Building a New Platform for Significantly Improving Performance of Hartree-Fock and CCSD(T) Correlation Energy Based on Two-Point Complete Basis Set Extrapolation Schemes.

The leading cause of high expense in gold standard coupled cluster theory is that calculations of electronic energies converge exceedingly slowly with an increased basis set size. Extrapolation principally allows for achieving higher-quality outcomes at reduced costs. Numerous extrapolation formulas have been developed, with attempts to predict energies up to the complete basis set limit. Unfortunately, since the intricate shape of the function hinges on the molecular properties with the highest angular momentum of the basis set, the accuracy of the extrapolated energies highly depends on the fitted empirical parameters, which rely on the quality of the data sets for fitting. In this work, to overcome the extrapolation deficiency caused by the very limited data sets and smaller basis sets in the early stages, we constructed a new benchmark platform that includes a broader data set of 183 species (containing open-shell, closed-shell, ionic, and neutral species) and a larger basis set up to aug-cc-pV6Z. The newly optimized parameters can significantly improve the energy-predictive abilities of ten published formulas. Notably, all ten formulas perform quite similarly under the new platform with the reoptimized parameters. Finally, we built an online calculator for researchers to use for these extrapolation schemes. Our work would reignite the interest and applications of the underestimated formulas.

Robust and Corrosion-Resistant Overall Water Splitting Electrode Enabled by Additive Manufacturing.

Electrolysis of water has emerged as a prominent area of research in recent years. As a promising catalyst support, copper foam is widely investigated for electrolytic water, yet the insufficient mechanical strength and corrosion resistance render it less suitable for harsh working conditions. To exploit high-performance catalyst supports, various metal supports are comprehensively evaluated, and Ti6 Al4 V (Ti64) support exhibited outstanding compression and corrosion resistance. With this in mind, a 3D porous Ti64 catalyst support is fabricated using the selective laser sintering (SLM) 3D printing technology, and a conductive layer of nickel (Ni) is coated to increase the electrical conductivity and facilitate the deposition of catalysts. Subsequently, Co0.8 Ni0.2 (CO3 )0.5 (OH)·0.11H2 O (CoNiCH) nanoneedles are deposited. The resulting porous Ti64/Ni/CoNiCH electrode displayed an impressive performance in the oxygen evolution reaction (OER) and reached 30 mA cm-2 at an overpotential of only 200 mV. Remarkably, even after being compressed at 15.04 MPa, no obvious structural deformation is observed, and the attenuation of its catalytic efficiency is negligible. Based on the computational analysis, the CoNiCH catalyst demonstrated superior catalytic activity at the Ni site in comparison to the Co site. Furthermore, the electrode reached 30 mA cm-2 at 1.75 V in full water splitting conditions and showed no significant performance degradation even after 60 h of continuous operation. This study presents an innovative approach to robust and corrosion-resistant catalyst design.

Design of N-N ylide bond-based high energy density materials: a theoretical survey.

The generally encountered contradiction between large energy content and stability poses great difficulty in designing nitrogen-rich high-energy-density materials. Although N-N ylide bonds have been classified as the fourth type of homonuclear N-N bonds (besides >N-N<, -N[double bond, length as m-dash]N-, and N[triple bond, length as m-dash]N), accessible energetic molecules with N-N ylide bonds have rarely been explored. In this study, 225 molecules with six types of novel structures containing N-N ylide bonds were designed using density functional theory and CBS-QB3 methods. To guide future synthesis, the effects of substitution on the thermal stability, detonation velocity, and detonation pressure of the structures were evaluated under the premise that the N-N ylide skeleton remains stable. The calculations show that the bond dissociation energy values of the N-N ylide bonds of the designed 225 structures were in the range of 61.21-437.52 kJ mol-1, except for N-1NNH2. Many of the designed structures with N-N ylide bonds exhibit high detonation properties, which are superior to those of traditional energetic compounds. This study convincingly demonstrates the feasibility of the design strategy of introducing an N-N ylide bond to develop new types of energetic materials.

The Association of Allergy-Related and Non-Allergy-Related Olfactory Impairment with Cognitive Function in Older Adults: Two Cross-Sectional Studies.

BACKGROUND: Evidence on the association of Olfactory Impairment (OI) with age-related cognitive decline is inconclusive, and the potential influence of allergy remains unclear. OBJECTIVE: We aimed to evaluate the cross-sectional associations of allergy-related and non-allergy- related OI to cognitive function. METHODS: We included 2,499 participants from the Health and Retirement Study (HRS)-Harmonized Cognitive Assessment Protocol (HCAP) sub-study and 1,086 participants from the English Longitudinal Study of Ageing (ELSA)-HCAP. The Olfactory Function Field Exam (OFFE) using Sniffin' Stick odor pens was used to objectively assess olfactory function and an olfactory score <6/11 indicated OI. Mini-Mental Status Examination (MMSE) was used to assess global cognitive function and define cognitive impairment (<24/30). A neuropsychologic battery was used to assess five cognitive domains. RESULTS: Compared to non-OI participants, individuals with OI had lower MMSE z-score [ßHRS = -0.33, 95% Confidence Interval (CI): -0.41 to -0.24; ßELSA = -0.31, -0.43 to -0.18] and higher prevalence of cognitive impairment [Prevalence Ratio (PR)HRS = 1.46, 1.06 to 2.01; PRELSA = 1.63, 1.26 to 2.11]. The associations were stronger for non-allergy-related OI (ßHRS = -0.36; ßELSA = -0.34) than for allergy-related OI (ßHRS = -0.26; ßELSA = 0.13). Similar associations were observed with domain- specific cognitive function measures. CONCLUSION: OI, particularly non-allergy-related OI, was related to poorer cognitive function in older adults. Although the current cross-sectional study is subject to several limitations, such as reverse causality and residual confounding, the findings will provide insights into the OI-cognition association and enlighten future attention to non-allergy-related OI for the prevention of potential cognitive impairment.

Enhanced Efficiency, Broadened Excitation, and Tailored Er3+ Luminescence Triggered by Te4+ Codoping in Cs2NaYbCl6 Crystals for Multifunctional Applications.

The quest for efficient and tunable luminescent materials has been at the forefront of research in the fields of chemistry and materials science. This work delves into the investigation of the luminescence properties of Er3+ ions triggered by 1% Te4+ in the environmentally benign perovskite Cs2NaYbCl6 (CNYC) crystals, aiming to enhance their efficiency and tune the luminescence color. The ratio of the green (2H11/2, 4S3/2-4I15/2) to red (4F9/2-4I15/2) emissions of Er3+ can be freely tunable by varying the concentration of Er3+ and producing the defects induced by codoping Te4+. The calculations reveal that the multiexcitonic excitations of Er3+ stem from f-f (4I15/2-4G11/2, 2H9/2) rather than d-f transitions. The broadened excitation, tuning of color, and enhancement of efficiency achieved in the luminescence perovskite crystals Cs2NaYbCl6:Te4+, Er3+ (CNYC:Te4+,Er3+) presents promising opportunities for the development of advanced optoelectronic devices with superior performance. Moreover, our investigation demonstrates the tunable luminescence response of CNYC:Er3+ to temperature variations, offering potential applications in temperature sensing.

Achieving Accuracy and Economy for Calculating Vertical Detachment Energies of Molecular Anions: A Model Chemistry Composite Methods.

The vertical detachment energy (VDE) is a vital factor for predicting the stability of anions that have important applications in the atom, molecule and cluster science. Due to the synthetic or characterization difficulty of anions, accurate and efficient predictions of VDE independent of laboratory data have always been an appealing task to remedy the experimental deficiencies. Unfortunately, the generally adopted CCSD(T) and electron propagator theory (EPT) methods have respectively been proven to be reliable but very cost-expensive, and cost-effective but sometimes problematic when Koopman's theorem is invalid. Here, we for the first time introduced and benchmarked a series of model chemistry composite methods (e. g., CBS-QB3, G4 and W1BD) on calculating VDE for 57 molecular anions. Notably, CBS-QB3 exceeds the accuracy of CCSD(T) while approaching the economy of EPT. Therefore, we highly recommend the composite method CBS-QB3 to compute VDEs for molecular anions in the attractive "killing two birds with one stone" manner.

Risk Factors of Premature Atherosclerotic Cardiovascular Disease in China: A Longitudinal Analysis of the China Health and Nutrition Survey Cohort.

The burden of premature atherosclerotic cardiovascular disease (ASCVD) has increased rapidly in China. Using the China Health and Nutrition Survey (CHNS) data, we assessed the risk factors of premature ASCVD (age of diagnosis: <55 years for men and <65 years for women). Propensity score matching was used to reduce selection bias. Multivariable Cox proportional-hazards analyses indicated that factors associated with increased risk of premature ASCVD included hypertension (adjusted hazard ratio [HRadj.] = 1.68), obesity (HRadj. = 1.64), and high carbohydrate intake (HRadj. = 1.46). Conversely, participants with medical insurance (HRadj. = 0.42), high urbanization index (HRadj. = 0.53), and high household income (HRadj. = 0.48) had lower risk of premature ASCVD. When comparing premature vs non-premature ASCVD participants, those who were obese (HRadj. = 2.08) or living in more urbanized areas had higher hazards of early onset (HRadj. = 2.29).

Enhancing Luminescence in Hue-Tunable White-Light Emitting K4CdCl6:Sb3+,Mn2+ All-Inorganic Halide Perovskites: Insights from Defect Engineering and Energy Transfer.

All-inorganic halide perovskites (AIHPs) have emerged as highly promising optoelectronic materials owing to their remarkable properties, such as high-optical absorption coefficients, photoluminescence efficiencies, and dopant tolerance. Here, we investigate the AIHPs K4CdCl6:Sb3+,Mn2+ that demonstrate hue-tunable white-light emission with an exceptional photoluminescence quantum yield of up to 97%. Through a detailed investigation, we reveal that efficient energy transfer from Sb3+ to Mn2+ plays a dominant role in the photoluminescence of Mn2+, instead of the conventional 4T1g → 6A1g transition of Mn2+. Thermodynamic analysis highlights the crucial role of a Cl-rich environment in obtaining the K4CdCl6 phase, while transformation from K4CdCl6 to KCdCl3 can be achieved under Cl-poor and K-poor conditions. The theoretical analysis reveals that defect Cli is more readily formed compared to defect VK, corroborating experimental findings that the K4CdCl6:Sb3+ phase is exclusively obtained when the solution contains HCl concentrations higher than 4 mol L-1. Our work provides valuable insights into the photoluminescence mechanism of Sb3+, defect engineering through heterovalent doping, and efficient energy transfer between Sb3+ and Mn2+ in K-Cd-Cl-based perovskites, which offers a new perspective for the design and development of novel AIHPs with superior optoelectronic performance.

The carbon reduction effects of stepped carbon emissions trading and carbon capture and storage on hybrid wind-PV-thermal- storage generation operating systems.

To accelerate the low-carbon transformation of the power industry, a range of carbon emission reduction policies and technologies have emerged. However, the current China's carbon emissions trading (CET) policy is inadequate in encouraging power generation enterprises to take proactive measures towards emission reduction due to challenges like fixed and low carbon prices. The high proportion of renewable energy in electricity consumption also faces significant challenges due to the unpredictable nature of wind and PV energy. Therefore, this paper applies stepped CET mechanism, energy storage system (ES) system and carbon capture and storage (CCS) mechanism together to hybrid renewable energy system, aiming to study their synergistic carbon emission reduction effect. Firstly, the paper constructs the stepped CET model considering incentives and penalties. Secondly, the stepped CET model, ES system and CCS are jointly introduced into the hybrid renewable energy system. Finally, a scenario analysis is conducted to investigate the synergistic effect of various carbon emissions reduction policies and technologies in the operation of power generation systems. The results show that: i) compared with traditional CET, the stepped CET increases renewable energy consumption by 0.12% and reduces carbon emissions by 0.6%; ii) the introduction of stepped CET and ES equipment together consumes an additional 36.1% of renewable energy and reduces carbon emissions by 32.4%; iii) based on stepped CET model and ES equipment, the introduction of CCS system reduces carbon emissions by 29.4%.

Differential evolution for population diversity mechanism based on covariance matrix.

Differential evolution (DE) is a heuristic global search algorithm based on population. It has exhibited great adaptability in solving continuous-domain problems, but sometimes suffered from insufficient local search ability and being trapped in local optimum when dealing with complicated optimization problems. To solve these problems, an improved differential evolution algorithm with population diversity mechanism based on covariance matrix (CM-DE) is proposed. First, a new parameter adaptation strategy is used to adapt the control parameters, in which the scale factor F is updated according to the improved wavelet basis function in the early stage and Cauchy distribution in the later stage and the crossover rate CR is generated according to normal distribution. The diversity of population and convergence speed are improved by employing the method above. Second, the perturbation strategy is incorporated into crossover operator to enhance the search ability of DE. Finally, the covariance matrix of the population is constructed, where the variance in the covariance matrix is used as indicator to measure the similarity between individuals in the population in order to prevent the algorithm from falling into local optimum resulted by low population diversity. The CM-DE is compared with the state-of-art DE variants including LSHADE (Tanabe and Fukunaga, 2014), jSO [1], LPalmDE [2], PaDE [3] and LSHADE-cnEpSin [4] under 88 test functions from CEC2013 [5], CEC2014 [6] and CEC2017 (Wu et al., 2017) test suites. From the experiment results, it is obvious that among 30 benchmark functions from CEC2017 on 50D optimization, the CM-DE algorithm has 22, 20, 24, 23, 28 better performances comparing with LSHADE, jSO, LPalmDE, PaDE, and LSHADE-cnEpsin. For CEC2017 on 30D optimization, the proposed algorithm secures better performance on 19 out of 30 benchmark functions in terms of convergence speed. In addition, a real-world application is also used to verify the feasibility of the proposed algorithm. The experiment results validate the highly competitive performance in terms of solution accuracy and convergence speed.

Reaction mechanism of nickel sulfide atomic layer deposition using bis(N,N'-di-tert-butylacetamidinato)nickel(II) and hydrogen sulfide.

As a unique nanofabrication technology, atomic layer deposition (ALD) has been used in the microelectronics, catalysis, environmental and energy fields. As an energy and catalytic material, nickel sulfide has excellent electrochemical and catalytic activities and has attracted extensive attention. In this work, the reaction mechanism for nickel sulfide ALD from an amidine metal precursor was investigated using density functional theory (DFT) calculations. The results show that the first amidine ligand of bis(N,N'-di-tert-butylacetamidinato)nickel(II) [Ni(tBu-MeAMD)2] can be easily eliminated on the sulfhydrylated surface. The second amidine ligand can also react with the adjacent sulfhydryl group to generate the N,N'-di-tert-butylacetamidine (tBu-MeAMD-H) molecule, which can strongly interact with the Ni atom on the surface and be difficult to be desorbed. In the subsequent H2S reaction, the tBu-MeAMD-H molecule can be exchanged with the H2S precursor. Ultimately, the tBu-MeAMD-H molecule can be desorbed and H2S can be dissociated to form two sulfhydrylated groups on the surface. Meanwhile, the -SH of a H2S molecule can be exchanged with the second tBu-MeAMD ligand. These insights into the reaction mechanism of nickel sulfide ALD can provide theoretical guidance to design the metal amidinate precursors and improve the ALD process for metal sulfides.

High-Capacity Sb/Fe2S3 Sodium-Ion Battery Anodes Fabricated by a One-Step Redox Reaction, Followed by Ball Milling with Graphite.

Antimony (Sb) has been considered a promising anode for sodium-ion batteries (SIBs) owing to its high theoretical capacity (660 mA h g-1) and low redox voltage (0.2-0.9 V vs Na+/Na). However, the capacity degradation caused by the volumetric variation during battery discharge/charge hinders the practical application. Herein, guided by the DFT calculation, Sb/Fe2S3 was fabricated by annealing Fe and Sb2S3 mixed powder. Next, Sb/Fe2S3 was blended with 15 wt % graphite by ball milling, yielding nano-Sb/Fe2S3 anchored on an exfoliated graphite composite (denoted as Sb/Fe2S3-15%). When applied as an anode of SIBs, Sb/Fe2S3-15% delivered reversible capacities of 565, 542, 467, 366, 285, and 236 mA h g-1 at current rates of 1, 2, 4, 6, 8, and 10 A g-1, respectively, surpassing most of the Sb-based anodes. The co-existence of highly conductive Fe2S3 and Sb minimizes the polarization of the anode. Our experiments proved that the Sb and Fe2S3 phases were reversible during discharge/charge cycling, and the exfoliated graphite can accelerate the Na+ diffusion and e- conduction. The proposed synthesis method of this work can also be applicable to synthesize various antimony/transition metal sulfide heterostructures (Sb/M1-xS), which may be applied in a series of fields.

Polycrystalline Fe- and Sn-based sulfides for high-capacity sodium-ion battery anodes.

Nano-polycrystalline Sn2S3/Sn3S4/FeS/Fe7S8 sulfides anchored on graphene were synthesized via annealing SnS2 and Fe followed by homogeneously combining them with exfoliated graphite. When applied as an anode for a sodium-ion battery, the reversible capacity reached 863 mA h g-1 at 100 mA g-1. This facial materials synthesis method may be applied in various fields.

Manageable Bubble Release Through 3D Printed Microcapillary for Highly Efficient Overall Water Splitting.

Porous metal foams (e.g., Ni/Cu/Ti) are applied as catalyst supports extensively for water splitting due to their large specific area and excellent conductivity, however, intrinsic bubble congestion is unavoidable because of the irregular three-dimensional (3D) networks, resulting in high polarization and degraded electrocatalytic performances. To boost the H2 O decomposition kinetics, the immediate bubble removal and water supply sequential in the gas-liquid-solid interface is essential. Inspired by the high efficiency of water/nutrient transport in the capillaries plants, this work designs a graphene-based capillary array with side holes as catalyst support to manage the bubble release and water supply via a Z-axis controllable digital light processing (DLP) 3D printing technology. Like planting rice, a low-cost, high-active CoNi carbonate hydroxide (CoNiCH) is planted on support. A homemade cell can reach 10 mA cm-2 in 1.51 V, and be kept at 30 mA cm-2 for 60 h without noticeable degradation, surpassing most of the known cells. This research provides a promising avenue to design and prepare advanced catalysts in various fields, including energy applications, pollutant treatment, and chemical synthesis.

Precise Hue Control in a Single-Component White-Light Emitting Perovskite Cs2 SnCl6 through Defect Engineering Based on La3+ Doping.

Single-component white light emitters based on the all-inorganic perovskites will act as outstanding candidates for applications in solid-state lighting thanks to their abundant energy states for self-trapped excitons (STE) with ultra-high photoluminescence (PL) efficiency. Here, a complementary white light is realized by dual STEs emissions with blue and yellow colors in a single-component perovskite Cs2 SnCl6 :La3+ microcrystal (MC). The dual emission bands centered at 450 and 560 nm are attributed to the intrinsic STE1 emission in host lattice Cs2 SnCl6 and the STE2 emission induced by the heterovalent La3+ doping, respectively. The hue of the white light can be tunable through energy transfer between the two STEs, the variation of excitation wavelength, and the Sn4+ /Cs+ ratios in starting materials. The effects of the doping heterovalent La3+ ions on the electronic structure and photophysical properties of the Cs2 SnCl6 crystals and the created impurity point defect states are investigated by the chemical potentials calculated using density functional theory (DFT) and confirmed by the experimental results. These results provide a facile approach to gaining novel single-component white light emitter and offer fundamental insights into the defect chemistry in the heterovalent ions doped perovskite luminescent crystals.

First-Principles Molecular Dynamics Simulations on Water-Solid Interface Behavior of H2O-Based Atomic Layer Deposition of Zirconium Dioxide.

As an important inorganic material, zirconium dioxide (ZrO2) has a wide range of applications in the fields of microelectronics, coating, catalysis and energy. Due to its high dielectric constant and thermodynamic stability, ZrO2 can be used as dielectric material to replace traditional silicon dioxide. Currently, ZrO2 dielectric films can be prepared by atomic layer deposition (ALD) using water and zirconium precursors, namely H2O-based ALD. Through density functional theory (DFT) calculations and first-principles molecular dynamics (FPMD) simulations, the adsorption and dissociation of water molecule on the ZrO2 surface and the water-solid interface reaction were investigated. The results showed that the ZrO2 (111) surface has four Lewis acid active sites with different coordination environments for the adsorption and dissociation of water. The Zr atom on the surface can interacted with the O atom of the water molecule via the p orbital of the O atom and the d orbital of the Zr atom. The water molecules could be dissociated via the water-solid interface reaction of the first or second layer of water molecules with the ZrO2 (111) surface. These insights into the adsorption and dissociation of water and the water-solid interface reaction on the ZrO2 surface could also provide a reference for the water-solid interface behavior of metal oxides, such as H2O-based ALD.

Free and Complexed Fluoropentazoles: Anomalous Ring Charge and Appreciable Kinetic Stability.

Fluoronitrogens are strongly related to high-energy density materials. Fluoropentazole (cyclo-FN5) with hitherto the highest N/F ratio at ambient pressure belongs to the family of well-known and 119-year-old pentazoles. Due to the presence of the overwhelmingly electronegative F element, cyclo-FN5 is the only pentazole to date that contains a cationic N5 ring. However, also due to F's large electronegativity, the reported ring-destruction barrier of cyclo-FN5 is nearly the lowest (6.7 kcal/mol), which has made its synthesis and characterization quite difficult. Here, cyclo-FN5 was re-predicted to bear an almost doubled ring-destruction barrier (∼12-14 kcal/mol) at the CBS-QB3, G4, W1BD, CCSD(T)/CBS//CCSD/cc-pVTZ, and CCSD(T)/CBS//CCSD(T)/aug-cc-pVTZ levels. Promisingly, upon further complexation with Lewis acid(s), the ring-destruction barrier of cyclo-FN5 might reach 23 kcal/mol, which is comparable to that of the well-known and already synthesized arylpentazoles (∼20 kcal/mol), and the positive charge on the N5 ring can be increased to 0.66 |e|.

Reaction mechanism of atomic layer deposition of zirconium oxide using zirconium precursors bearing amino ligands and water.

As a unique nanofabrication technology, atomic layer deposition (ALD) has been widely used for the preparation of various materials in the fields of microelectronics, energy and catalysis. As a high-κ gate dielectric to replace SiO2, zirconium oxide (ZrO2) has been prepared through the ALD method for microelectronic devices. In this work, through density functional theory calculations, the possible reaction pathways of ZrO2 ALD using tetrakis(dimethylamino)zirconium (TDMAZ) and water as the precursors were explored. The whole ZrO2 ALD reaction could be divided into two sequential reactions, TDMAZ and H2O reactions. In the TDMAZ reaction on the hydroxylated surface, the dimethylamino group of TDMAZ could be directly eliminated by substitution and ligand exchange reactions with the hydroxyl group on the surface to form dimethylamine (HN(CH3)2). In the H2O reaction with the aminated surface, the reaction process is much more complex than the TDMAZ reaction. These reactions mainly include ligand exchange reactions between the dimethylamino group of TDMAZ and H2O and coupling reactions for the formation of the bridged products and the by-product of H2O or HN(CH3)2. These insights into surface reaction mechanism of ZrO2 ALD can provide theoretical guidance for the precursor design and improving ALD preparation of other oxides and zirconium compounds, which are based ALD reaction mechanism.

Corrigendum: Reaction mechanism of atomic layer deposition of zirconium oxide using zirconium precursors bearing amino ligands and water.

[This corrects the article DOI: 10.3389/fchem.2022.1035902.].

All-nitrogen spiropentadiene-N5.

Of the pentanitrogen cation (N5 +) family, the only experimentally known isomer is the V-shaped structure 01. Here, we showed that a super-high-energy (∼100 kcal/mol above 01) all-nitrogen spiropentadiene 02 with considerable σ-delocalization deserves pursuit as the first spirocyclic all-nitrogen molecule, at least spectroscopical.