Showing papers in "Physical Chemistry Chemical Physics in 2021"
TL;DR: In this article, an efficient algorithm for the evaluation of molecular electrostatic potential (ESP) is proposed, which regroups the expression in terms of primitive Gaussian type orbitals (GTOs) with identical angular momentum types and nuclei centers.
Abstract: 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.
336 citations
TL;DR: In this article, the authors proposed an ultra-wideband (UWB) solar energy absorber composed of a Ti ring and SiO2-Si3N4-Ti thin films.
Abstract: 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 electricity for public use and reducing the side effects of coal-fired power generation. It can also be used in information detection and infrared thermal imaging owing to its UWB characteristics.
195 citations
TL;DR: In this article, the authors focus on the coupling between 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.
Abstract: 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 flowchart illustrates the different feedback loops that couple the various forms of degradation, whilst a table is presented to highlight the experimental conditions that are most likely to trigger specific degradation mechanisms. Together, they provide a powerful guide to designing experiments or models for investigating battery degradation.
188 citations
TL;DR: In this article, a four-band terahertz tunable narrow-band perfect absorber based on a bulk Dirac semi-metallic (BDS) metamaterial with a microstructure is designed.
Abstract: A four-band terahertz tunable narrow-band perfect absorber based on a bulk Dirac semi-metallic (BDS) metamaterial with a microstructure is designed. The three-layer structure of this absorber from top to bottom is the Dirac semi-metallic layer, the dielectric layer and the metal reflector layer. Based on the Finite Element Method (FEM), we use the simulation software CST STUDIO SUITE to simulate the absorption characteristics of the designed absorber. The simulation results show that the absorption rate of the absorber is over 93% at frequencies of 1.22, 1.822, 2.148 and 2.476 THz, and three of them have achieved a perfect absorption rate of more than 95%. We use the localized surface plasmon resonance (LSPR), impedance matching and other theories to analyze its physical mechanism in detail. The influence of the geometric structure parameters of the absorber and the incident angle of electromagnetic waves on the absorption performance has also been studied in detail. Due to the rotational symmetry of the structure, the designed absorber has excellent polarization insensitivity. In addition, the maximum adjustable range of absorption frequency is 0.051 THz, which can be achieved by changing the Fermi energy of BDS. We also define the refractive index sensitivity (S), which is 39.1, 75.4, 119.1 and 122.0 GHz RIU−1 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.
155 citations
TL;DR: In this article, 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.
Abstract: 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 porous architecture, GPC-3.0 (synthesized with a KOH : GPC ratio of 3.0, by wt.) exhibited the best capacitive behavior amongst the studied GPCs. The 3D hierarchically ordered architecture acts like well-designed ion highways that boost electron transportation, thereby enhancing electrochemical energy storage. A coin-cell-type symmetrical supercapacitor based on GPC-3.0 was tested in both 1.0 M Na2SO4 (salt-in-water) and 12.0 m NaNO3 (water-in-salt) electrolytes. The supercapacitor cell based on the water-in-salt electrolyte offered a wide operating voltage of 2.3 V. The obtained energy density and power density values were comparable to those of commercial high-performance electrical double-layer capacitors. Such notable findings will shed light on next-generation high-rate electrochemical energy storage systems based on biomass-derived carbonaceous materials.
99 citations
TL;DR: In this article, a two-dimensional InSe (B@2DInSe) catalyst was designed to separate CO2 and CH4 in different electric fields, which originates from different regulation mechanisms by an electric field (EF) on the electric properties.
Abstract: The separation of CO2 or CH4 from a CO2/CH4 mixture has drawn great attention in relation to solving air pollution and energy shortage issues. However, research into using bifunctional catalysts to separate CO2 and CH4 under different conditions is absent. We have herein designed a novel B-doped two-dimensional InSe (B@2DInSe) catalyst, which can chemically adsorb CO2 with covalent bonds. B@2DInSe can separate CO2 and CH4 in different electric fields, which originates from different regulation mechanisms by an electric field (EF) on the electric properties. The hybridization states between CO2 and B@2DInSe near the Fermi level have experienced gradual localization and eventually merged into a single narrow peak under an increased EF. As the EF further increased, the merged peak shifted towards higher energy states around the Fermi level. In contrast, the EF mainly alters the degree of hybridization between CH4 and B@2DInSe at states far below the Fermi level, which is different from the CO2 situation. These characteristics can also lead to perfect linear relationships between the adsorption energies of CO2/CH4 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.
83 citations
TL;DR: In this article, the authors have theoretically studied the NRR on TM dimer embedded N-doped porous graphene, denoted as M1M2@NG, and both homonuclear and heteronuclear DACs have been considered.
Abstract: 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 ultralow limiting potential of −0.24 V for the NRR and a strong capability of suppressing the competing hydrogen evolution reaction. Moreover, the synergetic effect for the heteronuclear DACs compared with the homonuclear counterparts has been studied in terms of energy and electronic structures. Based on this, we propose that combining a highly chemically active TM element (often the early TM) with another TM to form heteronuclear TM dimers on an appropriate substrate can help achieve efficient heteronuclear DACs for the NRR. Our studies not only highlight the important role of heteronuclear members in the application of DACs, but further provide a promising strategy to design efficient heteronuclear DACs for the NRR from the large chemical composition space.
77 citations
TL;DR: 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 as discussed by the authors.
Abstract: 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 atoms.
64 citations
TL;DR: In this paper, targeted modifications are discussed as a powerful tool to provide understanding and to enable design of ionic liquids, where a targeted modification is a deliberate change in the structure of an ionic liquid, such as chemical changes in an experiment as well as changes to the parameterisation in a computer simulation.
Abstract: 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 shows that understanding ionic liquids requires experimentalists and theoreticians to join forces and provides a tool to tackle the difficult transition from understanding to design.
57 citations
TL;DR: Several solutions to inhibit ion migration for better operational stability of perovskite solar cells were summarized, including bulk passivation, interface passivation and grain boundary passivation.
Abstract: The fundamental factor affecting the stability of perovskite solar cells, ion migration, has been reviewed, which is found to be closely related to the degradation of perovskite solar cells. Characterization methods like impedance spectroscopy and galvanostatic measurement to identify ion migration in perovskite films have been reviewed. The influence of light on ion migration was further discussed, which could largely explain the photo-stability decay in most perovskite solar cells. Finally, several solutions to inhibit ion migration for better operational stability of perovskite solar cells were summarized, including bulk passivation, interface passivation and grain boundary passivation. Several strategies have also been proposed to further improve the stablity of perovskite solar cells.
51 citations
TL;DR: In this article, the authors present a collection of major advancements in the field of computational modelling for the design and testing of the corrosion inhibition effectiveness of organic corrosion inhibitors, which 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.
Abstract: 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 descriptors/parameters, the inhibition effectiveness and nature of the metal–inhibitor interactions can also be predicted. The present review article is a collection of major advancements in the field of computational modelling for the design and testing of the corrosion inhibition effectiveness of organic corrosion inhibitors.
TL;DR: In this paper, the authors systematically analyzed transition metal (TM) single-atom (Ti, V, Cr, Mn, Zr, Nb, and Mo) anchored on graphyne (GY) as NRR catalysts using density functional theory calculations.
Abstract: 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 electronic properties, namely the Bader charge, charge density difference, partial density of states, and crystal orbital Hamilton population, of the TM@GY catalysts were analyzed in detail, and the results further confirmed that Mn@GY was an efficient electrocatalyst. The insights obtained from this comprehensive study can provide useful guidelines for designing new and efficient electrocatalysts.
TL;DR: In this paper, a three-band narrowband perfect absorber based on bulk Dirac semi-metallic (BDS) metamaterials was designed for optical switching, biochemical imaging, and space detection.
Abstract: In this paper, we designed a three-band narrowband perfect absorber based on bulk Dirac semi-metallic (BDS) metamaterials. The absorber consists of a hollow Dirac semi-metallic layer above, a gold layer below and a photonic crystal slab (PCS) in the middle. The study found that the terahertz wave absorber achieved three perfect absorption rates of more than 95% in the range of 1 to 2.4 THz. The minimum bandwidth (FWHM) is 0.02 THz, and the maximum quality factor (Q) is 106. A reasonable explanation of high absorption can be obtained by impedance matching, electric dipole and other principles. The absorption spectra of the two polarizations show different responses at different incident angles. In addition, we also obtained the influence of the structural parameters of the upper layer of the metamaterial on the absorption performance. We defined the refractive index sensitivity (S) with a maximum sensitivity of 0.1525 THz RIU-1 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.
TL;DR: In this article, a type-II heterojunction, C2N/MoSi2N4, is designed and systematically studied based on AIMD simulations and phonon dispersion verification, which shows sufficient thermodynamic stability.
Abstract: Very recently, an important two-dimensional material, MoSi2N4, was successfully synthesized. However, pure MoSi2N4 has some inherent shortcomings when used in photocatalytic water splitting to produce hydrogen, especially a low separation rate of photogenerated electron–hole pairs and a poor visible light response. Interestingly, we find that the MoSi2N4 can be used as a good modification material, and it can be coupled with C2N to form an efficient heterojunction photocatalyst. Here, using density functional theory, a type-II heterojunction, C2N/MoSi2N4, is designed and systematically studied. Based on AIMD simulations and phonon dispersion verification, C2N/MoSi2N4 shows sufficient thermodynamic stability. As well as its perfect interface electronic properties, its large interlayer charge transfer and good visible light response lay the foundation for its excellent photocatalytic performance. In addition, the oxidation and reduction potentials of the C2N/MoSi2N4 heterojunction not only can meet the requirements of water splitting well but can also maintain a delicate balance between oxidation and reduction reactions. More importantly, the |ΔGH*| value of the C2N/MoSi2N4 heterojunction is very close to zero, indicating great application potential in the field of photocatalytic water splitting. In brief, our research paves the way for the design of future MoSi2N4-based efficient heterojunction photocatalysts.
TL;DR: Based on first-principles calculations, a SiH/CeO2(111) type-II heterojunction with a very small lattice mismatch of less than 1% was constructed in this paper.
Abstract: 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 potential photocatalyst for splitting water to hydrogen.
TL;DR: In this article, 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.
Abstract: 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.
TL;DR: For 68% of the investigated complexes at least one low-energy conformer was found that is more stable than the respective crystal structure conformation, which signals the importance of conformational studies.
Abstract: Conformational energies are an important chemical property for which a performance assessment of theoretical methods is mandatory. Existing benchmark sets are often limited to biochemical or main group element containing molecules, while organometallic systems are generally less studied. A key problem herein is to routinely generate conformers for these molecules due to their complexity and manifold of possible coordination patterns. In this study we used our recently published CREST protocol [Pracht et al., Phys. Chem. Chem. Phys., 2020, 22, 7169-7192] to generate conformer ensembles for a variety of 40 challenging transition metal containing molecules, which were then used to form a comprehensive conformational energy benchmark set termed TMCONF40. Several low-cost semiempirical, density functional theory (DFT) and force-field methods were compared to high level DLPNO-CCSD(T1) and double-hybrid DFT reference values. Close attention was paid to the energetic ordering of the conformers in the statistical evaluation. With respect to the double-hybrid references, both tested low-cost composite DFT methods produce high Pearson correlation coefficients of rp,mean,B97-3c//B97-3c = 0.922 and rp,mean,PBEh-3c//B97-3c = 0.890, with mean absolute deviations close to or below 1 kcal mol-1. This good performance also holds for a comparison to DLPNO-CCSD(T1) reference energies for a smaller subset termed TMCONF5. Based on DFT geometries, the GFNn-xTB methods yield reasonable Pearson correlation coefficients of rp,mean,GFN1-xTB//B97-3c = 0.617 (MADmean = 2.15 kcal mol-1) and rp,mean,GFN2-xTB//B97-3c = 0.567 (MADmean = 2.68 kcal mol-1), outperforming the widely used PMx methods on the TMCONF40 test set. Employing the low-cost composite DFT method B97-3c on GFN2-xTB geometries yields an slightly improved correlation of rp,mean,B97-3c//GFN2-xTB = 0.632. Furthermore, for 68% of the investigated complexes at least one low-energy conformer was found that is more stable than the respective crystal structure conformation, which signals the importance of conformational studies. General recommendations for the application of the CREST protocol and DFT methods for transition metal conformational energies are given.
TL;DR: A review of the state-of-the-art in the theory of dissociative chemisorption (DC) of small gas phase molecules on metal surfaces can be found in this paper.
Abstract: We review the state-of-the-art in the theory of dissociative chemisorption (DC) of small gas phase molecules on metal surfaces, which is important to modeling heterogeneous catalysis for practical reasons, and for achieving an understanding of the wealth of experimental information that exists for this topic, for fundamental reasons. We first give a quick overview of the experimental state of the field. Turning to the theory, we address the challenge that barrier heights (Eb, which are not observables) for DC on metals cannot yet be calculated with chemical accuracy, although embedded correlated wave function theory and diffusion Monte-Carlo are moving in this direction. For benchmarking, at present chemically accurate Eb can only be derived from dynamics calculations based on a semi-empirically derived density functional (DF), by computing a sticking curve and demonstrating that it is shifted from the curve measured in a supersonic beam experiment by no more than 1 kcal mol-1. The approach capable of delivering this accuracy is called the specific reaction parameter (SRP) approach to density functional theory (DFT). SRP-DFT relies on DFT and on dynamics calculations, which are most efficiently performed if a potential energy surface (PES) is available. We therefore present a brief review of the DFs that now exist, also considering their performance on databases for Eb for gas phase reactions and DC on metals, and for adsorption to metals. We also consider expressions for SRP-DFs and briefly discuss other electronic structure methods that have addressed the interaction of molecules with metal surfaces. An overview is presented of dynamical models, which make a distinction as to whether or not, and which dissipative channels are modeled, the dissipative channels being surface phonons and electronically non-adiabatic channels such as electron-hole pair excitation. We also discuss the dynamical methods that have been used, such as the quasi-classical trajectory method and quantum dynamical methods like the time-dependent wave packet method and the reaction path Hamiltonian method. Limits on the accuracy of these methods are discussed for DC of diatomic and polyatomic molecules on metal surfaces, paying particular attention to reduced dimensionality approximations that still have to be invoked in wave packet calculations on polyatomic molecules like CH4. We also address the accuracy of fitting methods, such as recent machine learning methods (like neural network methods) and the corrugation reducing procedure. In discussing the calculation of observables we emphasize the importance of modeling the properties of the supersonic beams in simulating the sticking probability curves measured in the associated experiments. We show that chemically accurate barrier heights have now been extracted for DC in 11 molecule-metal surface systems, some of which form the most accurate core of the only existing database of Eb for DC reactions on metal surfaces (SBH10). The SRP-DFs (or candidate SRP-DFs) that have been derived show transferability in many cases, i.e., they have been shown also to yield chemically accurate Eb for chemically related systems. This can in principle be exploited in simulating rates of catalyzed reactions on nano-particles containing facets and edges, as SRP-DFs may be transferable among systems in which a molecule dissociates on low index and stepped surfaces of the same metal. In many instances SRP-DFs have allowed important conclusions regarding the mechanisms underlying observed experimental trends. An important recent observation is that SRP-DFT based on semi-local exchange DFs has so far only been successful for systems for which the difference of the metal work function and the molecule's electron affinity exceeds 7 eV. A main challenge to SRP-DFT is to extend its applicability to the other systems, which involve a range of important DC reactions of e.g. O2, H2O, NH3, CO2, and CH3OH. Recent calculations employing a PES based on a screened hybrid exchange functional suggest that the road to success may be based on using exchange functionals of this category.
TL;DR: In this paper, a review of the thermal transport properties of polymer-based nanocomposites with high thermal conductivity (TC) is presented, and the applications of various nanomaterials in polymer nanocompositionites for advanced TIMs are critically reviewed and the mechanism of TC enhancement is analyzed.
Abstract: Modern electronic devices are characterized by high-power and high-frequency with excessive heat accumulation. Thermal interface materials (TIMs) are of crucial importance for efficient heat dissipation to maintain proper functions and lifetime for these devices. The most promising TIMs are those polymer-based nanocomposites consisting of polymers and low-dimensional materials with high thermal conductivity (TC). This perspective summarizes the recent progress on the thermal transport properties of newly discovered one-dimensional (1D) nanomaterials and two-dimensional (2D) nanomaterials as well as three-dimensional (3D) nanostructures consisting of these 1D and 2D nanomaterials. Moreover, the applications of various nanomaterials in polymer nanocomposites for advanced TIMs are critically reviewed and the mechanism of TC enhancement is analysed. It is hoped that the present review could provide better understanding of the thermal transport properties of recently developed 2D nanomaterials and various 3D nanostructures as well as relevant polymer-based TIMs, shedding more light on the thermal management research.
TL;DR: In this article, the authors present a review of 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 between amorphization and crystallization.
Abstract: 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 between amorphization and crystallization. Furthermore, we provide the prospect of laser-generated metallic glass nanoparticles (MG-NPs) from MG targets. The current and potential applications of A-NPs are also discussed, categorized by the attractive application fields e.g. in catalysis and magnetism. The present work aims to give possible selection rules and perspective on the design of colloidal A-NPs as well as the synthesis criteria of MG-NPs from laser-based strategies.
TL;DR: In this article, the authors present a systematic investigation of the mechanical, electronic and optical properties of a B2P6 monolayer using first-principles calculations, and show that the B 2P6 has promising applications in photocatalytic and photovoltaic devices.
Abstract: Two-dimensional (2D) materials with a moderate bandgap and high carrier mobility are useful for applications in optoelectronics. In this work, we present a systematic investigation of the mechanical, electronic and optical properties of a B2P6 monolayer using first-principles calculations. Monolayer B2P6 was estimated to be an anisotropic material from direction-dependent in-plane Young's moduli and Poisson's ratios. Also, B2P6 exhibits an ultrahigh electron mobility of ∼5888 cm2 V−1 s−1, showing advantages for application in high-speed optoelectronic devices. More importantly, for the B2P6 monolayer, a desirable transformation from an indirect to direct band gap was observed at a biaxial tensile strain of ∼4%. Increasing the biaxial strain reduces the gap and preserves the suitable band edge positions for photocatalytic water splitting in the observed strain range of 1–8%. The decreased gap also enhances the visible light absorption of the B2P6 monolayer. These findings indicate that the B2P6 monolayer has promising applications in photocatalytic and photovoltaic devices.
TL;DR: In this paper, the structural, electronic, and mechanical properties of functionalized Ti2C and Ti3C2 monolayers were investigated by means of density functional theory calculations.
Abstract: 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 effects by tuning the energy of the Dirac cones. In addition, the computed linear-elastic parameters prove that functionalization is a powerful tool in tuning the mechanical properties of stiff monolayers of bare Ti2C and Ti3C2. Our study discloses that the electronic and structural properties of Ti2C and Ti3C2 MXene monolayers are suitable for surface modification, which is highly desirable for material property engineering and device integration.
TL;DR: In this article, the structural stability and optical properties of two-dimensional (2D) cadmium chalcogenide single-layers with a tetragonal crystal structure were investigated.
Abstract: 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 ability of these monolayers to absorb visible light. Due to the suitable band gaps and band edge positions of Tetra-CdX, these newly discovered 2D materials are promising for photocatalytic water splitting.
TL;DR: In this paper, the authors review the recent progress in molecular dynamics simulation studies of IDPs, including the development of force fields and sampling methods, as well as applications in IDP-involved protein-protein interactions.
Abstract: Intrinsically disordered proteins (IDPs) play important roles in cellular functions. The inherent structural heterogeneity of IDPs makes the high-resolution experimental characterization of IDPs extremely difficult. Molecular dynamics (MD) simulation could provide the atomic-level description of the structural and dynamic properties of IDPs. This perspective reviews the recent progress in atomic MD simulation studies of IDPs, including the development of force fields and sampling methods, as well as applications in IDP-involved protein-protein interactions. The employment of large-scale simulations and advanced sampling techniques allows more accurate estimation of the thermodynamics and kinetics of IDP-mediated protein interactions, and the holistic landscape of the binding process of IDPs is emerging.
TL;DR: In this article, the authors present an introductory tutorial to those with no formalized training in this area, which can be used when undertaking practical electrochemistry experiments for the first time.
Abstract: 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 electrochemical cell receives input signals and outputs data and data filtering. By reading the article, it is intended the reader will also gain a greater confidence in problem solving issues that arise with electrochemical cells, for example electrical noise, uncompensated resistance, reaching compliance voltage, signal digitisation and data interpretation. We also include trouble shooting tables that build on the information presented and can be used when undertaking practical electrochemistry.
TL;DR: In this article, a review of the conventional workflow of reaction prediction, including reaction network generation, ab initio thermodynamics and microkinetic modelling, is presented, as well as a promising alternative to full-ab initio calculations, machine learning interatomic potentials.
Abstract: 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 microkinetic modelling. An overview of the frequently used regression models in machine learning is presented. As a promising alternative to full ab initio calculations, machine learning interatomic potentials are highlighted. Furthermore, we survey applications assisted by these methods for accelerating reaction prediction, exploring reaction networks, and computational catalyst design. Finally, we envisage future directions in computationally investigating reactions and implementing machine learning algorithms in heterogeneous catalysis.
TL;DR: It is realized that the thermal-induced Luminescence enhancement is a form of recovery process against the strong luminescence quenching in the system, and the enhancement degree is closely associated with the extent of luminescent loss induced by various quench effects beforehand.
Abstract: Luminescence thermal stability is a major figure of merit of lanthanide-doped nanoparticles playing an essential role in determining their potential applications in advanced optics. Unfortunately, considering the intensification of multiple electron-vibration interactions as temperature increases, luminescence thermal quenching of lanthanide-doped materials is generally considered to be inevitable. Recently, the emergence of thermally enhanced upconversion luminescence in lanthanide-doped nanoparticles seemed to challenge this stereotype, and the research on this topic rapidly aroused wide attention. While considerable efforts have been made to explore the origin of this phenomenon, the key mechanism of luminescence enhancement is still under debate. Here, to sort out the context of this intriguing finding, the reported results on this exciting topic are reviewed, and the corresponding enhancement mechanisms as proposed by different researchers are summarized. Detailed analyses are provided to evaluate the contribution of the most believed “surface-attached moisture desorption” process on the overall luminescence enhancement of lanthanide-doped nanoparticles at elevated temperatures. The impacts of other surface-related processes and shell passivation on the luminescence behaviour of the lanthanide-doped materials are also elaborated. Lack of standardization in the reported data and the absence of important experimental information, which greatly hinders the cross-checking and reanalysis of the results, is emphasized as well. On the foundation of these discussions, it is realized that the thermal-induced luminescence enhancement is a form of recovery process against the strong luminescence quenching in the system, and the enhancement degree is closely associated with the extent of luminescence loss induced by various quenching effects beforehand.
TL;DR: In this article, the role of chloride as a function of water content was investigated using viscosity-corrected 35Cl NMR spectroscopy and molecular dynamics simulations to reveal three Cl- solvation regimes, with high-symmetry environments for pure and highly dilute DESs, and an unusual low-synmmetry interstitial region where the primary coordination sphere is most disordered.
Abstract: The Deep Eutectic Solvents/Systems (DESs) choline chloride:urea (xChCl = 0.33) and choline chloride:glycolic acid (xChCl = 0.5) were investigated using viscosity-corrected 35Cl NMR spectroscopy and molecular dynamics simulations to probe the role of chloride as a function of water content. Three Cl- solvation regimes are revealed, with high-symmetry environments for pure and highly dilute DES, and an unusual low-symmetry interstitial region where the primary coordination sphere is most disordered.
TL;DR: In this article, the authors discuss how to choose appropriate atomistic representations for the system under investigation, highlight the role of the exchange-correlation functional and the van der Waals correction employed in the calculation and provide tips and tricks how to efficiently converge the self-consistent field cycle and to obtain accurate geometries.
Abstract: 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 self-consistent field cycle and to obtain accurate geometries. We particularly focus on potentially unexpected pitfalls and the errors they incur. As a summary, we provide a list of best practice rules for interface simulations that should especially serve as a useful starting point for less experienced users and newcomers to the field.
TL;DR: In this article, the authors 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.
Abstract: 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 are systematically presented. Finally, the future prospects of 2D materials in chemiresistive- and FET-type gas sensing applications as well as the current existing problems are pointed out, which could be helpful for the development of 2D material-based gas sensors with better sensing performance to meet the requirements for practical application.