The 100 most-cited articles in Physical Chemistry Chemical Physics, 2023

-based, and bismuth-based semiconductor materials and their applications in the degradation of water pollutants are highlighted with recent illustrative examples. Furthermore, the future prospects of semiconductor photocatalysis for water treatment are critically analyzed.

This review outlines the recent accomplishments in the design and modification of interface structures in heterojunction photocatalysts, aiming to provide some useful perspectives for future research in this field.

values and bonding distances (∼2 Å) reveal that the interaction type is chemisorption. The ZnO nanostructures showed promising performance in the ALA drug functionalization, taking into account the interaction energy values. The band gap almost remains unchanged for both of the substrates under consideration after ALA adsorption, and the semiconductor properties of the substrates are preserved, according to the analyzed density of states (DOSs) spectra. The interaction nature of the ALA-ZnO nanostructures according to the atom in molecule (AIM) analysis was found to be polar attraction with partial covalent bonding between O and Zn. Our DFT based molecular dynamic (MD) simulation results demonstrate that, in the aqueous solution, ALA moves toward the interior sidewall of the ZnONTs and ZnO nanosheet surface and binds to the Zn atom through its O (carbonyl/hydroxyl groups) and N atoms and the hydroxyl H atom was dissociated and binds to the O atom of the ZnO surface. However, in the case of ALA adsorption onto the outer surface of ZnONTs, only the O atoms of carbonyl groups bind to…

Solubility plays a critical role in many aspects of research (drugs to materials). Solubility parameters are very useful for selecting appropriate solvents/non-solvents for various applications. In the present study, Hansen solubility parameters are predicted using machine learning. More than 40 machine models are tried in the search for the best model. Molecular descriptors and fingerprints are used as inputs to get a comparative view. Machine learning models trained using molecular descriptors have shown higher prediction ability than the model trained using molecular fingerprints. Machine learning models trained using molecular descriptors have shown their potential to be easy and fast models compared to the density functional theory (DFT)/thermodynamic approach. Machine learning creates a "black box" connection to the properties. Therefore, minimal computational cost is required. With the help of the best-trained machine learning model, green solvents are selected for small molecule donors that are used in organic solar cells. Our introduced framework can help to select solvents…

Counterfeit products have infiltrated numerous regions worldwide, causing substantial damage to the financial interests of individuals, businesses, and countries. Moreover, counterfeit goods can pose a severe risk to human health. Therefore, it is crucial to develop effective anti-counterfeiting methods and authentication technologies. Persistent luminescence (PersL) materials show great potential for anti-counterfeiting applications due to their distinctive spatial and temporal dynamic spectrum performance. The unique luminescence properties of PersL materials enable the creation of optical codes with high capacity. In this perspective, we provide a summary of the latest advancements in anti-counterfeiting technology using long persistent phosphors. We discuss the various construction strategies of optical codes for anti-counterfeiting, which include multicolor luminescence, orthogonal luminescence, dynamic luminescence, and stimulus-response luminescence. In addition, we explore the mechanisms of PersL-based anti-counterfeiting materials and consider potential areas for future…

Nanoparticles have become increasingly important for a variety of applications, including medical diagnosis and treatment, energy harvesting and storage, catalysis, and additive manufacturing. The development of nanoparticles with different compositions, sizes, and surface properties is essential to optimize their performance for specific applications. Pulsed laser ablation in liquid is a green chemistry approach that allows for the production of ligand-free nanoparticles with diverse shapes and phases. Despite these numerous advantages, the current production rate of this method remains limited, with typical rates in the milligram per hour range. To unlock the full potential of this technique for various applications, researchers have dedicated efforts to scaling up production rates to the gram-per-hour range. Achieving this goal necessitates a thorough understanding of the factors that limit pulsed laser ablation in liquid (PLAL) productivity, including laser, target, liquid, chamber, and scanner parameters. This perspective article explores these factors and provides a roadmap…

With the development of science and technology, intermediate infrared technology has gained more and more attention in recent years. In the research described in this paper, a tunable broadband absorber based on a Dirac semimetal with a layered resonant structure was designed, which could achieve high absorption (more than 0.9) of about 8.7 THz in the frequency range of 18-28 THz. It was confirmed that the high absorption of the absorber comes from the strong resonance absorption between the layers, and the resonance of the localised surface plasmon. The absorber has a gold substrate, which is composed of three layers of Dirac semimetal and three layers of optical crystal plates. In addition, the resonance frequency of the absorber can be changed by adjusting the Fermi energy of the Dirac semimetal. The absorber also shows excellent characteristics such as tunability, absorption stability at different polarisation waves and incident angles, and has a high application value for use in radar countermeasures, biotechnology and other fields.

calculations, about recent advances in the fields of dual solution-solid emitters and lasing applications based on organic dyes displaying an excited-state intramolecular proton transfer (ESIPT) process. ESIPT is known to be highly sensitive to the immediate environment leading to the engineering of a wide range of stimuli-responsive fluorescent dyes. With the structural diversity of ESIPT-capable fluorophores being large, many applications have been targeted over the years in the fields of optoelectronics, biology and luminescent displays. This review wishes to point out two emerging applications concerning ESIPT fluorophores, which are the answer for the quest for emitters fluorescing both in solution and in the solid state, and those capable of light amplification.

-polarization waves. The operation mechanism behind the phenomena can be explained by utilizing the electric field distribution and the coupled mode theory. Moreover, the influences of the Fermi energy of graphene and geometrical parameters on the CD and absorption spectra are discussed in detail. Our proposed switchable and tunable metamaterial can provide a platform for designing versatile functional devices in the terahertz region.

In tribology, a considerable number of computational and experimental approaches to understand the interfacial characteristics of material surfaces in motion and tribological behaviors of materials have been considered to date. Despite being useful in providing important insights on the tribological properties of a system, at different length scales, a vast amount of data generated from these state-of-the-art techniques remains underutilized due to lack of analysis methods or limitations of existing analysis techniques. In principle, this data can be used to address intractable tribological problems including structure-property relationships in tribological systems and efficient lubricant design in a cost and time effective manner with the aid of machine learning. Specifically, data-driven machine learning methods have shown potential in unraveling complicated processes through the development of structure-property/functionality relationships based on the collected data. For example, neural networks are incredibly effective in modeling non-linear correlations and identifying primary…

Magnetisation decay measurements are commonly being used to characterise very slow relaxation in single-molecule magnets. We explore measurement protocol and data analysis to define the best practise.

The effects of Auger capture coefficients in mixed-cation perovskites are analyzed employing SCAPS-1D simulations.

RIU. The results show that the proposed sensor combines the SPR effect, which is extremely sensitive to changes in the RI of the surrounding medium and realizes real-time detection of the external environment by analyzing the light signal modulated by the sensor. In addition, the detection range and sensitivity can be extended by adjusting the structural parameters. The proposed sensor has a simple structure with excellent sensing performance, which provides a new idea and implementation method for real-time detection, long-range measurement, complex environment monitoring and highly integrated sensing, and has a strong potential practical value.

. Resistively damped currents in microstructures and low-conducting oxide layers are shown to complicate trustworthy capacitance-based estimations of ECSAs. In the second part of this study, advanced equivalent circuits models to describe the measured EIS and CV responses are presented.

This perspective presents the state-of-the-art of photocatalytic overall water splitting and the challenges toward large-scale applications.

For noble metals, such as gold (Au) and silver (Ag), it is well-known that surface plasmons of their nanocrystals have significant spatial confinement and propagation loss due to the strong damping effect and the scattering between the plasmons and phonons. Noble metal nanostructures are usually referred to as "plasmonic nanostructures" in many studies. Based on the resonance effect of surface plasmons, the electromagnetic field can be localized on the subwavelength scale, which induces a booming new field of nanophotonics. Among the various nanostructures, Au nanostructures have received extensive attention both in fundamental research and technological fields due to their unique localized surface plasmon characteristics. These characteristics include strong optical extinction, near-field enhancement, and far-field scattering. By changing either the morphological parameters or the surrounding medium of nanostructures, the localized surface plasmon resonance (SPR) of Au nanostructures can be tuned in a large spectral region from visible to near infrared (Vis-NIR) wavelength.…

Cu 4 Se 4 nanosheet is predicted to be promising electrode materials due to its excellent electrical conductivity, high capacity, fast diffusion and little volume change. They are also applicable to aqueous Na/K batteries with decreased capacities.

The theory of electron transfer reactions establishes the conceptual foundation for redox solution chemistry, electrochemistry, and bioenergetics. Electron and proton transfer across the cellular membrane provide all energy of life gained through natural photosynthesis and mitochondrial respiration. Rates of biological charge transfer set kinetic bottlenecks for biological energy storage. The main system-specific parameter determining the activation barrier for a single electron-transfer hop is the reorganization energy of the medium. Both harvesting of light energy in natural and artificial photosynthesis and efficient electron transport in biological energy chains require reduction of the reorganization energy to allow fast transitions. This review article discusses mechanisms by which small values of the reorganization energy are achieved in protein electron transfer and how similar mechanisms can operate in other media, such as nonpolar and ionic liquids. One of the major mechanisms of reorganization energy reduction is through non-Gibbsian (nonergodic) sampling of the medium…

Time-resolved photoluminescence (TRPL) is an effective experimental technique to study charge carrier dynamic processes in halide perovskites on different time scales. In the past decade, several models have been proposed and employed to study the TRPL curves in halide perovskites, but there is still a lack of systematic summarization and comparative discussion. Here, we reviewed the widely employed exponential models to fit the TRPL curves, and focused on the physical meaning of the extracted carrier lifetimes, as well as the existing debates on the definition of the average lifetime. Emphasis was placed on the importance of the diffusion process in the carrier dynamics, especially for the halide perovskite thin films having transport layers. The solving of the diffusion equation, using both analytical and numerical methods, was then introduced to fit the TRPL curves. Furthermore, the newly proposed global fit and direct measurement of radiative decay rates were discussed.

Relationships between TD-DFT visualization tools are explored, with an emphasis on characterizing charge separation between the excited electron and the hole.

to within 1% of NMR values. The intermediate character of four-coordinated zinc in borate glasses of this series is evident by the far infrared profiles and the glass transition temperature behavior, which decreases non-monotonically with increasing ZnO content.

Hybrid quantum mechanical/molecular mechanical (QM/MM) methods are a powerful computational tool for the investigation of all forms of catalysis, as they allow for an accurate description of reactions occurring at catalytic sites in the context of a complicated electrostatic environment. The scriptable computational chemistry environment ChemShell is a leading software package for QM/MM calculations, providing a flexible, high performance framework for modelling both biomolecular and materials catalysis. We present an overview of recent applications of ChemShell to problems in catalysis and review new functionality introduced into the redeveloped Python-based version of ChemShell to support catalytic modelling. These include a fully guided workflow for biomolecular QM/MM modelling, starting from an experimental structure, a periodic QM/MM embedding scheme to support modelling of metallic materials, and a comprehensive set of tutorials for biomolecular and materials modelling.

The 1 S 0 → 3 P 1 transition energy of Bi 3+ in solids is predicted within ±0.35 eV.

. This research focuses on creating intelligent nanochannels by controlling mass concentration, charge density, and collapse length, improving system performance, and optimizing properties. It also offers valuable insights into ion transport mechanisms in nanochannel systems, advancing our understanding in this field.

The liquid-air surface tension of aqueous solutions is a fundamental quantity in multi-phase thermodynamics and fluid dynamics and thus relevant in many scientific and engineering fields. Various models have been proposed for its quantitative description. This Perspective gives an overview of the most popular models and their ability to reproduce experimental data of ten binary aqueous solutions of electrolytes and organic molecules chosen to be representative of different solute types. In addition, we propose a new model which reproduces sigmoidal curve shapes (Sigmoid model) to empirically fit experimental surface tension data. The surface tension of weakly surface-active substances is well reproduced by all models. In contrast, only few models successfully model the surface tension of aqueous solutions with strongly surface-active substances. For substances with a solubility limit, usually no experimental data is available for the surface tension of supersaturated solutions and the pure liquid solute. We discuss ways in which these can be estimated and emphasize the need for…

In this perspective, we review some recent advances in the concept of atoms-in-molecules from a real space perspective. We first introduce the general formalism of atomic weight factors that allows unifying the treatment of fuzzy and non-fuzzy decompositions under a common algebraic umbrella. We then show how the use of reduced density matrices and their cumulants allows partitioning any quantum mechanical observable into atomic or group contributions. This circumstance provides access to electron counting as well as energy partitioning, on the same footing. We focus on how the fluctuations of atomic populations, as measured by the statistical cumulants of the electron distribution functions, are related to general multi-center bonding descriptors. Then we turn our attention to the interacting quantum atom energy partitioning, which is briefly reviewed since several general accounts on it have already appeared in the literature. More attention is paid to recent applications to large systems. Finally, we consider how a common formalism to extract electron counts and energies can be…

The MX 2 Y 4 (M = Cr, Hf, Mo, Ti, W, Zr; X = Si, Ge; Y = N, P, As) monolayers possess potential advanced applications such as photocatalytic, electrocatalytic, and photovoltaic devices.

The recently synthesized novel figure-of-eight nanohoop with two strained oligoparaphenylenes (OPPs) was theoretically designed to collect and stabilize new allotropic carbon cyclo[18]carbon (C 18 ) through molecular assembly.

Energetic compounds, as a type of special material, are widely used in the fields of national defense, aerospace and exploration. Their research and production have received growing attention. Thermal stability is a crucial factor for the safety of energetic materials. Azole-rich energetic compounds have emerged as a research hotspot in recent years owing to their excellent properties. Due to the aromaticity of unsaturated azoles, many azole-rich energetic compounds have significant thermal stability, which is one of the properties that researchers focus on. This review presents a comprehensive summary of the physicochemical and energetic properties of various energetic materials, highlighting the relationship between thermal stability and the structural, physicochemical, and energetic properties of azole-rich energetic compounds. To improve the thermal stability of compounds, five aspects can be considered, including functional group modification, bridging, preparation of energetic salts, energetic metal-organic frameworks (EMOFs) and co-crystals. It was demonstrated that…

forming light-matter hybrid states, so-called polaritons. The perspective starts with the basic background of light-matter interactions, molecular quantum electrodynamics theory, and the challenges of modeling light-matter interactions in chemistry. Then, the recent advances in modeling plasmon and polariton chemistry are described, and future directions toward multiscale simulations of light-matter interaction-mediated chemistry are discussed.

-analogue linker. Applying density functional theory (DFT), suitable models for all UiO-66-MOF analogues were generated by assessing different exchange-correlation functionals. Afterwards, HSE06 hybrid functional calculations were performed to obtain the electronic structures and optical properties. The detailed HSE06 electronic structure calculations were validated with UV-Vis measurements to ensure reliable results. Finally, the refractive index dispersion of the seven UiO-66-type materials is compared, showing the possibility to tailor the optical properties by the use of functionalized linker molecules. Specifically, the refractive index can be varied over a wide range from 1.37 to 1.78.

An active environment is any atomic or molecular system changing a chromophore's nonadiabatic dynamics compared to the isolated molecule. The action of the environment on the chromophore occurs by changing the potential energy landscape and triggering new energy and charge flows unavailable in the vacuum. Surface hopping is a mixed quantum-classical approach whose extreme flexibility has made it the primary platform for implementing novel methodologies to investigate the nonadiabatic dynamics of a chromophore in active environments. This Perspective paper surveys the latest developments in the field, focusing on charge and energy transfer processes.

Chalcogenide perovskites have recently attracted enormous attention since they show promising optoelectronic properties and high stability for photovoltaic applications.

/SMe-TATPyr/gold (Au), and the PCE reached up to 20% with a fill factor (FF) of 81.89%.

Surface phenomena in aqueous environments such as long-range hydrophobic attraction, macromolecular adhesion, and even biofouling are predominantly influenced by a fundamental parameter-the water contact angle. The minimal contact angle required for these and related phenomena to occur has been repeatedly reported to be around 65° and is commonly referred to as the "Berg limit." However, the universality of this specific threshold across diverse contexts has remained puzzling. In this perspective article, we aim to rationalize the reoccurrence of this enigmatic contact angle. We show that the relevant scenarios can be effectively conceptualized as three-phase problems involving the surface of interest, water, and a generic oil-like material that is representative of the nonpolar constituents within interacting entities. Our analysis reveals that attraction and adhesion emerge when substrates display an underwater oleophilic character, corresponding to a "hydrophobicity under oil", which occurs for contact angles above approximately 65°. This streamlined view provides valuable…

RHE, which indicates a change of the dominant buffering species. Through scan rate-dependent voltammetry and chronopotentiometry experiments, the homogenous reactions are shown to reach equilibrium within the time scale of the pH measurements, so that the interfacial concentrations of different carbonaceous species can be calculated using equilibrium constants. Furthermore, pH measurements were also performed under different conditions to disentangle the relationship between the interfacial pH and other electrolyte effects. The buffer effect of alkali metal cations is confirmed, showing that weakly hydrated cations lead to less pronounced pH gradients. Finally, we probe to which extent increasing mass transport and the electrolyte buffer capacity can aid in suppressing the increase of the interfacial pH, showing that the buffer capacity is the dominant factor in suppressing interfacial pH variations.

(GST) layer could help to engineer the average emissivity of the proposed infrared emitter, achieving tunable mid-infrared (MIR) camouflage, radiation heat dissipation, and long-infrared (LIR) camouflage in wavelength ranges of 3-5 μm, 5-8 μm, and 8-14 μm, respectively. Finally, we numerically demonstrate the visible camouflage and infrared camouflage for different application scenarios by using the simulated visible and infrared images. This work has promising application potential in visible-infrared compatible camouflage technology.

data. Additionally, we show that fine-tuning with energy labels alone can suffice to obtain accurate atomic forces and run large-scale atomistic simulations, provided a well-designed fine-tuning data set. We also investigate possible limitations of transfer learning, especially regarding the design and size of the pre-training and fine-tuning data sets. Finally, we provide GM-NN potentials pre-trained and fine-tuned on the ANI-1x and ANI-1ccx data sets, which can easily be fine-tuned on and applied to organic molecules.

Light alkenes are the key building blocks in the chemical industry. As a propene on-purpose production technology, propane dehydrogenation has drawn particular attention due to the growing demand for propene and the discovery of large reserves of shale gas. The development of highly active and stable propane dehydrogenation catalysts is significant in the world-wide research field. Supported platinum-based catalysts are widely studied for propane dehydrogenation. This article reviews the developments of platinum-based catalysts in propane dehydrogenation, particularly focusing on the influence of the promoter effect and support effect on the structure and catalytic performance and especially on how promoters and supports enable Pt to form highly dispersed and stable active sites. At the end, we propose the prospective research directions of propane dehydrogenation.

Due to the physically unrestricted set of orthogonally helical modes of orbital angular momentum (OAM), it has contributed significantly to wireless communication and information capacity. Meanwhile, focusing has important applications in fields such as super-resolution microscopic imaging and optical integration. Plasmonic metasurfaces have a powerful ability to modulate electromagnetic (EM) waves, and diversified functionalities in them are strongly desired. As of today, few plasmonic metasurfaces are reported which have multi-function in a single flat device. Herein, by fine-tuning the geometric dimensions and orientation angle of the meta-atom, the geometric phase is combined with the propagation phase to produce an independent phase response when left-handed circular polarization (LCP) and right-handed circular polarization (RCP) waves illuminate the metasurface. This paper presents three plasmonic metasurfaces, and each of them implements multiple functions on a single plasmonic metasurface. Firstly, normal reflection of OAM and a focused beam is achieved. Secondly, we realize…

Computation of accurate geometrical structures and spectroscopic properties of large flexible molecules in the gas-phase is tackled at an affordable cost using a general exploration/exploitation strategy. The most distinctive feature of the approach is the careful selection of different quantum chemical models for energies, geometries and vibrational frequencies with the aim of maximizing the accuracy of the overall description while retaining a reasonable cost for all the steps. In particular, a composite wave-function method is used for energies, whereas a double-hybrid functional (with the addition of core-valence correlation) is employed for geometries and harmonic frequencies and a cheaper hybrid functional for anharmonic contributions. A thorough benchmark based on a wide range of prototypical molecular bricks of life shows that the proposed strategy is close to the accuracy of state-of-the-art composite wave-function methods, and is applicable to much larger systems. A freely available web-utility post-processes the geometries optimized by standard electronic structure codes…

nanocomposites is beneficial for the energy industry and environmental remediation applications.

We report for the first time that the red fluorescence of leaf-derived carbon dots is derived from chlorophyll, and a possible formation structure is proposed. By controlling the solvothermal reaction temperature, the new luminescence center of CDs can be adjusted. This work provides unprecedented insights into the luminescence mechanism of biomass-derived CDs.

economy. In this review, the recent progress on newer materials including metals, alloys, and transition metal oxides (manganese oxides, cobalt oxides, nickel oxides, PBA-derived metal oxides, and metal complexes) as photocatalysts/electrocatalysts has been overviewed together with some methodologies for efficient water splitting. Metal-organic framework (MOF)-based electrocatalysts have been highly exploited owing to their interesting functionalities. The photovoltaic-electrocatalytic (PV-EC) process focused on harvesting high solar-to-hydrogen efficiency (STH) among various solar energy conversion as well as storage systems. Electrocatalysts/photocatalysts with high efficiency have become an urgent need for overall water splitting. Also, cutting-edge achievements in the fabrication of electrocatalysts along with theoretical consideration have been discussed.

The QM/MM simulation method is provenly efficient for the simulation of biological systems, where an interplay of extensive environment and delicate local interactions drives a process of interest through a funnel on a complex energy landscape. Recent advances in quantum chemistry and force-field methods present opportunities for the adoption of QM/MM to simulate heterogeneous catalytic processes, and their related systems, where similar intricacies exist on the energy landscape. Herein, the fundamental theoretical considerations for performing QM/MM simulations, and the practical considerations for setting up QM/MM simulations of catalytic systems, are introduced; then, areas of heterogeneous catalysis are explored where QM/MM methods have been most fruitfully applied. The discussion includes simulations performed for adsorption processes in solvent at metallic interfaces, reaction mechanisms within zeolitic systems, nanoparticles, and defect chemistry within ionic solids. We conclude with a perspective on the current state of the field and areas where future opportunities for…

trehalose forms less hydrogen bonds to the protein surface than sucrose. Furthermore, the rotational motion around dihedrals between the two glucose rings of trehalose is slower than in the case of the dihedrals between the glucose and fructose rings of sucrose. This leads to a less perturbed protein structure in the case of trehalose. The observations indicate that an aqueous environment closest to the protein molecules is beneficial for an efficient bioprotective solution.

Multiple Spawning (AIMS) method alongside TSH. The three systems present different deactivation pathways after excitation to their ππ* bright states. When comparing DD-vMCG to AIMS and TSH, we obtain crucial differences in some cases, for which an explanation is provided by the classical nature and the chosen initial conditions of the TSH simulations.

, thus making possible their identification. In contrast to previous reports, we find a nontrivial dependence between CLBEs and the local electronic occupation at N sites. The assignment of spectral details in the XPS data to well-defined N-defects on CNTs is not straightforward and needs to be more deeply analyzed.

Janus SGa 2 Te monolayers have moderate direct gaps, suitable band edges for photocatalytic water splitting, and high light absorption coefficients for the visible light, suggesting their potential applications in optoelectronic and photocatalytic devices.

exsolution techniques are introduced and their related functionalities are also explained, respectively. While for the cathode, we focus on the perovskite-type materials because of their superior catalytic performance and relatively good stability. The optimization of perovskite composition, including A site alkali or alkali-earth metal doping and B site variable-valence transition metal doping, is discussed in detail based on their effects on oxygen reduction reaction (ORR). Besides, nanostructure assembly and 3D morphology design are also recent hotspots for cathode research. Finally, we also propose several research directions in this field, hoping to provide guidelines for future research.

In this study, we present an overview on the use of ionic liquids (ILs) as electrolytes in sodium-ion batteries (SIBs). The development of SIBs has gained traction over the last few years because Na is cheaper and more abundant than Li. In this case, although great efforts have been devoted to finding high-capacity and high cell potential materials for SIBs, electrolyte safety is an important factor in producing more competitive and reliable devices. Specifically, the intrinsic volatility of the organic solvent-based electrolytes commonly used in commercial systems is a safety risk during the operation of batteries, and thus replacing them with ILs is an alternative that should be considered. This family of electrolytes is more thermally stable than organic solvents, but they suffer from poor transport properties. Herein, we discuss these properties, considering neat ILs, effects of cations and anions, and effect of salt concentration. Moreover, the strategies to overcome the transport limitations are highlighted. Then, the recent applications of mixtures containing sodium salts and…

A geometric model to probe excited-state aromaticity and antiaromaticity termed HOMER is reported. When tested by quantum-chemical calculations on carbocyclic and heterocyclic systems, the model is found consistent with state-of-the-art magnetic data.

MoB can effectively activate CO 2 with a large interaction energy of −3.64 eV. At −0.62 V, the CO 2 reduction becomes a high-throughput reaction towards CH 4 . MoB can effectively inhibit the hydrogen evolution reaction at moderate potentials.

Formation of Ni-(oxy)-hydroxides on NiO x thin films in H 2 O vapor is studied by combined in situ XPS/XAS, SEM and DFT. Formation is mediated by structural defects and oxygen vacancies at high temperatures instigating H 2 O dissociation and metastable OH chemisorption.

C 4 F 7 N and C 5 F 10 O are the most promising SF 6 alternatives as eco-friendly insulating gaseous mediums in electrical engineering.

This manuscript provides an overview of the current state of the art in terms of the molecular modelling of the thermophysical properties of fluids. It is intended to manage the expectations and serve as guidance to practising physical chemists, chemical physicists and engineers in terms of the scope and accuracy of the more commonly available intermolecular potentials along with the peculiarities of the software and methods employed in molecular simulations while providing insights on the gaps and opportunities available in this field. The discussion is focused around case studies which showcase both the precision and the limitations of frequently used workflows.

), and electrochemical storage (batteries and supercapacitors) applications are described. However, although MOFs are efficient materials with versatile uses, they still have many challenges, limiting their practical applications. Therefore, finally, we highlight the challenges associated with MOFs and show the way forward in overcoming them for the development of these highly porous materials with large-scale practical utility.

A novel method for calculating rate constants for internal conversion ( k IC ) that simultaneously accounts for Duschinsky, anharmonic and Herzberg–Teller effects has been developed and implemented.

In this work, we investigated the effect of La-site cation deficiency and Sr-substitution on the thermoelectric properties of polycrystalline samples of the La 0.9− x Sr x CoO 3 ( x = 0, 0.03, 0.05) ceramic synthesized via a solid-state reaction.

ion in solution it is also one of the simpler rare earth ions, and the Nd(III) ion has characteristic optical properties that can be exploited as a handle in physicochemical studies. Here, we start with a critical review of the current concepts used to relate structure and electronic energy levels. We follow with our suggested approach of using the methodology from molecular photophysics to relate optical properties and structure, and conclude with selected literature examples.

-isopropylacrylamide) family and similar polymers. The key steps of membrane fabrication are discussed, namely the deposition into thin films, functionalization of pores, and the secondary crosslinking of pre-existing microgel particles into membranes. The latter may be free-standing and do not necessitate the presence of a porous support layer. The temperature-dependent swelling properties of polymers provide a means of controlling the size of pores, and thus size-sensitive gating. Throughout the review, we highlight "positive" (gates open) or "negative" (closed) gating effects with respect to increasing temperature. In the second part, the functionalization of porous organic or inorganic membranes of various origins by either microgel particles or linear polymer brushes is discussed. In this case, the key steps are the adsorption or grafting mechanisms. Finally, whenever provided by the authors, the suitability of smart gating membranes for specific applications is highlighted.

/spiro-OMeTAD/Ag, which achieves a power conversion efficiency of 14.08%, surpassing the conventional structure efficiency of 6.1%. It provides valuable guidance for the structure design of a lead-free double perovskite device and offers new insights into the development of optoelectronic devices for solar energy utilization.

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…

state) of two non-benzenoid non-alternant hydrocarbons, composed of odd-membered rings. The molecules considered here have identical chemical composition but different atomic configuration in space. The delicate interplay between structural and electronic factors that might induce inversion and its energy extension, only by a few meV, is systematically investigated here by state-of-the-art calculations. Qualitative and quantitative accurate predictions are obtained employing post-HF methods, thanks to the balanced and careful inclusion of electron correlation effects. The obtained results might guide and rationalize new searches for molecules violating Hund's rule, concomitantly demonstrating the importance of key contributions from the theoretical method of choice.

-1,2-diol are provided. The results of the challenge show promising predictive properties in both purely quantum mechanical approaches as well as regression and other machine learning strategies.

Perovskite oxides are widely used as excellent oxygen carriers for chemical looping partial oxidation and reforming of methane due to their unique ability to adapt to various A- and B-site cations, dopants, and oxygen/cation defects.

Traditional microwave absorbing materials (MAMs) have exposed more and more problems in multi-spectrum detection and a harsh service environment, which hinder their further application. Bionic materials and structures have attracted more and more attention from researchers in the field of stealth materials due to their excellent properties, such as high strength and high conductivity, along with easy access to scale adjustability and structural design. By introducing the concept of bionics into their structural design and material design, we can obtain highly efficient stealth materials with multiple properties. In addition, the concept of multispectral stealth is furthered by comparing the difference in the principle and methods of achievement between radar stealth and infrared stealth. This paper fundamentally summarizes the research status of bionic structure design ideas in stealth materials, analyzing the structure-activity relationship between the structural size effect and electromagnetic characteristics from low order to high order. Then, the design ideas and universal…

, thus enhancing the performance of supercapacitors. This review outlines the several schemes adopted to prepare diverse binary and ternary composites of PANI as the electrode material for flexible supercapacitors and the significant impact of composite formation on the flexibility and electrochemical performance of the fabricated pliable supercapacitors.

The search for materials for next-generation spintronic applications has witnessed exponentially increasing interest, mainly due to the explosive development of numerous two-dimensional (2D) materials discovered in the last decade. Among them, MXenes have emerged as promising candidates for many applications due to their unique and versatile tunability in structure and properties. In particular, their excellent combination of conductivity and highly charged surfaces leads to outstanding electrochemical properties that are significant in electronic applications. Moreover, the ease of modifying the atomic and electronic structures, and thus the functionalities of MXenes, further opens up the opportunity to realize MXenes-based spintronic device applications. The explosive development of MXenes, such as tuning the bandgap and enhancing their magnetic properties, could pave the way for the integration of MXenes in device configurations suitable for spintronics. In this article, we provide an overview of the potential applications of MXenes with a special focus on spintronic device…

Deep eutectic solvents (DESs) are considered "green" and "sustainable" alternatives to conventional organic solvents and ionic liquids (ILs) due to their characteristic properties and relatively low costs. DESs are considered IL analogs and have attracted consideration as benign media formulations for the synthesis of novel polymers because they satisfy the principle of sustainability. Over the past few years, the use of DESs has resulted in novel pathways for the synthesis of novel materials, biomaterials, functional materials, and ionic soft materials. Furthermore, DESs have been widely applied in the science, industrial, engineering, and technological fields. On the other hand, stimulus-responsive (smart) polymers have been widely utilized in intelligent devices owing to their virtues of good processibility, stimuli and environmental sensitivity, responsivity, and so on. With the introduction of a DES into the smart polymeric matrices, their potential characteristics, biocompatibility, and flexibility endow the corresponding DES-based polymeric materials with intriguing…

, a thermodynamically downhill alteration of the surface that must be independently ruled out before one can be fully confident in the apparent theory/vSFG agreement. Our study provides more insights into the ordering and structure of water monolayer at MgO(100) surface at ambient conditions and completes previous theoretical and experimental analysis performed at low temperature and ultra-high vacuum conditions.

-activated garnet-type phosphors. Nevertheless, the as-prepared NIR pc-LED device exhibits a NIR output of 16.52 mW with a NIR photoelectric conversion efficiency of 5.92% driven by 100 mA current, indicating the potential of this material for application in NIR pc-LED.

(A = Rb, Cs), whose efficiency can reach over 29% with a film thickness of 0.5 μm. Our study suggests that inorganic Au-based halide perovskites are potential alternatives for optoelectronic devices in solar cells.

tetrahedral sites and is random only within the octahedral and tetrahedral sublattices. The nanofibers are ferrimagnets with relatively low critical temperature more similar to cubic chromites and manganites than to ferrites. Replacing the magnetic cations Co or Ni with non-magnetic Zn lowers the critical temperature from 374 K (Cr,Mn,Fe,Co,Ni) to 233 and 105 K for (Cr,Mn,Fe,Ni,Zn) and (Cr,Mn,Fe,Co,Zn), respectively. The latter nanofibers additionally have a low temperature transition to a reentrant spin-glass-like state.

, the same order of magnitude as the CMD and experimental results but with a high computational accuracy. This work seeks to simulate the thermal transport properties of solid-liquid interfaces with DFT accuracy at large-system and long-time scales.

the Ag substrate in which charge transfer plays a pivotal role. To the best of our knowledge, this is the first investigation that has clarified the mechanism and advantage of semiconductor/metal (ZnO/Ag nanostructures) even over noble metals (Ag nanoparticles) in SERS applications. Moreover, the SERS behavior based on the ZnO/Ag substrate was also examined and the results indicated high sensitivity and good repeatability.

We systematically investigate the mechanical, dynamical, and piezoelectric properties of MA 2 Z 4 monolayers (M = Mo, W; A = Si, Ge and Z = N, P, As) based on first-principles calculations.

The ZnGeSe 2 monolayer exhibits excellent water-splitting photocatalyst performance due to high carrier separation efficiency, suitable band edges and high visible light absorption.

Metamaterials are a kind of artificial material with special properties, showing huge potential for applications in fields such as infrared measurement, solar cells, optical sensors, and optical stealth. A metamaterial perfect absorber (MPA) is designed based on a metamaterial, featuring strong absorption, small volume, light weight, ultra-bandwidth, tunability and other characteristics. This paper introduces the absorption mechanism of MPAs from microwave to optical wave band, and four directions of absorber design are elaborated. Equivalent impedance matching, plasma resonance and interference effect are the main absorption mechanisms of MPA. Multiband perfect absorption, ultra-wideband and ultra-narrowband perfect absorption, polarization and angle insensitive absorption, and dynamically controllable tunable absorption are the main design aspects. Among them, the proposal of a dynamically tunable absorber realizes the dynamic absorption. Finally, the problems and challenges of metamaterial perfect absorber design are discussed.

(ZFM1) thin film exhibits greatly enhanced gas sensing properties towards TMA, because of its high surface-to-volume ratio and rough surface with a small nanorod structure. The sensor's response to 10 ppm TMA was measured 13 weeks later for stability testing. The stability test results show that the coated ZFM1 film works well as a TMA gas sensor. This work shows that ZF thin films are effective in detecting TMA in the atmosphere.

Bio- or plant-based surfactants are a sustainable and renewable alternative to replace synthetic chemicals for environmental, drugs and food applications. However, these "green" surfactants have unique molecular structures, and their self-assembly in water might lead to complex morphologies and unexpected properties. The micellization of saponin molecules, such as glycyrrhizic acid (GA), differs significantly from those of conventional synthetic surfactants, yet these differences are often overlooked. Saponins self-assemble in complex hierarchical helical morphologies similar to bile salts, rather than the expected globular, ellipsoidal and wormlike micelles. Here, we review two potential routes for molecular self-assembly of GA, namely kinetics of crystallization and thermodynamic equilibrium, focusing on their structure as a function of concentration. Some uncertainty remains to define which route is followed by GA self-assembly, as well as the first type of aggregate formed at low concentrations, thus we review the state-of-the-art information about GA assembly. We compare the…

Ion concentrations of plasma activated water correlated well to changes in pH and conductivity with excellent agreement to theoretical calculations.

Machine learning was used to rationalize the molecular origin of the impact sensitivity of nitroaromatic explosives.

C-based MXenes upon tuning biaxial strain. They also give a guideline on what conditions are appropriate for practically implementing these MXenes as electrode materials in LIBs.

Rational design and development of efficient bifunctional catalysts for ORR and OER based on Mo 2 N materials provide a new idea for developing new renewable energy storage and conversion technologies.

Model validation of a well-known class of solid polymer electrolyte (SPE) is utilized to predict the ionic structure and ion dynamics of alternative alkali metal ions, leading to advancements in Na-, K-, and Cs-based SPEs for solid-state alkali metal batteries. A comprehensive study based on molecular dynamics (MD) is conducted to simulate ion coordination and the ion transport properties of poly(ethylene oxide) (PEO) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt across various LiTFSI concentrations. Through validation of the MD simulation results with experimental techniques, we gain a deeper understanding of the ionic structure and dynamics in the PEO/LiTFSI system. This computational approach is then extended to predict ion coordination and transport properties of alternative alkali metal ions. The ionic structure in PEO/LiTFSI is significantly influenced by the LiTFSI concentration, resulting in different lithium-ion transport mechanisms for highly concentrated or diluted systems. Substituting lithium with sodium, potassium, and cesium reveals a weaker cation-PEO…

materials, and the absorption is more than 99% across 3.64-6.96 THz, and it has excellent characteristics such as robustness. Ultra-narrowband perfect absorption has a quality factor greater than 2200 due mainly to the implementation of symmetrically protected BIC with a sensing sensitivity of 2.575 THz per RIU. Therefore, this research could be widely used in the fields of integrated optical circuits, optoelectronic sensing and perceptual modulation of energy, as well as providing additional design ideas for the design of terahertz multifunctional devices.

Vibrational circular dichroism (VCD) spectroscopy has become an important part of the (stereo-)chemists' toolbox as a reliable method for the determination of absolute configurations. Being the chiroptical version of infrared spectroscopy, it has also been recognized as being very sensitive to conformational changes and intermolecular interactions. This sensitivity originates from the fact that the VCD spectra of individual conformers are often more different than their IR spectra, so that changes in conformational distributions or band positions and intensities become more pronounced. What is an advantage for studies focussing on intermolecular interactions can, however, quickly turn into a major obstacle during AC determinations: solute-solvent interactions can have a strong influence on spectral signatures and they must be accurately treated when simulating VCD and IR spectra. In this perspective, we showcase selected examples which exhibit particularly pronounced solvent effects. It is demonstrated that it is typically sufficient to model solute-solvent interactions by placing…

dielectric spectroscopy. These results reinforce the idea that the SAP is a universal feature of liquid and glassy dynamics.

N/Blu-Pn system has the advantage of a small average voltage of approximately 0.24 V. Besides these properties, the proposed heterostructure is based on chemical elements that are widely available and technologically established and have low atomic mass, which are all advantages for Na-ion battery applications.

Catalyst activity affects the reaction rate, and an increasing number of studies have shown that strain can significantly increase the electrocatalytic activity. Catalysts such as alloys and core-shell structures can modulate their properties through strain effects. Reasonable simulation techniques can be used to predict and design the catalytic performance based on understanding the strain action mechanism. Therefore, the methodological flow of theoretical simulations is summarised in this review. The mechanism underlying the strain-adsorption-reaction relationship is discussed using density functional theory (DFT) calculations. An introduction to DFT is given first, followed by a quick rundown of the strain classification and application. Typical electrocatalytic reactions, namely, the hydrogen and oxygen evolution reactions and oxygen reduction reaction, are taken as examples. After briefly explaining these reactions, the relevant studies on simulating the strain to tune the catalyst performance are covered. The simulation methods are summarised and analysed to observe the…

ions lead to changes in the lattice parameters, porosity, and conduction behavior. These significant enhancements in co-substituted cobalt ferrites can be exploited for hydroelectric cell applications.

In recent decades, there are immense applications for bulk and few-layer magnetic insulators in biomedicine, data storage, and signal transfer. In these applications, the interaction between spin and lattice vibration has significant impacts on the device performance. In this article, we systematically review the fundamental physical aspects of magnon-phonon coupling in magnetic insulators. We first introduce the fundamental physics of magnons and magnon-phonon coupling in magnetic insulators and then discuss the influence of magnon-phonon coupling on the properties of magnons and phonons. Finally, a summary is presented, and we also discuss the possible open problems in this field. This article presents the advanced understanding of magnon-phonon coupling in magnetic insulators, which provides new opportunities for improving various possible applications.

In olivine phosphate cathode materials, the biaxial tensile strain perpendicular to the direction of Li + ion migration is the most favorable for Li + ion migration, and the b -axial strain has a greatest effect on the Li + ion migration barrier.

Recently, MA 2 Z 4 materials have received tremendous attention due to their amazing electronic, spintronic, and optoelectronic properties.

reduction. The results of the electronic properties revealed that the delicate matching of the projected band edges of the monolayers in the heterostructures is responsible for the high photocatalytic performance.

Bimetallic spinel and perovskite metal oxide materials are advanced electrode materials for supercapacitor (SC) applications because of their low-cost, distinct crystal structures, eco-friendly nature, and high conductivity. However, they suffer from the disadvantages of poor ion-diffusion kinetics and pulverization issues during cyclability tests. Along with a deeper understanding of redox chemistry, the role of oxygen vacancies (OVs) in electrode materials to support the reaction kinetics for excellence in SCs must be clarified. In this review, we highlight for the first time the importance of OVs and summarize various design strategies for the preparation of advanced bimetallic spinel oxides and perovskites with improved electrochemical performances for SC applications. With new insights, we envision that the SC research community would endeavor to utilize the benefits of OVs effectively for the development of high-performance SCs.

exhibit excellent catalytic activity with very low limiting potentials of -0.67 and -0.36 V, respectively, while simultaneously suppressing the HER. Thus, the current work provides important insights to advance the design of transition-metal free catalysts for electrochemical nitrogen fixation from an electronic structure point of view.

remedial therapy of various diseases and complications, capitalizing on their potential reactivity. Among the various influencers, herein, piezoelectric materials driven ROS generation activity is primarily considered. Intrinsic non-centrosymmetry of piezoelectric materials makes them suitable for distinct dipole formation in the presence of external mechanical stimuli. Such characteristics prompt the positioning of opposite charged carriers to execute associated redox transformations that effectively participate to generate ROS in the aqueous media of the cell cytoplasm, organelles and nucleus. The immense reactivity of piezoelectric material driven ROS is fostered to terminate cellular toxicity or curtail tumor cell growth, due to their higher specificity. This perspective considers the conjugated performance of piezoelectric materials and ultrasound which can remotely generate electrical charges that promote ROS production for therapeutic application. In particular, a substantial synopsis is provided for the remedial activity of numerous piezocatalytic materials in tumor cell…

A 2 NaIO 6 (A = Ca, Sr) double perovskites were investigated through first principles calculations and were found suitable for solar cells and thermoelectric power generators.