The 100 most-cited articles in Physical Chemistry Chemical Physics, 2021

The evaluation of molecular electrostatic potential (ESP) is a performance bottleneck for many computational chemical tasks like restrained ESP charge fitting or quantum mechanics/molecular mechanics simulations. In this paper, an efficient algorithm for the evaluation of ESP is proposed. It regroups the expression in terms of primitive Gaussian type orbitals (GTOs) with identical angular momentum types and nuclei centers. Each term is calculated using a computerized optimized code. This algorithm was integrated into the wavefunction analysis program Multiwfn and was tested on several large systems. In the cases of dopamine and remdesivir, the performance of this algorithm was comparable to or better than some popular state-of-the-art codes. For meta1-organic framework-5, where the number of GTOs and ESP points is 4840 and 259 262, respectively, our code could finish the evaluation in 1874 seconds on ordinary hardware. It also exhibits good parallelization scaling. The source code of this algorithm is freely available and can become a useful tool for computational chemists.

The expansion of lithium-ion batteries from consumer electronics to larger-scale transport and energy storage applications has made understanding the many mechanisms responsible for battery degradation increasingly important. The literature in this complex topic has grown considerably; this perspective aims to distil current knowledge into a succinct form, as a reference and a guide to understanding battery degradation. Unlike other reviews, this work emphasises the coupling between the different mechanisms and the different physical and chemical approaches used to trigger, identify and monitor various mechanisms, as well as the various computational models that attempt to simulate these interactions. Degradation is separated into three levels: the actual mechanisms themselves, the observable consequences at cell level called modes and the operational effects such as capacity or power fade. Five principal and thirteen secondary mechanisms were found that are generally considered to be the cause of degradation during normal operation, which all give rise to five observable modes. A…

Solar energy absorption is a very important field in photonics. The successful development of an efficient, wide-band solar absorber is an extremely powerful driver in this field. We propose an ultra-wideband (UWB) solar energy absorber composed of a Ti ring and SiO2-Si3N4-Ti thin films. In the range of 300-4000 nm, the wide band has an absorption efficiency of more than 90% and can reach 3683 nm, and it has four absorption peaks with a high absorptivity. Moreover, the weighted average absorption efficiency of the solar absorber under AM 1.5 is maintained above 97.03%, which indicates it has great potential for use in the field of solar energy absorption. Moreover, we proved that the polarization is insensitive by analyzing the absorption characteristics at arbitrary polarization angles. For both the transverse electric (TE) and transverse magnetic (TM) modes, the UWB absorption is maintained at more than 90% in the wide incidence angle range of 60°. The UWB solar energy absorber has great potential for use in a variety of applications, such as converting solar light and heat into…

for the four absorption modes when the refractive index varies in the range of 1 to 1.9. This high-performance absorber has a very good development prospect in the frontier fields of bio-chemical sensing and special environmental detection.

Molecular modelling of organic compounds using computational software has emerged as a powerful approach for theoretical determination of the corrosion inhibition potential of organic compounds. Some of the common techniques involved in the theoretical studies of corrosion inhibition potential and mechanisms include density functional theory (DFT), molecular dynamics (MD) and Monte Carlo (MC) simulations, and artificial neural network (ANN) and quantitative structure-activity relationship (QSAR) modeling. Using computational modelling, the chemical reactivity and corrosion inhibition activities of organic compounds can be explained. The modelling can be regarded as a time-saving and eco-friendly approach for screening organic compounds for corrosion inhibition potential before their wet laboratory synthesis would be carried out. Another advantage of computational modelling is that molecular sites responsible for interactions with metallic surfaces (active sites or adsorption sites) and the orientation of organic compounds can be easily predicted. Using different theoretical…

Two-dimensional (2D) materials have shown great potential for gas sensing applications due to their large specific surface areas and strong surface activities. In addition to the commonly reported chemiresistive-type gas sensors, field-effect transistor (FET)-type gas sensors have attracted increased attention due to their miniaturized size, low power consumption, and good compatibility with CMOS technology. In this review, we aim to discuss the recent developments in chemiresistive- and FET-type gas sensors based on 2D materials, including graphene, transition metal dichalcogenides, MXenes, black phosphorene, and other layered materials. Firstly, the device structure and the corresponding fabrication process of the two types of sensors are given, and then the advantages and disadvantages are also discussed. Secondly, the effects of intrinsic and extrinsic factors on the sensing performance of 2D material-based chemiresistive and FET-type gas sensors are also detailed. Subsequently, the current gas-sensing applications of 2D material-based chemiresistive- and FET-type gas sensors…

The tetrel bond (TB) recruits an element drawn from the C, Si, Ge, Sn, Pb family as electron acceptor in an interaction with a partner Lewis base. The underlying principles that explain this attractive interaction are described in terms of occupied and vacant orbitals, total electron density, and electrostatic potential. These principles facilitate a delineation of the factors that feed into a strong TB. The geometric deformation that occurs within the tetrel-bearing Lewis acid monomer is a particularly important issue, with both primary and secondary effects. As a first-row atom of low polarizability, C is a reluctant participant in TBs, but its preponderance in organic and biochemistry make it extremely important that its potential in this regard be thoroughly understood. The IR and NMR manifestations of tetrel bonding are explored as spectroscopy offers a bridge to experimental examination of this phenomenon. In addition to the most common σ-hole type TBs, discussion is provided of π-hole interactions which are a result of a common alternate covalent bonding pattern of tetrel…

A correct kinetic analysis of HOR/HER requires steady-state polarization curves and also account for the impact of H coverage and mass transport.

Biomass-derived carbonaceous materials have been deemed to be one of the up-and-coming electrode materials for high-performance energy storage systems due to their cost-neutral abundant resources, sustainable nature, easy synthesis methods, and environmentally benign features. In this work, various graphene-like porous carbon networks (GPCs) with three-dimensional (3D) hierarchically ordered "ion highways" have been synthesized by the carbonization/activation of orange-peel wastes for use as an electrode material in high-energy supercapacitors. The porous structures and surface morphologies of the GPCs were rationally fine-tuned as a function of the activation agent ratio. The prepared GPCs offered superior specific surface area in addition to a 3D porous structure with a fine-tuned pore size distribution. The electrochemical behaviors of all the GPCs were evaluated in 6.0 M KOH aqueous electrolyte via a three-electrode electrochemical setup. Owing to their synergistic characteristics, including superior specific surface area (1150 m2 g-1), large pore volume, and fine-tuned 3D…

Ionic liquids are extremely versatile and continue to find new applications in academia as well as industry. This versatility is rooted in the manifold of possible ion types, ion combinations, and ion variations. However, to fully exploit this versatility, it is imperative to understand how the properties of ionic liquids arise from their constituents. In this work, we discuss targeted modifications as a powerful tool to provide understanding and to enable design. A 'targeted modification' is a deliberate change in the structure of an ionic liquid. This includes chemical changes in an experiment as well as changes to the parameterisation in a computer simulation. In any case, such a change must be purposeful to isolate what is of interest, studying, as far as is possible, only one concept at a time. The concepts can then be used as design elements. However, it is often found that several design elements interact with each other - sometimes synergistically, and other times antagonistically. Targeted modifications are a systematic way of navigating these overlaps. We hope this paper…

Nanoarchitectonics approaches can produce functional materials from tiny units through combination of various processes including atom/molecular manipulation, chemical conversion, self-assembly/self-organization, microfabrication, and bio-inspired procedures. Existing fabrication approaches can be regarded as fitting into the same concept. In particular, the so-called layer-by-layer (LbL) assembly method has huge potential for preparing applicable materials with a great variety of assembling mechanisms. LbL assembly is a multistep process where different components can be organized in planned sequences while simple alignment options provide access to superstructures, for example helical structures, and anisotropies which are important aspects of nanoarchitectonics. In this article, newly-featured examples are extracted from the literature on LbL assembly discussing trends for composite functional materials according to (i) principles and techniques, (ii) composite materials, and (iii) applications. We present our opinion on the present trends, and the prospects of LbL assembly.…

Double-atom catalysts (DACs) have gained more and more attention to achieve efficient catalysts for the electrocatalytic nitrogen reduction reaction (NRR). It is expected that heteronuclear members could play an important role in the development of DACs, due to which the vast possible combinations of two different transition metal (TM) elements provide a large chemical composition space for the DAC design. Herein, to screen for efficient NRR DACs and, in particular, to further explore the synergetic effect as well as the TM combination pattern conductive to the NRR in the heteronuclear DACs, we have theoretically studied the NRR on TM dimer embedded N-doped porous graphene (TM = V, Cr, Mn, Fe, Co, Ni, and Cu), denoted as M1M2@NG, and both homonuclear and heteronuclear DACs have been considered. Our results indicate that most of the M1M2@NG systems exhibit comparable or better intrinsic NRR activity than the stepped Ru(0001) surface in terms of the calculated limiting potential. In particular, the heteronuclear DAC VCr@NG exhibiting metallic conductivity and high stability has an…

Amorphous metal nanoparticles (A-NPs) have aroused great interest in their structural disordering nature and combined downsizing strategies (e.g. nanoscaling), both of which are beneficial for highly strengthened properties compared to their crystalline counterparts. Conventional synthesis strategies easily induce product contamination and/or size limitations, which largely narrow their applications. In recent years, laser ablation in liquid (LAL) and laser fragmentation in liquid (LFL) as "green" and scalable colloid synthesis methodologies have attracted extensive enthusiasm in the production of ultrapure crystalline NPs, while they also show promising potential for the production of A-NPs. Yet, the amorphization in such methods still lacks sufficient rules to follow regarding the formation mechanism and criteria. To that end, this article reviews amorphous metal oxide and carbide NPs from LAL and LFL in terms of NP types, liquid selection, target elements, laser parameters, and possible formation mechanism, all of which play a significant role in the competitive relationship…

Routinely, cyclic voltammetry (CV) or electrochemical impedance spectroscopy (EIS) are used in electrochemistry to probe the current response of a specimen. For the interpretation of the response, constant phase elements (CPEs) are used in the frequency domain based impedance calculus to parameterize the double layer. In this study, the double layer responses to the two measurement techniques are compared by probing a model-type polished gold electrode under potential and amplitude variation. The equivalent circuit that describes the double layer includes a CPE and is parameterized by impedance data, while a computational impedance-based Fourier transform model (source code disclosed) is used to describe the CV response. With CV, the measured and modelled responses show good agreement at amplitudes below 0.2 V and within a certain scan rate window. At larger amplitudes, the ion arrangement in the double layer is actively changed by the measurement, leading to potential dependencies and deviations from the CPE behaviour. These varying contributions to the impedance measurements are…

and a highest quality factor (FOM) of 4.26 in the refractive index range of 1 to 1.8. The maximum adjustable range is 0.06 THz in the Fermi energy range of 60 to 140 meV. Because of its excellent characteristics, our absorber will have good development prospects in the fields of optical switching, biochemical imaging, and space detection.

Two views of the computed electrostatic potential on the 0.001 au surface of 2,4,6-trifluoro-1,3,5-triazine. Red is the most positive color range, while blue is the most negative.

Inspired by the recent successful growth of Ti2C and Ti3C2 monolayers, here, we investigate the structural, electronic, and mechanical properties of functionalized Ti2C and Ti3C2 monolayers by means of density functional theory calculations. The results reveal that monolayers of Ti2C and Ti3C2 are dynamically stable metals. Phonon band dispersion calculations demonstrate that two-surface functionalization of Ti2C and Ti3C2via chalcogenides (S, Se, and Te), halides (F, Cl, Br, and I), and oxygen atoms results in dynamically stable novel functionalized monolayer materials. Electronic band dispersions and density of states calculations reveal that all functionalized monolayer structures preserve the metallic nature of both Ti2C and Ti3C2 except Ti2C-O2, which possesses the behavior of an indirect semiconductor via full-surface oxygen passivation. In addition, it is shown that although halide passivated Ti3C2 structures are still metallic, there exist multiple Dirac-like cones around the Fermi energy level, which indicates that semi-metallic behavior can be obtained upon external…

Ammonia (NH3) is the main raw material for the organic chemical industry and a critical feedstock for the fertilizer industry with great significance for the global economy. The NH3 demand has gradually increased with modern society development. Moreover, the electrocatalytic nitrogen reduction reaction (NRR) is a promising NH3 synthesis technology. However, the design of efficient electrocatalysts for the NRR is still challenging. In this study, we systematically analyzed transition metal (TM) single-atoms (Ti, V, Cr, Mn, Zr, Nb, and Mo) anchored on graphyne (GY) as NRR catalysts using density functional theory calculations. The calculation results for the first and last hydrogenation steps (*NNH formation and *NH3 desorption, respectively) revealed that Mn@GY (with an end-on configuration) and V@GY (with a side-on configuration) were the most suitable catalytic substrates for the NRR. The free-energy profiles of the TM@GY catalysts indicated that Mn@GY was the best NRR electrocatalyst owing to its distal pathway with a minimum free-energy barrier of 0.36 eV. In addition, the…

Students who undertake practical electrochemistry experiments for the first time will come face to face with the potentiostat. To many this is simply a box containing electronics which enables a potential to be applied between a working and reference electrode, and a current to flow between the working and counter electrode, both of which are outputted to the experimentalist. Given the broad generality of electrochemistry across many disciplines it is these days very common for students entering the field to have a minimal background in electronics. This article serves as an introductory tutorial to those with no formalized training in this area. The reader is introduced to the operational amplifier, which is at the heart of the different potentiostatic electronic circuits and its role in enabling a potential to be applied and a current to be measured is explained. Voltage follower op-amp circuits are also highlighted, given their importance in measuring voltages accurately. We also discuss digital to analogue and analogue to digital conversion, the processes by which the…

Hot-injection synthesized CsSnCl 3 nanocrystals demonstrated promising morphology, crystallinity and photocatalytic ability. By employing experimental parameters, electronic band structure was calculated with greater accuracy using DFT simulations.

The theoretical description of dissociative chemisorption of isolated molecules on metal surfaces is discussed. Emphasis is put on methods that deliver chemical accuracy for the dissociative chemisorption probability S 0 , so that Δ ≤ 1 kcal mol −1 .

This perspective article provides a comprehensive but organized tutorial introduction of the kinetics related to photon upconversion (UC) by triplet-triplet annihilation (TTA) (TTA-UC). The field of TTA-UC is multi-disciplinary and rapidly growing with the involvement of researchers from diverse backgrounds. TTA-UC consists of a series of tangled photophysical processes, so a solid understanding of the kinetic features and consequences is important to develop and evaluate materials for TTA-UC. This tutorial starts with an introduction of the standard model of TTA-UC along with the assumptions used in the model. The essential concept of the spin statistics for TTA and how this concept is related to the singlet branching ratio, which directly affects the efficiency of UC, are then explained through step-by-step analyses. Using these foundations, solutions for the steady-state behaviors are derived, featuring the universal curve that describes the excitation intensity dependence of the UC quantum yield for any sample type. Various useful functions for analyzing experimental data are…

and the electric field, which may be beneficial for the prediction of the required EF without large volumes of calculations. Our results have not only provided novel clues for catalyst design, but they have also provided deep understanding into the mechanisms of bifunctional catalysts.

In this work, the authors have developed a reactive force field (ReaxFF) to investigate the effect of water molecules on the interfacial interactions with vacancy defective hexagonal boron nitride (h-BN) nanosheets by introducing parameters suitable for the B/N/O/H chemistry. Initially, molecular dynamics simulations were performed to validate the structural stability and hydrophobic nature of h-BN nanosheets. The water molecule dissociation mechanism in the vicinity of vacancy defective h-BN nanosheets was investigated, and it was shown that the terminal nitrogen and boron atoms bond with a hydrogen atom and hydroxyl group, respectively. Furthermore, it is predicted that the water molecules arrange themselves in layers when compressed in between two h-BN nanosheets, and the h-BN nanosheet fracture nucleates from the vacancy defect site. Simulations at elevated temperatures were carried out to explore the water molecule trajectory near the functionalized h-BN pores, and it was observed that the intermolecular hydrogen bonds lead to agglomeration of water molecules near these pores…

C 2 N/MoSi 2 N 4 is shown to be a perfect photocatalyst for splitting water to create hydrogen.

Lead halide perovskites have become a leading material in the field of emerging photovoltaics and optoelectronics. Significant progress has been achieved in improving the intrinsic properties and environmental stability of these materials. However, the stability of lead halide perovskites to ionising radiation has not been widely investigated. In this study, we investigated the radiolysis of lead halide perovskites with organic and inorganic cations under X-ray irradiation using synchrotron based hard X-ray photoelectron spectroscopy. We found that fully inorganic perovskites are significantly more stable than those containing organic cations. In general, the degradation occurs through two different, but not mutually exclusive, pathways/mechanisms. One pathway is induced by radiolysis of the lead halide cage into halide salts, halogen gas and metallic lead and appears to be catalysed by defects in the perovskite. The other pathway is induced by the radiolysis of the organic cation which leads to formation of organic degradation products and the collapse of the perovskite structure.…

Two-dimensional (2D) materials with a moderate bandgap and high carrier mobility are useful for applications in optoelectronics.

intermolecular H-bond content derived from different series of PVA/plasticizer films could be plotted into a master curve and exhibited good linearity, indicating that intermolecular H-bonds dominate the mechanical stretchability in PVA films. Our efforts contribute towards an in-depth understanding of performance optimization induced by H-bond manipulation from empirical, phenomenological aspects to intrinsic, numerical insights.

Polar solvents dissolve Li and Na salts at high concentrations and are used as electrolyte solutions for batteries. The solvents interact strongly with the alkali metal cations to form complexes in the solution. The activity (concentration) of the uncoordinated solvent decreases as the salt concentration is increased. At extremely high salt concentrations, all the solvent molecules are involved in the coordination of the ions and form the solvates of the salts. In this article, we review the structures, transport properties, and electrochemistry of Li/Na salt solvates. In molten solvates, the activity of the uncoordinated solvent is negligible; this is the main origin of their peculiar characteristics, such as high thermal stability, wide electrochemical window, and unique ion transport. In addition, the solvent activity greatly influences the electrochemical reactions in Li/Na batteries. We highlight the attractive features of molten solvates as promising electrolytes for next-generation batteries.

Very recently, the centimeter-scale MoSi2N4 monolayer was synthesized experimentally and exhibited a semiconducting nature with high mobility (Hong et al., Science, 2020, 369, 670-674). Here, we show that MoSi2N4 and its analogues, MoSi2P4 and MoSi2As4, are potential two-dimensional (2D) materials for valleytronics based on first-principles calculations. We demonstrate that the intrinsic inversion symmetry breaking and strong spin-orbital coupling lead to the remarkable spin-valley coupling in the inequivalent valleys at K and K' points, which result in not only the valley-contrasting transport properties, but also the spin and valley coupled optical selection rules. Moreover, the in-plane strain can tune the bandgaps and spin splitting or even induce an indirect-to-direct bandgap transition for promising application in the strain-tunable valleytronics. We find that the valley polarization can be generated by doping magnetic element. Our findings offer theoretical insight into the exotic physical properties of novel MoSi2N4-family materials beyond transition metal dichalcogenides.

The cis → trans photo-isomerisation of azobenzene, after excitation to the nπ* and ππ* states, is revisited theoretically using non-adiabatic dynamics simulations in order to reproduce and rationalize the experimentally measured quantum yields.

conical intersection(s), whose presence is favoured by the enhanced flexibility of the radical anions relative to their neutral counterparts. The origin of the discrepancy with the nanosecond lifetime of DCA˙-* reported previously is discussed. These very short lifetimes limit, but do not preclude, photochemical applications of the cyanoanthracene anions.

Proton transfer along the hydrogen bonds of DNA can lead to the creation of short-lived, but biologically relevant point mutations that can further lead to gene mutation and, potentially, cancer. In this work, the energy landscape of the canonical A-T and G-C base pairs (standard, amino-keto) to tautomeric A*-T* and G*-C* (non-standard, imino-enol) Watson-Crick DNA base pairs is modelled with density functional theory and machine-learning nudge-elastic band methods. We calculate the energy barriers and tunnelling rates of hydrogen transfer between and within each base monomer (A, T, G and C). We show that the role of tunnelling in A-T tautomerisation is statistically unlikely due to the presence of a small reverse reaction barrier. On the contrary, the thermal populations of the G*-C* point mutation could be non-trivial and propagate through the replisome. For the direct intramolecular transfer, the reaction is hindered by a substantial energy barrier. However, our calculations indicate that tautomeric bases in their monomeric form have remarkably long lifetimes.

density functional calculations. The calculated phonon spectrum, elastic stability conditions, and cohesive energy verified the stability of the studied SbXY monolayers. The mechanical properties reveal that all studied monolayers are stable and brittle. Based on PBE (PBE + SOC) functional calculations, the SbXY monolayers are semiconductors with indirect bandgaps. The calculated bandgaps using HSE (HSE + SOC) for SbSeBr, SbSeI, SbTeBr, and SbTeI monolayers are between 1.45 and 1.91 eV, which are appealing for applications in nanoelectronic devices. The signature of the Rashba effect appears in the SbXY monolayer. The SbXY monolayers are visible-light active. Hole doping can be an efficient way to increase the electricity production of SbXY monolayers from waste heat energy. This study suggests that SbXY (X = Se, Te; Y = Br, I) monolayers represent promising new electronic, optical, and energy conversion systems.

The conductive polymer-electrolyte interface plays an important role in many electrochemical devices. An unusual situation arises when a solvent-free ionic liquid (SF-IL) is used as the electrolyte because it behaves as a molten salt rather than an electrolyte solution. On the basis of Raman spectra, it was found that the presence of ion pairs of SF-IL in the vicinity of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) results in a decrease in the oxidation level of the polymer and an increase in the HOMO-LUMO gap. The process of polymer "dedoping" and the modification of the electronic structure of the polymer are illustrated by quantum chemical calculations.

Phenothiazine (PTZ) is one of the most extensively investigated S, N heterocyclic aromatic hydrocarbons due to its unique optical, electronic properties, flexibility of functionalization, low cost, and commercial availability. Hence, PTZ and its derivative materials have been attractive in various optoelectronic applications in the last few years. In this prospective, we have focused on the most significant characteristics of PTZ and highlighted how the structural modifications such as different electron donors or acceptors, length of the π-conjugated system or spacers, polar or non-polar chains, and other functional groups influence the optoelectronic properties. This prospective provides a recent account of the advances in phenothiazine derivative materials as an active layer(s) for optoelectronic (viz. dye sensitized solar cells (DSSCs), perovskite solar cells (PSCs), organic solar cells (OSCs), organic light-emitting diodes (OLEDs), organic field-effect transistor (OFETs), chemosensing, nonlinear optical materials (NLOs), and supramolecular self-assembly applications. Finally,…

]arenes, which have unique features like possessing hydrophobic cavities of different sizes, along with hydrophilic external surfaces, which are also amenable towards easy derivatizations, are versatile cavitands or host molecules to encapsulate diverse guest molecules to form stable host-guest complexes with many unique structures and properties. Interestingly, host-guest complexes possessing amphiphilic properties can easily lead to the formation of various advanced supramolecular assemblies, like pseudorotaxanes, rotaxanes, polyrotaxanes, supramolecular polymers, micelles, vesicles, supramolecular nanostructures, and so on. Moreover, these supramolecular assemblies, with varied morphologies and responsiveness towards external stimuli, have immense potential for applications in nanotechnology, materials science, biosensors, drug delivery, analytical chemistry and biomedical sciences. In this perspective, we present a stimulating overview, discussing simple host-guest systems to complex supramolecular assemblies in a systematic manner, aiming to encourage future researchers in this…

DFT-D based MD simulations on the interaction between amino acids and g-Mg 3 N 2 monolayer in aqueous solution are presented.

By analogy to heat and mass transfer film theory, a general approach is introduced for determining hyperpolarization transfer rates between dilute electron spins and a surrounding nuclear ensemble. These analyses provide new quantitative relationships for understanding, predicting, and optimizing the effectiveness of hyperpolarization protocols, such as Dynamic Nuclear Polarization (DNP) under magic-angle spinning conditions. An empirical DNP polarization-transfer coefficient is measured as a function of the bulk matrix 1H spin density and indicates the presence of two distinct kinetic regimes associated with different rate-limiting polarization transfer phenomena. Dimensional property relationships are derived and used to evaluate the competitive rates of spin polarization generation, propagation, and dissipation that govern hyperpolarization transfer between large coupled spin ensembles. The quantitative analyses agree closely with experimental measurements for the accumulation, propagation, and dissipation of hyperpolarization in solids and provide evidence for…

The computational characterization of inorganic-organic hybrid interfaces is arguably one of the technically most challenging applications of density functional theory. Due to the fundamentally different electronic properties of the inorganic and the organic components of a hybrid interface, the proper choice of the electronic structure method, of the algorithms to solve these methods, and of the parameters that enter these algorithms is highly non-trivial. In fact, computational choices that work well for one of the components often perform poorly for the other. As a consequence, default settings for one materials class are typically inadequate for the hybrid system, which makes calculations employing such settings inefficient and sometimes even prone to erroneous results. To address this issue, we discuss how to choose appropriate atomistic representations for the system under investigation, we highlight the role of the exchange-correlation functional and the van der Waals correction employed in the calculation and we provide tips and tricks how to efficiently converge the…

Heterogeneous catalysis plays a significant role in the modern chemical industry. Towards the rational design of novel catalysts, understanding reactions over surfaces is the most essential aspect. Typical industrial catalytic processes such as syngas conversion and methane utilisation can generate a large reaction network comprising thousands of intermediates and reaction pairs. This complexity not only arises from the permutation of transformations between species but also from the extra reaction channels offered by distinct surface sites. Despite the success in investigating surface reactions at the atomic scale, the huge computational expense of ab initio methods hinders the exploration of such complicated reaction networks. With the proliferation of catalysis studies, machine learning as an emerging tool can take advantage of the accumulated reaction data to emulate the output of ab initio methods towards swift reaction prediction. Here, we briefly summarise the conventional workflow of reaction prediction, including reaction network generation, ab initio thermodynamics and…

In this work, motivated by the fabrication of an AlSb monolayer, we have focused on the electronic, mechanical and optical properties of AlSb and InSb monolayers with double-layer honeycomb structures, employing the density functional theory approach. The phonon band structure and cohesive energy confirm the stability of the XSb (X = Al and In) monolayers. The mechanical properties reveal that the XSb monolayers have a brittle nature. Using the GGA + SOC (HSE + SOC) functionals, the bandgap of the AlSb monolayer is predicted to be direct, while InSb has a metallic character using both functionals. We find that XSb (X = Al, In) two-dimensional bodies can absorb ultraviolet light. The present findings suggest several applications of AlSb and InSb monolayers in novel optical and electronic usages.

, where the axes of the Raman tensor do not coincide with the crystallographic axes and all elements are non-zero. We show that the Raman tensor elements are, in general, given by complex numbers and that phase differences between tensor elements are needed to describe the experimental results. We discuss the dependence of the Raman tensors on the excitation laser energy and thickness of the sample within the framework of the quantum model for the Raman intensities. We show that the wavevector dependence of the electron-phonon interaction is essential for explaining the distinct Raman tensor for each phonon mode. Finally, we close with our concluding remarks and perspectives to be explored using angle-resolved polarized Raman spectroscopy in optically anisotropic 2D materials.

Electrochemical impedance spectroscopy (EIS) is a versatile tool to understand complex processes in batteries. This technique can investigate the effects of battery components like the electrode and electrolyte, electrochemical reactions, interfaces, and interphases forming in the electrochemical systems. The interpretation of the EIS data is typically made using models expressed in terms of the so-called electrical equivalent circuits (EECs) to fit the impedance spectra. Therefore, the EECs must unambiguously represent the electrochemistry of the system. EEC models with a physical significance are more relevant than the empirical ones with their inherent imperfect description of the ongoing processes. This review aims to present the readers with the importance of physical EEC modeling within the context of battery research. A general introduction to EIS and EEC models along with a brief description of the mathematical formalism is provided, followed by showcasing the importance of physical EEC models for EIS on selected examples from the research on traditional, aqueous, and newer…

Surface active per- and polyfluoroalkyl substances (PFAS) released in the environment generate great concern in the US and worldwide. The sequestration of PFAS amphiphiles from aqueous media can be limited by their strong tendency to form micelles that plug the pores in the adsorbent material, rendering most of the active surface inaccessible. A joint experimental and simulation approach has been used to investigate the structure of perfluorooctanoate ammonium (PFOA) micelles in aqueous solutions, focusing on the understanding of ethanol addition on PFOA micelle formation and structure. Structurally compact and slightly ellipsoidal in shape, PFOA micelles in pure water become more diffuse with increasing ethanol content, and break into smaller PFOA clusters in aqueous solutions with high ethanol concentration. A transition from a co-surfactant to a co-solvent behavior with the increase of ethanol concentration has been observed by both experiments and simulations, while the latter also provide insight on how to achieve co-solvent conditions with other additives. An improved…

The standard state enthalpy of formation and the enthalpy of sublimation are essential thermochemical parameters determining the performance and application prospects of energetic materials (EM). Direct experimental measurements of these properties are complicated by low volatility and high heat release in bomb calorimetry experiments. As a result, the uncertainties in the reported enthalpies of formation for a number of even well-known CHNO-containing compounds might amount up to tens kJ mol-1, while for some novel high-nitrogen molecules they reach even hundreds of kJ mol-1. The present study reports a facile approach to determining the solid-state formation enthalpies comprised of complementary high-level quantum chemical calculations of the gas-phase thermochemistry and advanced thermal analysis techniques yielding sublimation enthalpies. The thermogravimetric procedure for the measurement of sublimation enthalpy was modified by using low external pressures (down to 0.2 Pa). This allows for observing sublimation/vaporization instead of thermal decomposition of the compounds…

monolayer tunes the bandgap of the spin-down channel in the half-metal phase. By contrast, for FeTeS, the biaxial strain transforms the ferromagnetic metal into a half-metal. The electric field applied to the FeSeS monolayer in a parallel direction transforms the half-metal to a ferromagnetic metal by closing the gap in the spin-down channel.

= 78.5 μM) were observed for the twisted BODIPY, and thus the cellular studies demonstrate its potential as a novel potent heavy atom-free photodynamic therapy (PDT) agent.

the molecular orbital origin of the molecule. Under this premise we can better explore the richness of such bonding patterns. For that, we will study old, recent and new systems, trying to pinpoint some misinterpretations that are often associated with them. We will use as exemplars the triel bonds, a couple of metal complexes, a discussion on convergent σ-holes, and many cases of anti-electrostatic hole interactions.

To render the sodium ion battery (SIB) competitive among other technologies, the processes behind sodium storage in hard carbon anodes must be understood. For this purpose, electrochemical impedance spectroscopy (EIS) is usually undervalued, since fitting the spectra with equivalent circuit models requires an a priori knowledge about the system at hand. The analysis of the distribution of relaxation times (DRT) is an alternative, which refrains from fitting arbitrarily nested equivalent circuits. In this paper, the sodiation and desodiation of a hard carbon anode is studied by EIS at different states of charge (SOC). By reconstructing the DRT function, highly resolved information on the number and relative contribution of individual electrochemical processes is derived. During the sloping part of the sodiation curve, mass transport is found to be the most dominant source of resistance but rapidly diminishes when the plateau phase is reached. An equivalent circuit model qualitatively reproducing the experimental data of the sloping region was built upon the DRT results, which is…

O ice mixtures, has been performed. The corresponding infrared spectra were simulated with density functional theory. The main spectral features observed in the various solid samples are interpreted with the help of the theoretical results. Infrared band strengths are also provided for amorphous and crystalline urea. The infrared spectroscopic information given in this work is expected to be useful for the detection and quantification of urea in astrophysical ices.

Zinc-bromine batteries (ZBBs) receive wide attention in distributed energy storage because of the advantages of high theoretical energy density and low cost. However, their large-scale application is still confronted with some obstacles. Therefore, in-depth research and advancement on the structure, electrolyte, anode, cathode and membrane are of great significance and impendency. Herein, we review the past and present investigations on ZBBs, discuss the key problems and technical challenges, and propose perspectives for the future, with the focus on materials and chemistry. This perspective would provide valuable information on further development of ZBBs.

We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3PnA- (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A- and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.

Perovskite solar cells are the rising star of third-generation photovoltaic technology. With a power conversion efficiency of 25.5%, the record efficiency is close to the theoretical maximum efficiency of a single-junction solar cell. However, lead toxicity threatens commercialization efforts and market accessibility. In this context, Sn-based perovskites are a safe alternative. Nevertheless, the efficiency of Sn-based devices falls far behind the efficiency of Pb-based counterparts. This concise review sheds light on the challenges that the field faces toward making Sn-based perovskites the perovskite photovoltaic benchmark. We identified four key challenges: materials and solvents, film formation, Sn(II) oxidation, and energy band alignment. We illustrate every single challenge and highlight the most successful attempts to overcome them. Finally, we provide our opinion on the most promising trends of this field in the future.

ρ and a negative value of H(r) if the non-covalent bond is partially covalent in nature. The analysis of G(r) suggests that it dominates the H(r) of non-covalent bonds with greater than 50% contribution, whereas the contribution of G(r) varies between 35 and 50% in the case of bonds which are partially covalent in nature. The criterion based on topological parameters is likely to be very helpful to comprehend and ascertain the non-covalent bonds in the chemical as well as complex biological systems.

Ag-doped TaS 2 monolayers show an obvious change in work function and short recovery time for NO 2 , which indicates that TaS 2 -based nanomaterials might be a promising candidate for constructing high-performance NO 2 gas sensors.

The initial stages of the nitrate radical (NO3) initiated oxidation of isoprene, in particular the fate of the peroxy (RO2) and alkoxy (RO) radicals, are examined by an extensive set of quantum chemical and theoretical kinetic calculations. It is shown that the oxidation mechanism is highly complex, and bears similarities to its OH-initiated oxidation mechanism as studied intensively over the last decade. The nascent nitrated RO2 radicals can interconvert by successive O2 addition/elimination reactions, and potentially have access to a wide range of unimolecular reactions with rate coefficients as high as 35 s-1; the contribution of this chemistry could not be ascertained experimentally. The chemistry of the alkoxy radicals derived from these peroxy radicals is affected by the nitrate moiety, and can lead to the formation of nitrated epoxy peroxy radicals in competition with isomerisation and decomposition channels that terminate the organic radical chain by NO2 elimination. The theoretical predictions are implemented in the FZJ-NO3-isoprene mechanism for NO3-initiated atmospheric…

The strongly attractive noncovalent interactions of charged atoms or molecules with π-systems are important binding motifs in many chemical and biological systems. These so-called ion-π interactions play a major role in enzymes, molecular recognition, and for the structure of proteins. In this work, a molecular test set termed IONPI19 is compiled for inter- and intramolecular ion-π interactions, which is well balanced between anionic and cationic systems. The IONPI19 set includes interaction energies of significantly larger molecules (up to 133 atoms) than in other ion-π test sets and covers a broad range of binding motifs. Accurate (local) coupled cluster values are provided as reference. Overall, 19 density functional approximations, including seven (meta-)GGAs, eight hybrid functionals, and four double-hybrid functionals combined with three different London dispersion corrections, are benchmarked for interaction energies. DFT results are further compared to wave function based methods such as MP2 and dispersion corrected Hartree-Fock. Also, the performance of semiempirical QM…

The use of water as a component of deep eutectic systems (DES) has raised some questions regarding its influence on the nature of the mixture. Does it form a DES or an aqueous solution and what is the role of water? In this work, the nature of citric acid:l-arginine:water mixtures was explored through phase equilibria studies and spectroscopic analysis. In a first step, PC-SAFT was validated as a predictive tool to model the water influence on the solid liquid equilibria (SLE) of the DES reline using the individual-component approach. Hence, activity coefficients in the ternary systems citric acid:l-arginine:water and respective binary combinations were studied and compared using ePC-SAFT. It was observed that the water-free mixtures citric acid:l-arginine showed positive deviation from Raoult's law, while upon addition of water strong negative deviation from Raoult's law was found, yielding melting depressions around 100 K. Besides these strong interactions, pH was found to become acidic (pH = 3.5) upon water addition, which yields the formation of charged species ([H2Cit]- and…

It has recently been shown that cycl[3.3.3]azine and heptazine (1,3,4,6,7,9,9b-heptaazaphenalene) as well as related azaphenalenes exhibit inverted singlet and triplet states, that is, the energy of the lowest singlet excited state (S1) is below the energy of the lowest triplet excited state (T1). This feature is unique among all known aromatic chromophores and is of outstanding relevance for applications in photocatalysis and organic optoelectronics. Heptazine is the building block of the polymeric material graphitic carbon nitride which is an extensively explored photocatalyst in hydrogen evolution photocatalysis. Derivatives of heptazine have also been identified as efficient emitters in organic light emitting diodes (OLEDs). In both areas, the inverted singlet-triplet gap of heptazine is a highly beneficial feature. In photocatalysis, the absence of a long-lived triplet state eliminates the activation of atmospheric oxygen, which is favourable for long-term operational stability. In optoelectronics, singlet-triplet inversion implies the possibility of 100% fluorescence…

Sulfur-containing iron materials such as sulfidized nanoscale zerovalent iron (SNZVI) have shown outstanding water remediation performance in many recent studies, which is largely attributed to its high hydrophobicity compared to that of NZVI. However, the role of sulfur in the reactions, and the origin of the hydrophobicity of SNZVI, were still unclear. In this paper, for the first time, we conducted ab initio molecular dynamics simulation using an explicitly solvated model on both Fe and S-containing Fe surfaces, to explore the hydrophobicity of S-containing Fe materials. We found that the high hydrophobicity of these S-containing Fe surfaces originates from the hydrophobic nature of S: both doping S on top of the Fe surface and inserting S onto an Fe surface can significantly improve the surface hydrophobicity by increasing the distance between the water layer and the Fe surface. This exposes empty Fe sites which do not interact with water and in turn reduces hydrogen evolution. To compare with the theoretical analysis, we experimentally analyzed the hydrophobicity of both NZVI…

Brownian motion. The calculated diffusion coefficient also showed a strong dependence on the nanobubble size. However, this active mobility of small nanobubbles also triggered a mutable nanobubble shape over time. Nanobubbles were also found to coalesce when they were sufficiently close. A critical distance between two nanobubbles was thus identified to avoid coalescence. These results provide insight into the behavior of nanobubbles in solution and the mechanism of their unique stability while withstanding high inner pressures.

Intramolecular charge transfer (ICT) is an important factor in the nonlinear optical (NLO) properties of organic molecules. In order to study the effect of ICT on two-photon absorption (TPA) and excited-state absorption (ESA), three chalcone derivatives (1, 2 and 3) with different electron push-pull systems were designed and synthesized. The ICT performance of these chalcone derivatives depends on the electron push-pull systems and mainly includes ultrafast ICT in the femtosecond time domain and long-lived charge transfer state (CTS) in the picosecond time domain, which dominate the performance of molecular TPA and ESA respectively. Hole-electron analysis and femtosecond Z-scan experiment indicate that the TPA cross section of these chalcone derivatives can be effectively enhanced by introducing stronger ultra-fast ICT in the case of little difference in ground-state absorption and expanding the molecular π-conjugated structure. Transient absorption spectrum (TAS) experiments of these compounds in solvents of varying polarities were conducted to visualize the establishment of CTS.…

Searching for economical low-dimensional materials to construct the highly efficient type-II heterojunction photocatalysts for splitting water into hydrogen is very strategic. In this study, using the first-principles calculations, we construct a novel SiH/CeO2(111) type-II heterojunction with a very small lattice mismatch of less than 1%. Based on AIMD simulation and phonon dispersion calculations, the SiH/CeO2(111) heterojunction reveals sufficient stability, and is easy to synthesize. Due to the vdW interaction between SiH and CeO2(111) components, electron and hole accumulation regions form at the heterojunction interface, which is very conducive to the separation of photoexcited electron-hole pairs. Besides, the SiH/CeO2(111) heterojunction has good visible light response, and even a strong absorption peak of up to 8.7 × 105 cm-1 in the high-energy visible region. More importantly, the SiH/CeO2(111) heterojunction exhibits good OER and HER performance because its oxidation and reduction potentials well meet the requirements of water splitting. Consequently, SiH/CeO2(111) is a…

The AlnC5- (n = 1-5) clusters were detected in the gas-phase and were investigated via mass-selected anion photoelectron spectroscopy. The structures of AlnC5-/0 (n = 1-5) were explored by theoretical calculations. It is found that the structures of AlC5-/0 and Al2C5-/0 are linear while those of Al3C5-/0, Al4C5-/0, and Al5C5-/0 are two-dimensional. The most stable structures of AlC5-/0 and Al2C5-/0 are linear with the Al atoms attached to the ends of C5 chain. The most stable structures of Al3C5-/0 can be viewed as three Al atoms interacting with a nonlinear C5 chain. The most stable structure of Al4C5- anion is a planar structure composed of a C2 unit, a C3 unit, and two Al2 units, while that of the neutral Al4C5 cluster has four Al atoms connected to different positions of a distorted C5 chain. The global minimum structures of Al5C5-/0 are planar structures composed of an Al4C quadrilateral, two C2 groups, and an Al atom connected to two C2 groups. Planar tetracoordinate carbon (ptC) has been identified in the structures of both anionic and neutral Al5C5. It is worth mentioning…

clusters. The selected examples are discussed from the perspective of the atmospheric and interstellar chemistry, and several future directions are proposed.

. In particular, compared with the barrier of the pristine NCM in Li divacancy, the barrier of V-doped NCM reaches the lowest. In conclusion, V is the most favorable dopant for NCM811 to improve the electrochemical properties and achieve both high capacity and cycling stability.

To achieve single-ion conducting liquid electrolytes for the rapid charge and discharge of Li secondary batteries, improvement in the Li+ transference number of the electrolytes is integral. Few studies have established a feasible design for achieving Li+ transference numbers approaching unity in liquid electrolytes consisting of low-molecular-weight salts and solvents. Previously, we studied the effects of Li+-solvent interactions on the Li+ transference number in glyme- and sulfolane-based molten Li salt solvates and clarified the relationship between this transference number and correlated ion motions. In this study, to deepen our insight into the design principles of single-ion conducting liquid electrolytes, we focused on the effects of Li+-anion interactions on Li ion transport in glyme-Li salt equimolar mixtures with different counter anions. Interestingly, the equimolar triglyme (G3)-lithium trifluoroacetate (Li[TFA]) mixture ([Li(G3)][TFA]) demonstrated a high Li+ transference number, estimated via the potentiostatic polarization method (tPPLi = 0.90). Dynamic ion…

In this work, we investigate the microscopic mechanism of ion rejection phenomena during the freezing of aqueous NaCl solutions through molecular dynamics simulations. It is found that the hydration energy for the ion-water interaction is stronger than that between ions and ice, which is the fundamental reason giving rise to the phenomenon of ion rejection. The probability of ions being rejected by ice is determined by the competition between the energy barrier at the ice-water interface and the thermal effect. The ion rejection rate increases with increasing temperature. Furthermore, it is found that the rejection rate of Na+ is higher than that of Cl- because of the relatively large hydration energy difference between Na+-water and Na+-ice interactions. The role of temperature in the applications of ion rejection in freeze desalination is also discussed.

analysis, we identify that the mass transfer overpotential inside the porous electrode and the resistance of the ion exchange membrane are the two major factors limiting the efficiency and power density, pointing to directions for future improvements.

Lithium diffusion is a key factor in determining the charge/discharge rate of Li-ion batteries. Herein, we study the tracer diffusion coefficient (D*) of lithium ions in the c-axis oriented LiCoO2 thin film using secondary ion mass spectrometry (SIMS). We applied a step-isotope-exchange method to determine D* in the Li-extracted LixCoO2. The observed values of D* ranged from 2 × 10-12 to 3 × 10-17 cm2 s-1 depending on the compositions in the range of 0.4 < x < 1.0. Approaching the stoichiometric composition (x = 1.0), D* decreases steeply to the minimum, which can be explained by the vacancy diffusion mechanism. Electrochemically determined diffusion coefficients corrected by thermodynamic factors are found to be in good agreement with D* determined by our method, over a wide range of compositions. The c-axis diffusion was explained by the migration of Li+ ions from one layer to another through additional diffusion channels, such as antiphase boundaries and a pair of Li antisite and oxygen vacancies in cobalt oxide layers.

Recently, the introduction of novel deep eutectic solvents having a hydrophobic character with greener starting materials has motivated researchers to explore these water-immiscible solvents, owing to their new potential applications. In this regard, herein atomistic molecular dynamics simulations have been performed to understand the bulk phase morphology present in dl-menthol based hydrophobic deep eutectic solvents (HDESs) with organic acids of different chain lengths used as hydrogen bond donors. From the appearance of a prepeak in the simulated total X-ray scattering structure function (S(q)), we found an evidence of intermediate-range structural organization in these HDESs. We show that the prepeak originates from the self-segregation of dl-menthol and the polar hydroxyl groups of the acids, as witnessed from partitioning of the total S(q). Surprisingly, even for a very long tail containing HDES, the apolar-apolar component shows only nominal contribution to the prepeak. We show that the structure of these HDESs is dominated by a set of very strong intermolecular hydrogen…

Low Li + /Na + diffusion barrier, high theoretical-capacity and shallow averaged open-circuit-voltage make the VS 2 /graphene heterostructure a promising anode material for LIBs and NIBs.

with flexible and/or unsaturated tails) reduce the water/oil IFT more effectively than surfactants which yield highly ordered interfacial films. Our results shed light on some of the factors that control IFT and could have important practical implications in industrial applications such as the design of cosmetics, food products, and detergents.

AsP systems and ultrafast diffusivity with the low energy barriers of 0.17/0.15 eV and 0.08/0.07 eV of the P/As sides for Li and Na, respectively. Given these exceptional properties, the synthesis of a buckled b-AsP monolayer is desired to achieve a promising electrode material for Li- and Na-ion batteries.

Bismuth-containing borate glasses, xBi2O3-(1 - x)B2O3, were synthesized in the broad composition range 0.20 ≤ x ≤ 0.80 by melting in Pt crucibles and splat-quenching between two metal blocks. Infrared reflectance spectra, measured in the range 30-5000 cm-1, were transformed into absorption coefficient spectra and then deconvoluted into component bands to probe the glass structure as a function of composition. Integrated intensities of bands above 800 cm-1 were used in combination with mass and charge balance equations to quantify the short-range borate structure in terms of the molar fractions X4m, X4o, X3, X2, X1 and X0 for borate units BØ4-, BØ2O23-, BØ3, BØ2O-, BØO22- and BO33-, where Ø and O- denote bridging and non-bridging oxygen atoms. Borate tetrahedral units were found to be present in both the meta-borate, BØ4-, and ortho-borate, BØ2O23-, forms with BØ4- constituting the dominating tetrahedral species for 0.20 ≤ x ≤ 0.70. The BØ2O23- units prevail at higher Bi2O3 levels (x > 0.7), and coexist with their isomeric triangular borate species BO33- (BØ2O23- ⇌ BO33-). The…

data. Special attention is paid to methods of diabatization, high fidelity construction of multi-state coupled potential energy surfaces and property surfaces, as well as quantum mechanical characterization of nonadiabatic nuclear dynamics. To illustrate the tremendous progress made by these new developments, several examples are discussed, in which direct comparison with quantum state resolved measurements led to either confirmation of the observation or sometimes reinterpretation of the experimental data. The insights gained in these prototypical systems greatly advance our understanding of nonadiabatic dynamics in chemical systems.

Quantum and classical reaction rate constant calculations come at the cost of exploring potential energy surfaces. Due to the "curse of dimensionality", their evaluation quickly becomes unfeasible as the system size grows. Machine learning algorithms can accelerate the calculation of reaction rate constants by predicting them using low cost input features. In this perspective, we briefly introduce supervised machine learning algorithms in the context of reaction rate constant prediction. We discuss existing and recently created kinetic datasets and input feature representations as well as the use and design of machine learning algorithms to predict reaction rate constants or quantities required for their computation. Amongst these, we first describe the use of machine learning to predict activation, reaction, solvation and dissociation energies. We then look at the use of machine learning to predict reactive force field parameters, reaction rate constants as well as to help accelerate the search for minimum energy paths. Lastly, we provide an outlook on areas which have yet to be…

In this study, in situ electrochemical Raman spectroscopy was applied to clarify the charge storage mechanism in three types of anodes, synthetic graphite, reduced graphene oxide (rGO), and nitrogen-doped reduced graphene oxide (N-rGO). The Li+ intercalation phenomenon was measured in LiPF6 electrolyte solution using a modified coin cell setup. The synthetic graphite anode showed the splitting of the G peak at the potential E < 0.2 V vs. Li/Li+, corresponding to the formation of a graphite intercalation compound (GIC) and its second-order 2D peak was found to be red-shifted due to charge transfer and induced strain in the potential region of 0.5 to 0.15 V vs. Li/Li+. In the case of rGO, the lattice defects assisted in large and early intercalation of electrolyte ions, which is confirmed by the red-shift in the G peak (∼36 cm-1) and its early disappearance below 0.3 V vs. Li/Li+, respectively. Unlike rGO, nitrogen vacancies in N-rGO provide active sites for Li+ intercalation, resulting in enhanced charge transfer, displayed by the large red-shift in the G peak (∼55 cm-1) and…

Pure hydrogen production via water splitting is an ideal strategy for producing clean and sustainable energy. Two-dimensional (2D) cadmium chalcogenide single-layers with a tetragonal crystal structure, namely Tetra-CdX (X = S, Se, and Te) monolayers, are theoretically predicted by means of density functional theory (DFT). Their structural stability and electronic and optical properties are investigated. We find that Tetra-CdX single-layers are thermodynamically stable. Their stability decreases as we go down the 6A group in the periodic table, i.e., from X = S to Se, and Te which also means that the electronegativity decreases. All considered novel monolayers are indirect band gap semiconductors. Using the HSE06 functional the electronic band gaps of CdS, CdSe, and CdTe monolayers are predicted to be 3.10 eV, 2.97 eV, and 2.90 eV, respectively. The impact of mechanical strain on the physical properties was studied, which indicates that compressive strain increases the band gap and tensile strain decreases the band gap. The optical properties of the Tetra-CdX monolayers show the…

Ordered mesoporous metal oxides with a high specific surface area, tailored porosity and engineered interfaces are promising materials for electrochemical applications. In particular, the method of evaporation-induced self-assembly allows the formation of nanocrystalline films of controlled thickness on polar substrates. In general, mesoporous materials have the advantage of benefiting from a unique combination of structural, chemical and physical properties. This Perspective article addresses the structural characteristics and the electrical (charge-transport) properties of mesoporous metal oxides and how these affect their application in energy storage, catalysis and gas sensing.

Type V natural deep eutectic solvents based on monoterpenoids (cineole, carvone, menthol, and thymol) are studied using a combined experimental and molecular modeling approach. The reported physicochemical properties showed low viscous fluids whose properties were characterized as a function of temperature. The theoretical study combining quantum chemistry and classical molecular dynamics simulations provided a nanoscopic characterization of the fluids, particularly for the hydrogen bonding network and its relationship with the macroscopic properties. The considered fluids constitute a suitable type of solvents considering their properties, cost, origin, and sustainability in different technological applications and sow the possibility of developing type V NADES from different types of molecules, especially in the terpenoid family of compounds.

Recently, two-dimensional (2-D) materials with a Penta-atomic-configuration such as Penta-graphene have received considerable attention because of their potential applications in electronics, spintronics and ion batteries. Previously, Penta-graphene has been proposed as an excellent anode material for Li-/Na-ion batteries with a high theoretical capacity (1489 mA h g-1). Here, based on the first-principles calculations, we report that a new 2-D material namely Penta-B2C can become another excellent anode material with even higher theoretical capacity for Li-/Na-ion batteries than Penta-graphene. Our results demonstrate that Li/Na atoms can be stably adsorbed on Penta-B2C. Meanwhile, Penta-B2C shows metallic conductivity during the adsorption. Most strikingly, the theoretical capacities of Penta-B2C are as high as 1594 for Li and 2391 mA h g-1 for Na, which are superior to those of the most known 2-D anode materials. Especially, the Na theoretical capacity of Penta-B2C sets a new record among known 2-D anode materials. In addition, Penta-B2C possesses relatively low open-circuit…

Plasma technology, combined with activation on surfaces, is a novel way to convert CO 2 using green electricity.

We have investigated the crystal structure and the nature of the magnetic ground state of the polycrystalline compound Pr2FeCrO6 (PFCO) through X-ray diffraction (XRD), magnetization, and magnetocaloric effect studies. Analysis of the XRD pattern reveals that the PFCO compound exhibits a B-site disordered orthorhombic crystal structure. The random distribution of Fe3+ and Cr3+ magnetic sublattices at the B-sites of the crystallographic unit cell helps to generate several fascinating magnetic properties. The compound exhibits three distinct anomalies in both the temperature dependence of the magnetization and the magnetic entropy change (-ΔS) curves, namely, (i) a G-type canted antiferromagnetic (AFM) ordering of the transition metal ions (TN1), (ii) a progressive spin reorientation (SR) transition (TSR), and (iii) an AFM ordering of Pr3+ sublattices at very low temperature (TN2). Surprisingly, a novel "diamagnetism-like" behavior appears in the low-temperature region for low applied field values. Moreover, we have also constructed the thermal evolution of the magnetic crystal…

protofibrils mainly via hydrogen-bonding and hydrophobic interactions. For comparison, we also explore the effects of RSV/EGCG molecules on the aggregation inhibition and protofibril disruption of the Iowa mutant (D23N) Aβ. Our findings may pave the way for the design of more effective drug candidates as well as the utilization of cocktail therapy using RSV and EGCG for the treatment of AD.

In recent years, the problem of electromagnetic wave (EMW) pollution has attracted more and more attention with the development of science and technology. In order to solve this complex problem, the research and development of EMW-absorbing materials is crucial. The new absorbing materials should have the characteristics of light weight, high efficiency, wide bandwidth, environmental protection, oxidation resistance, and other characteristics. Traditional single-phase Ni materials exhibit remarkable ferromagnetic behavior and double-loss mechanisms (dielectric loss and magnetic loss), and are considered as efficient EMW absorbers. However, under the action of EMWs, especially in the GHz frequency band, Ni materials tend to produce an eddy current effect, which limits their application prospects. For Ni-based materials, there is much interest in modifying the composite materials by designing a hierarchical structure for their preparation. Traditional, single-phase, carbon-based materials have been widely used in related fields because of their light weight and good conductivity.…

In this work, a theoretical method, taking into account the anisotropy of the internal magnetic field (B[combining right harpoon above]int), is proposed to predict the rate of quantum tunneling of magnetization (QTM), i.e., τQTM-1, for Kramers single-ion magnets (SIMs). Direct comparison to both experimental and previous theoretical results of three typical Kramers SIMs indicates the necessity of the inclusion of the anisotropy of B[combining right harpoon above]int for accurate description of QTM. The predictions of the method here are consistent with the theory proposed by Prokof'ev and Stamp (PS). For Kramers SIMs of high magnetic axiality, the QTM rates, predicted by the method here, are almost linearly proportional to the results by the PS method. The dependence of τQTM-1 on various parameters is analyzed for model systems. The averaged magnitude of B[combining right harpoon above]int (Bave) and principal g value of the axial direction (gZ) are the parameters on which τQTM-1 is linearly dependent. The ones on which τQTM-1 is quadratically dependent are gXY, i.e., the principal…

Two-dimensional (2D) ferroelectric materials are promising for use in high-performance nanoelectronic devices due to the non-volatility, high storage density, low energy cost and short response time originating from their bistable and switchable polarization states. In this mini review, we first discuss the mechanism and operation principles of ferroelectric devices to facilitate understanding of these novel nanoelectronics and then summarize the latest research progress of electronic devices based on 2D ferroelectrics. Finally, the perspectives for future research and development directions in various fields are provided. We expect this will provide an overview regarding the application of 2D ferroelectrics in electronic appliances.

Cation-π interactions are essential for many chemical, biological, and material processes, and these processes usually involve an aqueous salt solution. However, there is still a lack of a full understanding of the hydrated cation-π interactions between the hydrated cations and the aromatic ring structures on the molecular level. Here, we report a molecular picture of hydrated cation-π interactions, by using the calculations of density functional theory (DFT). Specifically, the graphene sheet can distort the hydration shell of the hydrated K+ to interact with K+ directly, which is hereafter called water-cation-π interactions. In contrast, the hydration shell of the hydrated Li+ is quite stable and the graphene sheet interacts with Li+ indirectly, mediated by water molecules, which we hereafter call the cation-water-π interactions. The behavior of hydrated cations adsorbed on a graphene surface is mainly attributed to the competition between the cation-π interactions and hydration effects. These findings provide valuable details of the structures and the adsorption energy of hydrated…

Sum frequency generation (SFG) spectroscopy is a unique and powerful tool for investigating surfaces and interfaces at the molecular level. Phase-sensitive SFG (PS-SFG) is an upgraded technique that can overcome the inherent drawbacks of conventional SFG. Here we review several methods of PS-SFG developed and reported in 1990-2020. We introduce how and by which group each PS-SFG method was designed and built in terms of interferometer implementation for optical heterodyne detection, with one exception of a recent numerical method that does not rely on interferometry. We also discuss how PS-SFG solved some typical problems for aqueous interfaces that were once left open by conventional SFG. These problems and their solutions are good examples to demonstrate why PS-SFG is essential. In addition, we briefly note a few terminology issues related with PS-SFG to avoid confusion.

The high efficiency of organic-inorganic hybrid perovskites has attracted the attention of many scholars all over the world, the chemical formula of which is ABX3, where A is an organic cation, B is a metal cation, and X is a halogen ion. In addition, the micro-mechanism behind the efficient photoelectric conversion needs more in-depth exploration. Therefore, in this work, based on time-dependent density functional theory (TD-DFT), the electron transfer mechanism from the ground state to the first singlet excited state was systematically investigated by electron and hole analysis and an inter-fragment charge transfer amount method (IFCT). In this work, we optimized and analyzed 99 different perovskite cluster configurations, where A sites are CH3NH3+ (MA+), NH2CHNH2+ (FA+), CH3CH2NH3+ (EA+), NH2CHOH+ (JA+), NH3OH+ (BA+), N(CH3)4+ (DA+), CH3CH2CH2NH3+ (KB+), CH3CH2CH2CH2NH3+ (KC+), C3N2H5+ (RA+), CH(CH3)2+ (TA+), and CH3NH(CH3)2+ (UA+), B sites are Ge2+, Sn2+ and Pb2+, and X sites are Cl-, Br- and I-. According to the analysis of a series of perovskite clusters of the hole-electron…

is the difference of basicity. This solubility criterion has been validated by the solubility data of 19 polymers (11 acidic and 8 basic) in 11 ILs (7 acidic and 4 basic). These principles based on KAT parameters can be applied to other systems dominated by hydrogen bonding.

We report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV, on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes. The associated cross-over point from predominant (known) electronically inelastic to quasi-elastic scattering seems to arise at surprisingly large electron kinetic energies, of approximately 10-14 eV. Concomitantly, we present evidence for the onset of indirect, autoionization phenomena (occurring via superexcited states) within a few eV of the primary and secondary ionization thresholds. These…

COVID-19 has recently caused a global health crisis and an effective interventional therapy is urgently needed. Remdesivir is one effective inhibitor for SARS-CoV-2 viral RNA replication. It supersedes other NTP analogues because it not only terminates the polymerization activity of RNA-dependent RNA polymerase (RdRp), but also inhibits the proofreading activity of intrinsic exoribonuclease (ExoN). Even though the static structure of Remdesivir binding to RdRp has been solved and biochemical experiments have suggested it to be a "delayed chain terminator", the underlying molecular mechanisms is not fully understood. Here, we performed all-atom molecular dynamics (MD) simulations with an accumulated simulation time of 24 microseconds to elucidate the inhibitory mechanism of Remdesivir on nucleotide addition and proofreading. We found that when Remdesivir locates at an upstream site in RdRp, the 1'-cyano group experiences electrostatic interactions with a salt bridge (Asp865-Lys593), which subsequently halts translocation. Our findings can supplement the current understanding of the…

Raman spectroscopy has been established as a valuable tool to study and characterize two-dimensional (2D) systems, but it exhibits two drawbacks: a relatively weak signal response and a limited spatial resolution. Recently, advanced Raman spectroscopy techniques, such as coherent anti-Stokes spectroscopy (CARS), stimulated Raman scattering (SRS) and tip-enhanced Raman spectroscopy (TERS), have been shown to overcome these two limitations. In this article, we review how useful physical information can be retrieved from different 2D materials using these three advanced Raman spectroscopy and imaging techniques, discussing results on graphene, hexagonal boron-nitride, and transition metal di- and mono-chalcogenides, thus providing perspectives for future work in this early-stage field of research, including similar studies on unexplored 2D systems and open questions.

We report a comprehensive computational study of unsupervised machine learning for extraction of chemically relevant information in X-ray absorption near edge structure (XANES) and in valence-to-core X-ray emission spectra (VtC-XES) for classification of a broad ensemble of sulforganic molecules. By progressively decreasing the constraining assumptions of the unsupervised machine learning algorithm, moving from principal component analysis to a variational autoencoder to t-distributed stochastic neighbor embedding (t-SNE), we find improved sensitivity to steadily more refined chemical information. Surprisingly, even in merely two dimensions, t-SNE distinguishes not just oxidation state and general sulfur bonding environment but the aromaticity of the bonding radical group with 87% accuracy as well as identifying even finer details in electronic structure within aromatic or aliphatic sub-classes. We find that the chemical information in XANES and VtC-XES is very similar, although they exhibit an unexpected tendency to have different sensitivity within a given molecular class.

The valley degree of freedom of carriers in crystals is useful to process information and perform logic operations, and it is a key factor for valley application to realize valley polarization, which can be achieved by strain.

The current theoretical perception of enzymatic activity is highly reliant on the determination of the activation energy of the reactions, which is often calculated using computationally demanding quantum mechanical calculations. With the ever-increasing use of bioengineering techniques that produce too many variants of the same enzyme, a fast and accurate way to study the relative efficiency of enzymes is currently in high demand. Here, we propose the local electric field (LEF) of the enzyme along the reaction axis as a descriptor for the enzymatic activity using the example of chorismate mutase in its native form and several variants (R90A, R90G, and R90K/C88S). The study shows a direct correlation between the calculated enzymatic EF and the enzymatic activity for all the complexes. MD simulations of the Michaelis complex and the transition state analog (TSA) show a stabilizing force on the TSA due to the enzymatic EF. QM/MM and QM-only DFT calculations in the presence of an external electric field (EEF) oriented along the reaction axis show that the electric field can interact…

Electrophilic aromatic substitution (EAS) is one of the most widely researched transforms in synthetic organic chemistry. Numerous studies have been carried out to provide an understanding of the nature of its reactivity pattern. There is now a need for a concise and general, but detailed and up-to-date, overview. The basic principles behind EAS are essential to our understanding of what the mechanisms underlying EAS are. To date, textbook overviews of EAS have provided little information about the mechanistic pathways and chemical species involved. In this review, the aim is to gather and present the up-to-date information relating to reactivity in EAS, with the implication that some of the key concepts will be discussed in a scientifically concise manner. In addition, the information presented herein suggests certain new possibilities to advance EAS theory, with particular emphasis on the role of modern instrumental and theoretical techniques in EAS reactivity monitoring.