeneous and stable all-organic PVDF dielectric composite films based on the hydrogen bonding construction strategy. [ABSTRACT FROM AUTHOR]

Effective spacecraft thermal control technologies are essential to avoid undesirable effects caused by extreme thermal conditions. In this paper, we demonstrate a transparent smart radiation device (TSRD) based on vanadium dioxide (VO2) and a hyperbolic metamaterial (HMM) structure. Using the topological transition property of HMM, high transmission in the visible band and high reflection in the infrared can be achieved simultaneously. The variable emission essentially originates from the phase change material VO2 film. Due to the high reflection of HMM in the infrared band, it can form Fabry–Pérot (FP) resonance with the VO2 film after adding the dielectric layer SiO2, which further enhances the emission modulation. Under optimized conditions, solar absorption can be reduced to 0.25, while emission modulation can reach 0.44 and visible transmission can be up to 0.7. It can be found that the TSRD can simultaneously achieve infrared variable emission, high visible transparency and low solar absorption. The HMM structure instead of traditional metal reflectors offers the possibility to achieve high transparency. In addition, the formation of FP resonance between the VO2 film and HMM structure is the key to achieving variable emission. We believe that this work can not only provide a new approach for the design of spacecraft smart thermal control devices, but also show great potential for application in spacecraft solar panels. [ABSTRACT FROM AUTHOR]

This work investigates the mixed site occupancy of aluminium and silicon atoms in the β-AlFeSi phase. For this purpose, the six mixed Al/Si sites of the β-AlFeSi structure were considered independent and alternatively substituted by Al or Si, thus generating 64 ordered structures or end-members. The enthalpy of formation of each end-member was calculated by DFT. These calculations allowed us to derive the enthalpy of mixing of the solid solution at 0 K, over a wide range of chemical compositions, from the Al–Fe binary system to the Si–Fe binary system. In addition, the heat capacities of the solid solution were determined using a Debye model based on the calculation of the elastic constants and the equation of state of each end-member. These heat capacity values were used along with the enthalpy of formation we calculated to determine the Gibbs free energies of all the end-members of the β-AlFeSi structure. Finally, the configurational entropy of mixing from the Compound Energy Formalism (CEF) for the configurational entropy of mixing was subsequently used to calculate the occupation fractions of the Si sites on the Al sites of the β-AlFeSi structure, at 300 K and 938 K, the latter being the thermal decomposition temperature of this compound. These original site occupancy data were used to quantify the chemical ordering of the solid solution and to compare different sublattice (SL) models. We thus highlight that the SL model of the β-AlFeSi solution most commonly accepted in the literature generates considerable errors in its thermodynamic description, contrary to the model proposed in this paper, which is both simple and particularly accurate, consisting in merging the sites Al(1)–Al(6), the sites Al(2)–Al(3) as well as the sites Al(4)–Al(5). [ABSTRACT FROM AUTHOR]

The basis sets that are used in the quantum chemical calculations of 31P NMR chemical shifts have always been one of the most important factors of accuracy. Regardless of what high-quality approach is employed, using basis sets of insufficient flexibility in the important angular regions may give poor results and lead to misassignments of the signals in the 31P NMR spectra. In this work, it was found that the existing nonrelativistic basis sets for phosphorus atom of double- and triple-ζ quality, specialized for the 31P NMR chemical shifts calculations, are essentially undersaturated in the d-angular space that occurred to play a significant role in the overall accuracy of these calculations. This problem has been thoroughly investigated, and new pecS-n (n = 1, 2) basis sets for phosphorus chemical shifts calculations were proposed. The exponents and contraction coefficients for the pecS-n basis sets were generated with the property-energy consistent method that has been introduced in our earlier paper, and has been proven useful in the creation of efficient property-oriented basis sets. New basis sets were optimized using the GIAO-DFT method with the B97-2 functional. Extensive benchmark calculations showed that the pecS-1 and pecS-2 basis sets provide very good accuracy, characterized by the corrected mean absolute percentage errors against the experiment of about 7.03 and 4.42 ppm, respectively. In particular, the accuracy of 31P NMR chemical shifts calculations achieved with the pecS-2 basis set is one of the most favorable accuracies for today. We believe that our new pecS-n (n = 1, 2) basis sets for phosphorus atom will prove useful in modern large-scale quantum chemical calculations of 31P NMR chemical shifts. [ABSTRACT FROM AUTHOR]

Nanoclusters represent a connection between (i) solid state systems and (ii) species in the atomic and molecular domains. Additionally, nanoclusters can also have very interesting electronic, optical and magnetic properties. For example, some aluminium clusters behave as superatoms and the doping of these clusters might strengthen their adsorption capabilities. Thus, we address herein the structural, energetic and electronic characterisation of scandium-doped aluminium clusters (AlnSc (n = 1–24)) by means of density functional theory calculations and quantum chemical topology wave function analyses. We studied the effect of Sc-doping on the structure and charge distribution by considering pure Al clusters as well. The quantum theory of atoms in molecules (QTAIM) reveals that interior Al atoms have large negative atomic charges (≈2a.u.) and hence the atoms surrounding them are considerably electron deficient. The Interacting Quantum Atoms (IQA) energy partition allowed us to establish the nature of the interaction between the Al13 superatom and the Al12Sc cluster with Al to form the complexes Al14 and Al13Sc, respectively. We also used the IQA approach to examine (i) the influence of Sc on the geometry of the AlnSc complexes along with (ii) the cooperative effects in the binding of AlnSc and Aln+1 clusters. We also exploited the QTAIM and IQA approaches to study the interaction of the electrophilic surface of the examined systems with CO2. Overall, we observe that the investigated Sc-doped Al complexes with a marked stability towards disproportionation reactions exhibit strong adsorption energies with CO2. Concomitantly, the carbon dioxide molecule is considerably distorted and destabilised, conditions which might prepare it for further chemical reactions. Altogether, this paper gives valuable insights on the tuning of the properties of metallic clusters for their design and exploitation in custom-made materials. [ABSTRACT FROM AUTHOR]

Resistive random access memory has been widely studied as a powerful candidate for building future memories and realizing high-efficiency artificial neuromorphic systems. In this paper, gold nanoparticles (Au NPs) are doped in a leaf solution of Scindapsus aureus (SA) as the active layer to fabricate Al/SA:Au NPs/ITO/glass resistive random access memory. The device exhibits stable bipolar resistance switching characteristics. More importantly, the device's multilevel storage capabilities and synaptic potentiation and depression behaviour have been proven. Compared with the device without doped Au NPs in the active layer, the device has a higher ON/OFF current ratio, which is attributed to the Coulomb blockade effect caused by the Au NPs. The device plays an important role in realizing high-density memory and efficient artificial neuromorphic systems. [ABSTRACT FROM AUTHOR]

The health hazards caused by low concentrations of Pb2+ ions in drinking water systems are of significant concern. In order to remove Pb2+ ions and retain Na+, K+, Ca2+ and Mg2+ as harmless competitive ions without simultaneous removal, nickel foam (NF)/Mn2CoO4@tannic acid (TA)-Fe3+ electrodes were prepared by a hydrothermal method and a coating method and an asymmetric capacitive deionization (CDI) system is established using the prepared electrodes and a graphite paper positive electrode. The designed asymmetric CDI system exhibited a high Pb2+ adsorption capacity of 375 mg g−1 with high removal efficiency and significant regeneration behavior at 1.4 V at neutral pH. When the asymmetric CDI system is used to enrich a hydrous solution of mixed Na+, K+, Ca2+, Mg2+ and Pb2+ ions each with a concentration of 10 ppm and 100 ppm by electrosorption at a 1.4 V operating voltage, the removal rate of Pb2+ is as high as 100% and 70.8% respectively, and the relative selectivity coefficients are 4.51–43.22. According to the different adsorption mechanisms of lead ions and coexisting ions, the separation and recovery of ions can be realized by a two-step desorption process, thereby providing a new method for removing Pb2+ ions from drinking water with excellent application potential. [ABSTRACT FROM AUTHOR]

Narrow bandgap inorganic compounds are extremely important in many areas of physics. However, their basic parameter database for surface analysis is incomplete. Electron inelastic mean free paths (IMFPs) are important parameters in surface analysis methods, such as electron spectroscopy and electron microscopy. Our previous research has presented a machine learning (ML) method to describe and predict IMFPs from calculated IMFPs for 41 elemental solids. This paper extends the use of the same machine learning method to 42 inorganic compounds based on the experience in predicting elemental electron IMFPs. The in-depth discussion extends to including material dependence discussion and parameter value selections. After robust validation of the ML method, we have produced an extensive IMFP database for 12 039 narrow bandgap inorganic compounds. Our findings suggest that ML is very efficient and powerful for IMFP description and database completion for various materials and has many advantages, including stability and convenience, over traditional methods. [ABSTRACT FROM AUTHOR]

For many years, the atomic structures of several defects in diamond with high wavenumber (>4000 cm−1), including "amber centers", H1b, and H1c, have been investigated, but a conclusive explanation is still lacking. In this paper, we propose a novel model for the N–H bond under repulsion, with an expected vibrational frequency exceeding 4000 cm−1. Additionally, potential defects called NVH4 are proposed to investigate their correlation with these defects. Three NVH4 defects are considered, denoting a charge of e = +1, e = 0, and e = −1 for NVH4+, NVH 04 , and NVH4−, respectively. Subsequently, the geometry, charge, energy, band structure, and spectroscopic characterization of the three defects NVH4+, NVH 04 , and NVH4− are analysed. Then, the calculated harmonic modes of N3VH defects are used as a benchmark for studying NVH4. The simulations indicate that, with the use of scaling factors, the highest NVH4+ harmonic infrared peaks are 4072 cm−1, 4096 cm−1, and 4095 cm−1 with PBE, PBE0, and B3LYP, respectively, along with a calculated anharmonic infrared peak at 4146 cm−1. These calculated characteristic peaks closely match those observed in "amber centers" (4065 cm−1 and 4165 cm−1). However, based on the additional simulated anharmonic infrared peak at 3792 cm−1, NVH4+ cannot be assigned to the 4165 cm−1 band. It is possible to assign the 4065 cm−1 band to NVH4+; even though it can remain stable in diamond at 1973 K, establishing and measuring this benchmark could be challenging. Although NVH4+ is uncertain as a structure in "amber centers", a model of the N–H bond under repulsion stretching is proposed, which can generate a vibrational frequency surpassing 4000 cm−1. It may provide a useful avenue for investigating high wavenumber defect structures in diamond. [ABSTRACT FROM AUTHOR]

Although the design of graphene-based tunable broadband terahertz (THz) absorbers has attracted much attention, improving the functionality of the absorbers to adapt to different scenarios is still worth studying. This paper presents an innovative design of a quad-functional metasurface absorber (QMA) in the THz region, which can switch the absorption frequency/band by means of dual voltage/thermal manipulation. By electrically manipulating the chemical potential of graphene, the QMA can switch freely between the narrowband absorption mode ("NAM") and the broadband absorption mode ("BAM"), while thermally manipulating the phase transition of VO2 allows switching between the low-frequency absorption mode ("LAM") and the high-frequency absorption mode ("HAM"). Detailed mechanistic analysis shows that the "NAM" and "BAM" are due to the switching of the fundamental and second order graphene surface plasmon polariton (SPP) resonances, respectively, and the switching between "LAM" and "HAM" is due to the phase transformation of VO2. Furthermore, the QMA is polarization insensitive in all absorption modes and maintains excellent absorption performance at large angular incidence of TE- and TM-polarized waves. All the results indicate that the proposed QMA has great potential for stealth, sensing, switching, and filtering applications. [ABSTRACT FROM AUTHOR]

This paper describes a compact new instrument, conceived specifically for measurements of Photo Electron Elliptical Dichroism (PEELD) and designed for simplicity of use as a prototype for a practical analytical device. PEELD is an asymmetry in the electron angular distribution obtained from resonantly enhanced multi-photon ionisation of a chiral molecule, where there is also a non-linear dependence on the polarization ellipticity. Despite the fact that PEELD can provide a unique signature of molecular structure and dynamics it has only been investigated in a few molecules to date. This is addressed in the present study in a range of measurements of several terpenes and phenyl-alcohols. These show that the PEELD signatures in structural isomers can be dramatically different and can also be influenced by the intensity of the light. A systematic study in phenyl-alcohols containing the same chromophore and chiral centre configuration shows consistent PEELD behaviour across the molecules except that the magnitude reduces as the distance from the chromophore to the chiral centre increases. These achievements demonstrate that this relatively simple set up can be used for scientific studies as well as providing a blueprint for a practical chiral analysis instrument. [ABSTRACT FROM AUTHOR]

With the nanotechnology boom, artificially designed nucleic acid nanotubes have aroused interest due to their practical applications in nanorobotics, vaccine design, membrane channels, drug delivery, and force sensing. In this paper, computational study was performed to investigate the structural dynamics and mechanical properties of RNA nanotubes (RNTs), DNA nanotubes (DNTs), and RNA–DNA hybrid nanotubes (RDHNTs). So far, the structural and mechanical properties of RDHNTs have not been examined in experiments or theoretical calculations, and there is limited knowledge regarding these properties for RNTs. Here, the simulations were carried out using the equilibrium molecular dynamics (MD) and steered molecular dynamics (SMD) approaches. Using in-house scripting, we modeled hexagonal nanotubes composed of six double-stranded molecules connected by four-way Holliday junctions. Classical MD analyses were performed on the collected trajectory data to investigate structural properties. Analyses of the microscopic structural parameters of RDHNT indicated a structural transition from the A-form to a conformation between the A- and B-forms, which may be attributable to the increased rigidity of RNA scaffolds compared to DNA staples. Comprehensive research on the elastic mechanical properties was also conducted based on spontaneous thermal fluctuations of nanotubes and employing the equipartition theorem. The Young's modulus of RDHNT (E = 165 MPa) and RNT (E = 144 MPa) was found to be almost the same and nearly half of that found for DNT (E = 325 MPa). Furthermore, the results showed that RNT was more resistant to bending, torsional, and volumetric deformations than DNT and RDHNT. We also used non-equilibrium SMD simulations to acquire comprehensive knowledge of the mechanical response of nanotubes to tensile stress. [ABSTRACT FROM AUTHOR]

This paper investigated the defect generation mechanism of two self-made ytterbium-doped fibers (a Yb-doped fiber and a Yb/Ce-doped fiber) under proton irradiation and the influence of Ce-doping on proton radiation defects. The macroscopic damage of different optical fibers caused by proton irradiation energy and irradiation doses was further studied. Fluorescence spectroscopy, EPR electron paramagnetic resonance and SEM experiments were used to characterize the micro defects and macro damage of the fibers. The following conclusions are drawn: the damage on the surface of optical fibers increases continuously with the increase of irradiation dose, and does not change significantly with the increase of proton energy. The main defect in the irradiated fibers is proved to be the Al-OHC defect which leads to energy loss in the visible light region and a photon darkening effect. After Ce doping, the change trend of the amount of Al-OHC defect is greatly suppressed, while it shows little effect on the oxygen defect (intrinsic), and basically does not change this trend. On the other hand, Ce doping can also effectively reduce the generation of Si-E′ defects in the irradiated fibers according to the EPR electron paramagnetic resonance experiment. In conclusion, due to the presence of two valence states of Ce ions, Ce doping prominently improves the performance of high-power Yb-doped fibers under proton irradiation. [ABSTRACT FROM AUTHOR]