The 100 most-cited articles in Physical Chemistry Chemical Physics, 2017

We present the GMTKN55 benchmark database for general main group thermochemistry, kinetics and noncovalent interactions. Compared to its popular predecessor GMTKN30 [Goerigk and Grimme J. Chem. Theory Comput., 2011, 7, 291], it allows assessment across a larger variety of chemical problems-with 13 new benchmark sets being presented for the first time-and it also provides reference values of significantly higher quality for most sets. GMTKN55 comprises 1505 relative energies based on 2462 single-point calculations and it is accessible to the user community via a dedicated website. Herein, we demonstrate the importance of better reference values, and we re-emphasise the need for London-dispersion corrections in density functional theory (DFT) treatments of thermochemical problems, including Minnesota methods. We assessed 217 variations of dispersion-corrected and -uncorrected density functional approximations, and carried out a detailed analysis of 83 of them to identify robust and reliable approaches. Double-hybrid functionals are the most reliable approaches for thermochemistry and…

) is then derived that uniquely defines intermolecular interaction regions. An attractive feature of the IGM methodology is to provide a workflow that automatically generates data composed solely of intermolecular interactions for drawing the corresponding 3D isosurface representations.

Metal-oxide-semiconductor (MOS) based gas sensors have been considered a promising candidate for gas detection over the past few years. However, the sensing properties of MOS-based gas sensors also need to be further enhanced to satisfy the higher requirements for specific applications, such as medical diagnosis based on human breath, gas detection in harsh environments, etc. In these fields, excellent selectivity, low power consumption, a fast response/recovery rate, low humidity dependence and a low limit of detection concentration should be fulfilled simultaneously, which pose great challenges to the MOS-based gas sensors. Recently, in order to improve the sensing performances of MOS-based gas sensors, more and more researchers have carried out extensive research from theory to practice. For a similar purpose, on the basis of the whole fabrication process of gas sensors, this review gives a presentation of the important role of screening and the recent developments in high throughput screening. Subsequently, together with the sensing mechanism, the factors influencing the sensing…

A covalently-bonded atom typically has a region of lower electronic density, a "σ-hole," on the side of the atom opposite to the bond, along its extension. There is frequently a positive electrostatic potential associated with this region, through which the atom can interact attractively but noncovalently with negative sites. This positive potential reflects not only the lower electronic density of the σ-hole but also contributions from other portions of the molecule. These can significantly influence both the value and also the angular position of the positive potential, causing it to deviate from the extension of the covalent bond. We have surveyed these effects, and their consequences for the directionalities of subsequent noncovalent intermolecular interactions, for atoms of Groups IV-VII. The overall trends are that larger deviations of the positive potential result in less linear intermolecular interactions, while smaller deviations lead to more linear interactions. We find that the deviations of the positive potentials and the nonlinearities of the noncovalent interactions…

units) or -NH- groups. The electronic, chemical and optical functionalities are determined by the nature of the local to extended structures as well as the chemical composition of the materials. Because of their typically amorphous to nanocrystalline nature and variable composition, significant challenges remain to fully assess and calibrate the structure-functionality relationships among carbon nitride materials. It is also important to devise a useful and consistent approach to naming the different classes of carbon nitride compounds that accurately describes their chemical and structural characteristics related to their functional performance. Here we evaluate the current state of understanding to highlight key issues in these areas and point out new directions in their development as advanced technological materials.

Future lithium-ion batteries must use lithium metal anodes to fulfill the demands of high energy density applications with the potential to enable affordable electric cars with 350-mile range. However, dendrite growth during charging prevents the commercialization of this technology. It has been demonstrated that the presence of a compressive mechanical stress field around a dendritic protrusion prevents growth. Several techniques based on this concept, such as protective layers, externally applied pressure and solid electrolytes have been investigated by other researchers. Because of the low coulombic efficiencies associated with the stiff protective layers and high-pressure conditions, implementation of these techniques in commercial cells is complicated. Polymer-based solid electrolytes demonstrate better efficiency and capacity retention capabilities. However, dendrite growth is still possible in polymer electrolytes at higher current densities. The simulations described in this article provide guidance on the conditions under which dendrite growth is possible in polymer cells…

). When studied by microscopy and X-ray scattering experiments, and under applied electric fields, the nematic phases are practically identical. However, calorimetry experiments refute the possibility of an intervening smectic mesophase, and the transformation between the nematic phases was associated with a weak thermal event. Analysis of measured dielectric data, along with molecular properties obtained from DFT calculations, applying the Maier-Meier relationship allowed for the degree of antiparallel pairing of dipoles in both nematic phases to be quantified. Based on the results, we conclude that the onset of the lower temperature phase is driven by the formation of antiparallel molecular associations.

has a very low lattice thermal conductivity, potentially giving it superior performance to SnS as a candidate thermoelectric material.

The technological interest of oxygen reduction and evolution reactions, ORR and OER, for the clean use and storage of energy has resulted in the discovery of multiple catalysts; and the physical and catalytic properties of the most active compositions are only comprehensible with the consideration of magnetic interactions. Spin dependent potentials via exchange interactions, spin-orbit coupling or through magneto-electric effects catalyse the oxygen electrochemistry. The best catalysts show metal sites with localized spins and electron delocalization; a correlation exists between the rate constant for charge transfer reactions and spin-dependent electron mobility. Since during the OER and ORR the number of unpaired electrons is not conserved, magnetic potentials in optimum catalysts act as selective gates to enhance the transport of local spin currents. Overall magnetic potentials can reduce the bonding properties of the, donor or acceptor, orbitals in the catalyst, and electrons more easily transfer over the conduction band. The influence of spin dependent forces is generally…

In this study the recently developed electron density of delocalized bonds (EDDB) is used to define a new measure of aromaticity in molecular rings.

formation or removal of oxygenates, though some contribution around the equatorial belt, and in select regions, cannot be excluded.

Cellulose is the most abundant polymer and a very important renewable resource. Since cellulose cannot be shaped by melting, a major route for its use for novel materials, new chemical compounds and renewable energy must go via the solution state. Investigations during several decades have led to the identification of several solvents of notably different character. The mechanisms of dissolution in terms of intermolecular interactions have been discussed from early work but, even on fundamental aspects, conflicting and opposite views appear. In view of this, strategies for developing new solvent systems for various applications have remained obscure. There is for example a strong need for using forest products for higher value materials and for environmental and cost reasons to use water-based solvents. Several new water-based solvents have been developed recently but there is no consensus regarding the underlying mechanisms. Here we wish to address the most important mechanisms described in the literature and confront them with experimental observations. A broadened view is helpful…

Using density functional theory, we systematically investigate the lattice thermal conductivity and carrier mobility of monolayer SnX 2 (X = S, Se).

Perovskite solar cells (PSC) are shown to behave as coupled ionic-electronic conductors with strong evidence that the ionic environment moderates both the rate of electron-hole recombination and the band offsets in planar PSC. Numerous models have been presented to explain the behaviour of perovskite solar cells, but to date no single model has emerged that can explain both the frequency and time dependent response of the devices. Here we present a straightforward coupled ionic-electronic model that can be used to explain the large amplitude transient behaviour and the impedance response of PSC.

The terms tetrel bond, pnictogen bond and chalcogen bond were coined recently to describe non-covalent interactions involving group 14, 15 and 16 atoms, respectively, acting as the electrophilic site that seeks a nucleophilic region of another molecule, for example a non-bonding electron pair or π-electron pair of a Lewis base. Many complexes containing these non-covalent bonds were identified and characterised in isolation in the gas phase by rotational and vibrational spectroscopy long before they were given these names. In this article, the geometries so determined for selected examples of complexes of each type are rationalised in terms of the molecular electrostatic surface potentials of the component molecules. Examples of chalcogen-bonded complexes considered are based mainly on sulfur dioxide, with the region near the sulfur atom as the electrophilic site that interacts with n-electron and π-electron pairs for a range of simple Lewis base molecules. For tetrel bonds, the examples discussed involve the carbon atom of carbon dioxide as the electrophilic centre, while for…

A combined theoretical and experimental study of the electronic properties of reduced molybdenum oxides with stoichiometries ranging from MoO 3 to MoO 2 .

Blue phosphorene (BlueP) is a graphene-like phosphorus nanosheet which was synthesized very recently for the first time [Nano Lett., 2016, 16, 4903-4908]. The combination of electronic properties of two different two-dimensional materials in an ultrathin van der Waals (vdW) vertical heterostructure has been proved to be an effective approach to the design of novel electronic and optoelectronic devices. Therefore, we used density functional theory to investigate the structural and electronic properties of two BlueP-based heterostructures - BlueP/graphene (BlueP/G) and BlueP/graphene-like gallium nitride (BlueP/g-GaN). Our results showed that the semiconducting nature of BlueP and the Dirac cone of G are well preserved in the BlueP/G vdW heterostructure. Moreover, by applying a perpendicular electric field, it is possible to tune the position of the Dirac cone of G with respect to the band edge of BlueP, resulting in the ability to control the Schottky barrier height. For the BlueP/g-GaN vdW heterostructure, BlueP forms an interface with g-GaN with a type-II band alignment, which is a…

), a green food antioxidant additive, is used as the electrolyte for providing both a phosphorus source and an electrolysis environment. The obtained P-GQDs exhibit excellent scavenging activity of free radicals, such as hydroxyl radicals (˙OH) and 2,2-diphenyl-1-picrylhydrazyl (DPPH). Combined with Raman, FT-IR, and XPS spectral analyses, the reason for high phosphorus content and the mechanism of free radical scavenging of P-GQDs are investigated in our work.

Large-scale energy storage technologies are in high demand for effective utilization of intermittent electricity generations and efficient electric power transmission. The feasibility of lithium-ion batteries for large-scale energy storage is under debate due to the scarcity and uneven distribution of lithium resources in the Earth's crust. Therefore, there arises tremendous interest in pursuing alternative energy storage systems based on earth-abundant materials. Recently, non-aqueous potassium-ion batteries (KIBs) are emerging as a promising energy storage system due to the abundance of potassium and the encouraging battery performance. Here, the recent research progress in non-aqueous KIBs is summarized, including electrode materials, electrolytes, battery architectures and fundamental electrochemical processes. The challenges and future research opportunities are also briefly discussed.

The issue of hysteresis in perovskite solar cells has now been convincingly linked to the presence of mobile ions within the perovskite layer. Here we test the limits of the ionic theory by attempting to account for a number of exotic characterization results using a detailed numerical device model that incorporates ionic charge accumulation at the perovskite interfaces. Our experimental observations include a temporary enhancement in open-circuit voltage following prolonged periods of negative bias, dramatically S-shaped current-voltage sweeps, decreased current extraction following positive biasing or "inverted hysteresis", and non-monotonic transient behaviours in the dark and the light. Each one of these phenomena can be reproduced and ultimately explained by our models, providing further evidence for the ionic theory of hysteresis as well as valuable physical insight into the factors that coincide to bring these phenomena about. In particular we find that both interfacial recombination and carrier injection from the selective contacts are heavily affected by ionic accumulation,…

rises with increasing cycle number. With this approach, a differentiation between "simple" irreversible capacities and truly detrimental "active Li losses" is possible and, thus, Coulombic efficiency can be directly related to the remaining useable cell capacity for the first time. Overall, the exact determination of the remaining active lithium content of the cell is of great importance, because it allows a statement on whether the reduction in lithium content is crucial for capacity fading or whether the fading is related to other degradation mechanisms such as material or electrode failure.

Kamlet Taft solvatochromic parameters, namely the hydrogen-bond acidity, hydrogen-bond basicity and dipolarity/polarizability and E T N parameters of a wide range of DESs composed of cholinium chloride, dl -menthol and a quaternary ammonium salt ([N 4444 ]Cl), and corresponding ILs are here presented.

) in reline, a feature herein discussed for the first time. In reline, urea molecules form a wide range of hydrogen bonds, from soft contacts to stronger associations, the latter being responsible for the deviation from ideality. The chloride's interactions with choline are largely conserved at the hydroxyl end while becoming weaker at the cationic headgroup. The interplay of soft and strong interactions confers flexibility to the newly formed hydrogen-bond network and allows the ensemble to remain liquid at room temperature.

NCs were annealed in vacuum at various temperatures. It was found that the NCs exhibited significant thermal degradation of PL at thermal annealing temperatures above 320 K. The transmission electron microscopy, X-ray diffraction and PL spectroscopy demonstrated that the size of NCs almost kept constant at thermal annealing temperatures below 360 K while it significantly enlarged at higher thermal temperatures above 380 K. The PL intensities, peak energies and linewidths of the annealed NCs, as a function of temperature, are discussed in detail. The PL degradation of the NCs was related to the formation of nonradiative recombination centers due to the loss of ligands and growth of NCs under thermal annealing.

We examine grain boundaries (GBs) with respect to non-GB regions in high-quality perovskite films using fluorescence-lifetime imaging. We show that recombination happens in the non-GB regions and that GBs are not transparent to photogenerated carriers.

Organic cocrystals, formed by a combination of electron-rich donors and electron-poor acceptors, play an important role in tailoring the optoelectronic properties of molecular materials. Charge transfer interactions in cocrystals not only endow them with an ordered three-dimensional (3D) supramolecular network in different constituent units, but also render them ideal scaffolds to control the intermolecular interactions in multicomponent solids. In this perspective, we firstly introduce preparation methods, molecular packing modes and charge transfer in organic cocrystals. Then, we focus on the novel and promising optoelectronic properties of organic cocrystals based on charge transfer interactions. Finally, we briefly discuss the outlook for the future development of these multicomponent crystalline materials.

We developed and constructed a novel model that could make reliable predictions on the adsorption of methylene blue dye and Cd 2+ ions from an aqueous medium.

Identifying a suitable electrode material with desirable electrochemical properties remains a primary challenge for rechargeable Al-ion batteries.

Subnanometric transition-metal (TM) clusters have attracted great attention due to their unexpected physical and chemical properties, leastwise compared to their bulk counterparts.

Cu/Pd/Cu adatoms diffuse on a MoS 2 monolayer with higher energy barriers and lower mobilities than those of Ag/Au adatoms.

for the other composites. The enhanced EMI shielding in the PVDF/FeC composite is attributed to the increased interfaces of the nanoscale particles, which facilitate enhanced Maxwell-Wagner interfacial polarization. The homogenous dispersion of iron and iron-carbide phases in the carbon matrix of the FeC sample enhances the interfacial polarization and multiple internal scattering of the penetrated EM waves, which get synergistically attenuated by the Ohmic, magnetic and dielectric losses. Based on complex permittivity and permeability results we have calculated the Reflection Loss (RL) of the PVDF/FeC composite. The PVDF-FeC composite shows a RL peak of -40.5 dB for a 4.3 mm thick specimen positioned at 5 GHz frequency. The RL peak is explained using the quarter-wave cancellation model. Our work demonstrates that incorporating carbon globules containing nanoscale magnetic and conducting particles in a polymer matrix, provides an effective way to enhance EMI shielding via absorption of the EM wave in a lightweight thin composite coating.

and the work required of the H electron to fill the unoccupied electronic states of the TMDs. Based on such linear relationships, the various defects (B-, C-, N-, O-, F-, P-, Se-doping and S-vacancy) were used to activate the inert basal planes of the 2H-phase molybdenum disulfide, which can introduce impurity states in the lower energy level to effectively accommodate the H electron. Furthermore, HER activity can be further optimized with the increasing concentration of the defects. These findings provide a practicable map of the HER performances, as well as indicating an appropriate direction for optimizing HER activity.

It has been long recognized that the surface chemistry of silica, and in particular the type and relative amount of surface bound silanol groups, plays a critical role in many of the properties associated with the material, where a typical example is the discrepant adsorption behavior observed depending on the pretreatment history of the surface. However, in spite of its importance, the direct probing of specific surface silanol groups under water has been hampered by instrumental limitations. Here we make use of vibrational sum frequency spectroscopy (VSFS) to first, identify under water the OH stretch of isolated surface silanols, and second, explore its acid/base behavior and dependence on the surface pretreatment method. The properties of other types of silanol groups (i.e. hydrogen bonded/geminal) are also inferred from the data. The ability to directly probe these functional groups under water represents a crucial step to further improving our understanding of this widely used mineral oxide.

Machine-learning regression has been demonstrated to precisely emulate the potential energy and forces that are output from more expensive electronic-structure calculations. However, to predict new regions of the potential energy surface, an assessment must be made of the credibility of the predictions. In this perspective, we address the types of errors that might arise in atomistic machine learning, the unique aspects of atomistic simulations that make machine-learning challenging, and highlight how uncertainty analysis can be used to assess the validity of machine-learning predictions. We suggest this will allow researchers to more fully use machine learning for the routine acceleration of large, high-accuracy, or extended-time simulations. In our demonstrations, we use a bootstrap ensemble of neural network-based calculators, and show that the width of the ensemble can provide an estimate of the uncertainty when the width is comparable to that in the training data. Intriguingly, we also show that the uncertainty can be localized to specific atoms in the simulation, which may…

is anticipated to be of paramount significance to further engineer the composition and improve device performances.

) compounds. The probes include the local electron attachment energy [E(r)], the average local ionization energy [Ī(r)], and the electrostatic potential [V(r)] and are evaluated on isodensity surfaces located at distances corresponding to typical interaction distances. These probes have previously been successful in characterizing molecular interactions. Good correlations are found between Lewis acidity and maxima in V(r), appearing as a consequence of σ-holes, as well as minima in E(r), of the noble metal nanoparticles. Similarly are Lewis basic sites successfully described by surface minima in V(r) and Ī(r); the former are indicative of σ-lumps, i.e. regions of enhanced σ-density. The investigated probes are anticipated to function as reliable tools in nanoparticle reactivity and interaction characterization, and may act as suitable descriptors in large-scale screenings for materials of specific properties, e.g. in heterogeneous catalysis. Because of the similarity between the noble metal nanoparticle's interactions with Lewis bases and the concepts of halogen and hydrogen…

We report a systematic investigation on the role of excess PbI 2 content in CH 3 NH 3 PbI 3 perovskite film properties, solar cell parameters and device storage stability.

I, with X equal to F, Cl, Br, and I, the σ-hole trend is exactly opposite to the trend in binding energy with common electron pair donors. Using energy decomposition analysis (EDA) applied to a potential energy scan as well as the recent adiabatic EDA technique, we show that the observed trend is a result of charge transfer. Therefore a picture of the halogen bond that excludes charge transfer cannot be complete, and permanent and induced electrostatics do not always provide the dominant stabilizing contributions to halogen bonds. Overall, three universally attractive factors, polarization, dispersion and charge transfer, together with permanent electrostatics, which is usually attractive, drive halogen bonding, against Pauli repulsion.

A detailed look at CO 2 electroreduction on a polycrystalline gold surface and a mechanistic discussion on the formation of methanol.

states. This contributes to the small activation energies for molecules exhibiting a large optical gap, identifies limitations of the present design procedures and provides a basis from which to construct TADF molecules with simultaneous high radiative and rISC rates.

nanocrystals obtained at 160 °C exhibited excellent photodegradation of Rhodamine under ultraviolet light irradiation, which was found to be related to the surface energy and the types of clusters formed on the surface of the catalyst.

Although the bulk conductivity of lithium ion conducting Li 3x La 0.67−x TiO 3 electrolytes reaches the level of 10 −3 S cm −1 , the grain boundary conductivity is orders of magnitude lower; the origin of the low grain boundary conductivity should be thoroughly understood as a prerequisite to improve the overall conductivity.

The understanding of excimer formation in organic materials is of fundamental importance, since excimers profoundly influence their functional performance in applications such as light-harvesting, photovoltaics or organic electronics. We present a joint experimental and theoretical study of the ultrafast dynamics of excimer formation in the pyrene dimer in a supersonic jet, which is the archetype of an excimer forming system. We perform simulations of the nonadiabatic photodynamics in the frame of TDDFT that reveal two distinct excimer formation pathways in the gas-phase dimer. The first pathway involves local excited state relaxation close to the initial Franck-Condon geometry that is characterized by a strong excitation of the stacking coordinate exhibiting damped oscillations with a period of 350 fs that persist for several picoseconds. The second excimer forming pathway involves large amplitude oscillations along the parallel shift coordinate with a period of ≈900 fs that after intramolecular vibrational energy redistribution leads to the formation of a perfectly stacked dimer.…

Here we demonstrate that the solubility of GO, and the stability of as-formed solutions depend not just on the solute and solvent cohesion parameters, as commonly believed, but mostly on the chemical interactions at the GO/solvent interface.

Vanadium flow batteries (VFBs) have received increasing attention due to their attractive features for large-scale energy storage applications. However, the relatively high cost and severe polarization of VFB energy storage systems at high current densities restrict their utilization in practical industrial applications. Optimization of the performance of key VFB materials, including electrodes, electrolytes and membranes, can realize simultaneous minimization of polarization and capacity decay. The power density and energy density of VFBs are thus simultaneously enhanced. Moreover, relevant theoretical mechanisms and foundations based on virtual investigations of VFB models and simulations can guide these optimizations. The improved power density and energy density can reduce the cost of VFB energy storage systems, accelerating their successful industrialization. In this perspective, modification methods to optimize the performance of key VFB materials and investigations of models and simulations of VFBs will be discussed. Therefore, the available ideas and approaches will be…

The history and evolution of molecular threshold photoelectron spectroscopy and threshold photoelectron photoion coincidence spectroscopy (TPEPICO) over the last fifty years are reviewed. Emphasis is placed on instrumentation and the extraction of dynamical information about energy selected ion dissociation, not on the detailed spectroscopy of certain molecules. Three important advances have expanded greatly the power of the technique, and permitted its implementation on modern synchrotron radiation beamlines. The use of velocity focusing of threshold electrons onto an imaging detector in the 1990s simultaneously improved the sensitivity and electron energy resolution, and also facilitated the subtraction of hot electron background in both threshold electron spectroscopy and TPEPICO studies. The development of multi-start multi-stop collection detectors for both electrons and ions in the 2000s permitted the use of the full intensity of modern synchrotron radiation thereby greatly improving the signal-to-noise ratio. Finally, recent developments involving imaging electrons in a range…

Galvanostatic and potentiodynamic measurements reveal an oxidative stability of common LiPF6 salt/carbonate solvent based electrolytes > 5 V vs. Li/Li + .

Earth-abundant NiO/TiO 2 heterostructures lead to enhanced H 2 production by methanol photoreforming due to favorable band bending at the interface of the NiO/anatase TiO 2 p–n heterojunction.

occupancy in the lithium layer enhances the electrochemical performance of layered NMC materials and that this occurs through a "pillaring" effect. The results provide new insights into "cation mixing" as a new concept for material design utilization of layered cathodes for lithium-ion batteries, thereby promoting their further application in lithium-ion batteries with new functions and properties.

Size dependence of exciton activation energy, electron–phonon coupling strength, and thermal expansion of the bandgap of CsPbBr 3 QDs were studied.

Chemical modification of silver nanoparticles (AgNPs) with a stabilizing agent, such as poly(vinyl alcohol) (PVA), plays an important role in shape-controlled seeded-growth and colloidal stability. However, theoretical aspects of the stabilizing mechanism of PVA are still poorly understood. To gain a better understanding of the role of PVA in water protecting effects for silver nanoparticles, we developed an atomistic model of a AgNP grafted with single-chain PVA of various lengths. Our model, designed for classical molecular dynamics (MD) simulations, approximates the AgNP as a quasi-spherical silver nanocrystal with 3.9 nm diameter and uses a united-atom representation for PVA with its polymer chain length varying from 220 up to 1540 repeating units. We found that PVA adsorbs onto the AgNP surface through multiple non-covalent interactions, among which non-covalent bonding of the hydroxyl groups plays a key role. The analysis of adsorption isotherms by using the Hill, Scatchard, and McGhee & von Hippel models exhibits evidence for positive binding cooperativity with the…

Single transition metal atoms supported by porpyrin-like graphene exhibit high catalytic activity for the electroreduction of CO 2 .

We have recently developed a novel computational methodology (termed RSF for Real-Space Fluctuations) to quantify the bending rigidity and tilt modulus of lipid membranes from real-space analysis of fluctuations in the tilt and splay degrees of freedom as sampled in molecular dynamics (MD) simulations. In this article, we present a comprehensive study that combines results from the application of the RSF method to a wide range of lipid bilayer systems that encompass membranes of different fluidities and sizes, including lipids with saturated and unsaturated lipid tails, single and multi-component lipid systems, as well as non-standard lipids such as the four-tailed cardiolipin. By comparing the material properties calculated with the RSF method to those obtained from experimental data and from other computational methodologies, we rigorously demonstrate the validity of our approach and show its robustness. This should allow for future applications of even more complex lipidic assemblies, whose material properties are not tractable by other computational techniques. In addition, we…

Triplet-triplet annihilation photon upconversion (TTA-UC) can, through a number of energy transfer processes, efficiently combine two low frequency photons into one photon of higher frequency. TTA-UC systems consist of one absorbing species (the sensitizer) and one emitting species (the annihilator). Herein, we show that the structurally similar annihilators, 9,10-diphenylanthracene (DPA, 1), 9-(4-phenylethynyl)-10-phenylanthracene (2) and 9,10-bis(phenylethynyl)anthracene (BPEA, 3) have very different upconversion efficiencies, 15.2 ± 2.8%, 15.9 ± 1.3% and 1.6 ± 0.8%, respectively (of a maximum of 50%). We show that these results can be understood in terms of a loss channel, previously unaccounted for, originating from the difference between the BPEA singlet and triplet surface shapes. The difference between the two surfaces results in a fraction of the triplet state population having geometries not energetically capable of forming the first singlet excited state. This is supported by TD-DFT calculations of the annihilator excited state surfaces as a function of phenyl group…

reduction and hydrogen evolution, our results represent an essential step towards a better understanding of how cation effects control the product distribution.

An overview of performance of state-of-the-art thermodynamic model COSMO-RS in capturing various effects of structure on interactions in ionic liquid binary systems, expressed in terms of limiting activity coefficients of molecular solutes, is presented.

fatty acids can be used to better predict the health and climate impact of particles with significant concentrations of medium-chain fatty acids.

max) and extended the temperature sensitivity range from 100 K to 850 K. The size of the nanophosphors had negligible impact on the performance of the studied materials.

Deep eutectic solvents (DES) have recently been postulated as possible environments where protein structure may be preserved in the absence of water. Here we present our results towards understanding protein conformation in choline chloride-based DES and mixtures with water. Lysozyme and bovine serum albumin have been investigated by means of circular dichroism and small-angle neutron scattering.

Plasma-assisted catalysis populates vibrationally excited CH 4 interacting with catalyst, leading to small energy barriers and enhanced rates to activate CH 4 .

The adsorption of Au n ( n = 1–4) clusters on perfect and defective MoS 2 monolayers is studied using density functional theory.

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model to aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible…

Microviscosity is a key parameter controlling the rate of diffusion and reactions on the microscale. One of the most convenient tools for measuring microviscosity is by fluorescent viscosity sensors termed 'molecular rotors'. BODIPY-based molecular rotors in particular proved extremely useful in combination with fluorescence lifetime imaging microscopy, for providing quantitative viscosity maps of living cells as well as measuring dynamic changes in viscosity over time. In this work, we investigate several new BODIPY-based molecular rotors with the aim of improving on the current viscosity sensing capabilities and understanding how the structure of the fluorophore is related to its function. We demonstrate that due to subtle structural changes, BODIPY-based molecular rotors may become sensitive to temperature and polarity of their environment, as well as to viscosity, and provide a photophysical model explaining the nature of this sensitivity. Our data suggests that a thorough understanding of the photophysics of any new molecular rotor, in environments of different viscosity,…

Carbon vacancies that are usually considered as defects substantially endow MXenes with improved flexibility and enhanced electronic conductivity.

In this article, composites consisting of porous Ni cores coated with boehmite/nickel aluminum oxide nanoflakes were successfully prepared by a versatile method. The crystal constituents and shapes of the boehmite/nickel aluminum oxide nanoflakes were strongly influenced by reaction temperature, and their microwave absorption properties were investigated in terms of complex permittivity and permeability. The results reveal that the composites comprising porous Ni cores coated with boehmite/nickel aluminum oxide synthesized at 180 °C present superior absorption properties. The optimal reflection loss is -44.3 dB (>99.99% attenuation) at 14.4 GHz, and the effective absorption (below -10 dB) bandwidth can be monitored in the frequency range of 5.8-18.0 GHz for an absorber with thickness in the range of 1.5-3.5 mm. The high dissipation capability, good impedance match and multiple reflection of the porous flaky structure are responsible for the improvement in microwave absorption. Moreover, a new absorption mechanism was proposed for the porous structure. In this mechanism, the porous…

Microsecond molecular dynamics simulations were performed to provide molecular insights into the nucleation of CO 2 hydrate.

ion, all functionals except M11-L correctly predict the ground spin state to be quintet. However, quantitatively, most of the functionals are not close to the experimentally determined spin-state splitting energies. For FeO all functionals predict quintet to be the ground spin state. For the 14 iron complexes, the hybrid functionals B3LYP, MPW1B95 and MN15 correctly predict the ground spin state of 13 out of 14 complexes and PW6B95 gets all the 14 complexes right. The local functionals, OPBE, OLYP and M06-L, predict the correct ground spin state for 12 out of 14 complexes. Two of the tested functionals are not recommended to be used for this type of study, in particular M08-SO and M11-L, because M08-SO systematically overstabilizes the high spin state, and M11-L systematically overstabilizes the low spin state.

To date, there have been only a few studies focusing on the assignment of X-ray diffraction (XRD) patterns in graphitic carbon nitrides (g-C 3 N 4 ) and contradictory determination for a broad peak around 12°–14° has been perplexing.

that play the crucial role in the degradation of dyes. As a result, the noble-metal free photocatalyst degrades nearly 100% of rhodamine B (RhB) within 80 min and methylene blue (MB) in 40 min under visible light. The photocatalytic activity is 10 times higher than that of the pure flower-like ZnO and two times higher than that of the SnS material. Moreover, the photocatalyst is easily separated and reused at least four times without obvious change in efficiency and properties. This work provides an effective strategy for the synthesis of 3D porous p-n heterojunction semiconductor-based photocatalysts with low cost and low toxicity, which present promising applications in the field of solar energy storage and conversion.

photocatalyst was magnetically separable and exhibited stable catalytic activity, which is beneficial to its practical application.

There are several possible pathways in the macrocycle of large porphyrinoids and, among aromaticity indices, only AV min is capable of recognizing the most aromatic one.

, respectively. The 5% Ni-doped sample showed an excellent cyclic stability and maintained 94% of its maximum specific capacitance after 1000 cycles.

along the x and y directions, respectively, both of which are higher than that in graphene. For borophane, despite its superhigh Fermi velocity, the carrier mobility is lower than that in 8B-Pmmn owing to its smaller elastic constant under shear strain.

For various interactions electron charge shifts try to protect the former doublet or octet electronic structure of the Lewis acid centre.

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when…

Surface-specific vibrational sum-frequency generation spectroscopy (V-SFG) is frequently used to obtain information about the molecular structure at charged interfaces. Here, we provide experimental evidence that not only screening of surface charges but also interference limits the extent to which V-SFG probes interfacial water at sub-mM salt concentrations. As a consequence, V-SFG yields information about the ∼single monolayer interfacial region not only at very high ionic strength, where the surface charge is effectively screened, but also for pure water due to the particularly large screening length at this low ionic strength. At these low ionic strengths, the large screening lengths cause destructive interference between contributions in the surface region. A recently proposed theoretical framework near-quantitatively describes our experimental findings by considering only interference and screening. However, a comparison between NaCl and LiCl reveals ion specific effects in the screening efficiency of different electrolytes. Independent of electrolyte, the hydrogen bonding…

Graphene supported single atoms show improved reactivity towards electrochemical CO 2 reduction with the best candidates identified for producing CH 4 by computational screening.

intermediate, is identified experimentally using in situ probing of the surface potentials of the metals, under conditions of continuous control of the humidity and the gas exposure. The derived activity trends give clear indication that the electrocatalytic activity for hydrogen evolution reaction is a consequence of an interplay between metal-hydrogen and metal-water interactions. In other words it is shown that the M-H bond formation strongly depends on the nature of the metal-water interaction. In fact, it seems that water dipoles at the metal/electrolyte interface play a critical role for electron and proton transfer in the double layer.

Half-Heusler (HH) compounds are important high temperature thermoelectric (TE) materials and have gained ever-increasing popularity. In recent years, p-type FeNbSb-based heavy-band HH compounds have attracted considerable attention with the record-high zT value of 1.5. Here, we use first-principles based methods to predict a very high zT value of 1.54 at 1200 K in p-type RuTaSb alloys. The high band degeneracy and low band effective mass contribute to a high power factor. Although the electrical thermal conductivity is high due to the high carrier mobility and hence electrical conductivity, the total thermal conductivity is moderate because of the low lattice thermal conductivity. The predicted high zT demonstrates that the p-type RuTaSb HH alloys are promising as TE materials for high temperature power generation.

TFSI are characterized by UV/Vis spectroscopy. Varying the cation and the solvent reveals their mutual interplay in stabilizing different polysulphide species. To our knowledge, this is the first time that chemically synthesized Mg polysulphides in solutions are studied. The results of this work provide essential knowledge for further development of the economically, ecologically, and also in terms of energy density and safety, attractive Mg/S batteries.

possesses the advantages of a small diffusion barrier (∼0.5 eV) and low average open-circuit voltages (∼0.4 V). Our results highlight a new class of promising anode materials, i.e. 2D phosphide, as potential rechargeable lithium batteries with ultrahigh-capacity, superior ionic conductivity, and low average open-circuit voltage.

Due to “CO-Promoted O 2 Activation”, the termolecular Eley–Rideal (TER) mechanism is the most relevant one for CO oxidation over the SAC, Ag 1 /BN.

Herein we report the observation of room-temperature phosphorescence from carbon dots (CDs) embedded in a silica gel matrix. The precursors used in the synthesis (malonic acid and ethylene diamine) were chosen to have the surface of the CDs rich in C[double bond, length as m-dash]O and C[double bond, length as m-dash]N functionalities. The CDs in an aqueous dispersion exhibit an intense blue fluorescence and upon incorporation into silica gel demonstrate a green after-glow, which is visible even to the naked eye. The phosphorescence measurements indicated that the life-time of phosphorescence emission is about 1.8 s, under 380 nm excitation, which is the highest magnitude reported for CDs in solid-state matrices. Moreover, the 1931 CIE color parameters corresponding to the phosphorescence emission are in the white gamut region of the chromaticity diagram.

(263-363 K) in the one-component, binary, and ternary adsorbate systems. The optimal configurations of vitrinite are similar to graphite/graphene, while ΔE is significantly lower than graphite/graphene. Simulation data are in good agreement with the experimental results.

. The highest efficiency (17.62%) is achieved via decoration with 7% GQDs, which is an 8.2% enhancement with respect to a pure perovskite based device. Various analyses including electrochemical impedance spectroscopy, time-resolved photoluminescence decay and open-circuit voltage decay measurements are employed in investigating the mechanism behind the improvement in device performance. The findings reveal two important roles played by GQDs in promoting the performance of perovskite solar cells - that GQDs are conducive to facilitating electron extraction and can effectively passivate the electron traps at the perovskite grain boundaries.

Mechanical degradation phenomena in layered oxide cathode materials during electrochemical cycling have limited their long-term usage because they deteriorate the structural stability and result in a poor capacity retention rate. Among them, intra-granular cracking inside primary particles progressively degrades the performance of the cathode but comprehensive understanding of its intrinsic origin is still lacking. In this study, the mechanical properties of the primary particle in a Ni-rich layered oxide cathode material (LiNi0.8Co0.1Mn0.1O2) are investigated under tensile and compressive deformation towards both in-plane and out-of-plane directions within the density functional theory framework. The Young's modulus and maximum strength values indicate that the pristine structure is more vulnerable to tensile deformation than compression. In addition, delithiation significantly deteriorates the mechanical properties regardless of the direction of deformation. In particular, a substantial degree of anisotropy is observed, indicating that the mechanical properties in the out-of-plane…

Good adsorption of Hg 2+ on molybdenum disulfide was observed; multilayer Hg 2+ was adsorbed on molybdenum disulfide; Hg–S complexation existed in the adsorption of Hg 2+ on molybdenum disulfide.

During laser synthesis of colloids, cavitation bubbles with lifetimes in the microsecond-scale form and shield the laser pulse leading to a decrease in nanoparticle output. A second type of productivity-limiting bubble that severely affects the productivity of the process is often neglected. With lifetimes from milliseconds to seconds, these persistent bubbles are systematically studied in this work by quantifying their composition, amount, size and dwell time in liquids with different viscosities and by relating the results to the nanoparticle productivities. It is found that during synthesis in water, water splitting occurs leading to persistent bubbles consisting of hydrogen and oxygen. In glycols, hydrogen and molecular carbon species containing microbubbles are formed. These persistent microbubbles shield up to 65% of the incoming laser beam depending on the liquid as well as the laser fluence and require attention by means of reducing their dwell time in the ablation zone and enhancing the nanoparticle output by liquid flow. The highest productivities and monodisperse quality…

A gas sensor based on a thiocyanate ion-doped organometal halide perovskite can sensitively and selectively detect acetone vapour and nitrogen dioxide with good repeatability and improved stability.

Vacancies in graphene present sites of altered chemical reactivity and open possibilities to tune graphene properties by defect engineering. The understanding of chemical reactivity of such defects is essential for successful implementation of carbon materials in advanced technologies. We report the results of a systematic DFT study of atomic adsorption on graphene with a single vacancy for the elements of rows 1-6 of the periodic table of elements (PTE), excluding lanthanides. The calculations have been performed using the PBE, long-range dispersion interaction-corrected PBE (PBE+D2 and PBE+D3) and non-local vdW-DF2 functionals. We find that most elements strongly bind to the vacancy, except for the elements of groups 11 and 12, and noble gases, for which the contribution of dispersion interaction to bonding is most significant. The strength of the interaction with the vacancy correlates with the cohesive energy of the elements in their stable phases: the higher the cohesive energy is, the stronger bonding to the vacancy can be expected. As most atoms can be trapped at the SV site…

/C as a cathode. The battery based on Al metal with a very thin oxide film showed high capacity and stable surface corrosion.

Graphene is emerging as a versatile material with a diverse field of applications. Synthesis techniques for graphene introduce several topological defects such as vacancies, dislocations and Stone-Thrower-Wales (STW) defects. Among them STW defects are generated without deleting any atom from the lattice position, but are introduced by rotating single C-C bonds. In this article, molecular dynamics based simulations have been performed to study the effect of STW defects on the fracture toughness of pristine graphene as well as graphene with crack edges passivated with hydrogen atoms. STW defects help in generating out of plane displacement in conjunction with redistribution of stress around the crack edges that can be used to improve the fracture toughness of brittle graphene. An overall improvement in the fracture toughness of pristine graphene as well as graphene containing hydrogen at the crack edges was predicted in this work.

χ (2) and χ (3) at charged interfaces in SFG spectroscopy are distinctively calculated using MD simulations.

result in a favorable catalytic efficiency and cycling stability. Nano-catalysts with this kind of morphology can also be applied to other metal hydrides to improve their kinetics performance and cycling stability.

Three essential experimental parameters in the ultrasonic emulsification process, namely sonication time, acoustic amplitude and processing volume, were individually investigated, theoretically and experimentally, and correlated to the emulsion droplet sizes produced. The results showed that with a decrease in droplet size, two kinetic regions can be separately correlated prior to reaching a steady state droplet size: a fast size reduction region and a steady state transition region. In the fast size reduction region, the power input and sonication time could be correlated to the volume-mean diameter by a power-law relationship, with separate power-law indices of -1.4 and -1.1, respectively. A proportional relationship was found between droplet size and processing volume. The effectiveness and energy efficiency of droplet size reduction was compared between ultrasound and high-pressure homogenisation (HPH) based on both the effective power delivered to the emulsion and the total electric power consumed. Sonication could produce emulsions across a broad range of sizes, while…

Machine learning techniques are being increasingly used as flexible non-linear fitting and prediction tools in the physical sciences. Fitting functions that exhibit multiple solutions as local minima can be analysed in terms of the corresponding machine learning landscape. Methods to explore and visualise molecular potential energy landscapes can be applied to these machine learning landscapes to gain new insight into the solution space involved in training and the nature of the corresponding predictions. In particular, we can define quantities analogous to molecular structure, thermodynamics, and kinetics, and relate these emergent properties to the structure of the underlying landscape. This Perspective aims to describe these analogies with examples from recent applications, and suggest avenues for new interdisciplinary research.

The effect of in-plane strain on monolayer InSe has been systematically investigated by using first-principles calculations. It is found that monolayer InSe exhibits superior mechanical flexibility, which can sustain a tensile strain up to 27% in the armchair direction. More importantly, a new phase with inversion symmetry denoted as phase-II is obtained when the tensile strain increases over 25% along the zigzag direction, which is predicted to be metallic and thermodynamically stable at room temperature. And the phase-II InSe could show an out-of-plane negative Poisson's ratio after the uniaxial tensile strain is larger than 5%. Moreover, both uniaxial and biaxial compressive strains can trigger the indirect-to-direct band gap transition in the pristine monolayer InSe and its band gap decreases monotonously with the applied tensile strain, which offers an effective method to tune the electronic properties of monolayer InSe for its promising application in electronics and optoelectronics.

is achieved at 193 K with the intensity ratio of anti-Stokes bands to the ZPL under 488 nm excitation by a Xenon lamp. This work presents a new method to realize optical thermometry at low temperature by controlling the intensity ratio of the anti-Stokes bands to the ZPL.

Protonation not only changes the primary interaction mode between α/β-furanCF 3 / p -PyCF 3 and NH 3 but also prominently enhances the strength of the Si/Ge⋯N tetrel bond.

Adsorption at charged interfaces plays an important role across all aspects of physical chemistry, from biological interactions within living organisms to chemical processes such as catalysis and separations. With recent advances in materials chemistry, there are a host of modified electrodes being investigated for electrosorption, especially in separations science. In this perspective, we provide an overview of functional interfaces being used for electrosorption, ranging from electrochemical separations such as deionization and selective product recovery to biological applications. We cover the various molecular mechanisms which can be used to enhance ion capacity, and in some cases, provide selectivity; as well as discuss the parasitic Faradaic reactions which often impair electrosorption performance. Finally, we point to the importance of electrochemical configurations, in particular the advantages of asymmetric cell design, and highlight the opportunities for selective electrosorption brought about by redox-mediated systems.