Theoretical study of spin-orbit coupling and intersystem crossing in the two-state reaction between Nb(NH_2)_3 and N_2O

The two-state mechanism of the reaction of Nb(NH2)3 with N2O on the singlet and triplet potential energy surfaces has been investigated at the B3LYP level.Crossing points between the potential energy surfaces have been located using different methods.Analysis of the strain model shows that the singlet state of the four-coordinate(N2O)Nb(NH2)3 complex with N2O bonded via terminal N atom coordination(12) is more stable in the initial stage of reaction,since the bending of the N2O fragment [Edef(N2O) = 86.1 kcal mol-1] results in an energy splitting of the doubly degenerate LUMO;the low-energy LUMO can now strongly couple with the occupied Nb-localized d orbitals,forming a back-bond and transferring charge(q = 0.82 e) from Nb(NH2)3 to the N2O ligand.Going from 32 to 12,the reacting system changes spin multiplicity near the MECP(minimal energy crossing point) region,which takes place with a spin crossing barrier of 9.6-10.0 kcal mol-1.Analysis of spin-orbit coupling(SOC) indicates that MECP will produce a significant SOC matrix element.The value of SOC is 111.52 cm-1,due to the electron shift between two perpendicular φ orbitals with the same rotation direction,and the magnitude of the spin-multi-plicity mixing increases in the small energy gap between high-and low-spin states,greatly enhancing the probability of intersystem crossing.The probabilities of single(P1 ISC) and double(P2 ISC) passes estimated at MECP(SOC = 111.52 cm-1) are approximately 1.17×10-2 and 2.32×10-2,respectively.

Theoretical study of spin-orbit coupling and zero-field splitting in the spin-forbidden two-state reaction between cobaltacyclopentadiene and isocyanate

The two-state reaction mechanism of CpCo(C_4H_4)with isocyanate on the triplet and singlet potential energy surfaces has been investigated at the B3LYP level.A study is described for the computation of spin-orbit coupling of triplet state of the minimal energy crossing point(CP)with their singlet states and of the zerofield splitting(ZFS)parameters of the triplet states,including the full one-and two-electron terms of the BreitPauli Hamiltonian.There are two key crossing points along this two-state reaction pathway.The first crossing point—CP2 exists near^1B.The reacting system will change its spin multiplicity from the triplet state to the singlet state near this crossing region.Although the spin-orbit coupling interaction and ZFS D-tensor of the CP2 region are very strong,the reaction system will occur the reverse intersystem crossing from T_1 to S_0.Therefore,its spin-flip efficiency may be lower.The second crossing point,CP3will again change its spin multiplicity from the singlet state to the triplet state in the Co-Cr bond activation pathway,leading to a decrease in the barrier height of^1TS(CF)from19.5 to 9.5 kcal/mol(1cal=4.182 J),and the efficiency of intersystem crossing from S_0 to T_1 is high because the larger spin-orbit coupling(SOC)matrix elements will result in the overpopulations of the three sublevels of T_1(3.30×10^(-1),3.32×10^(-1),and 3.38×10^(-1),respectively).

Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction

Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.

Boosting Oxygen Evolution Reaction Performance on NiFe‑Based Catalysts Through d‑Orbital Hybridization

Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.

Two-state energy model and experimental study of coal adsorb methane

There are two states of methane existing in coal, free methane and adsorptive methane. The two states of methane exchanged with each other which need the energy exchange with outside. It is released heat when methane adsorption on coal, instead of absorbed heat. According to the gas molecules Boltzmann energy distribution, is obtained the equilibrium equations of the two states of methane in coal, as well as the heat of adsorption equation when exchanged into each other. At the same time, high temperature experiments of methane adsorption on coal have been certificated to the theoretical model. At last the experimental results presented that： the two-state energy model could be accurately described the distribution of the two states of methane in the coal; the adsorption heat is related to the initial equilibrium state of methane adsorption; the adsorption heats are different with different coal ranks.

Effective Two-State Model and NOON States for Double-Well Bose-Einstein Condensates in Strong-Interaction Regime

The model of double-well Bose-Einstein condensates in the strong-interaction regime is shown to reduce adiabatically to an effective two-state model describing the Rabi oscillations between the two atomic Fock states ｜N, 0〉 and [0, N〉, and the NOON states of arbitrary ultracold atoms can therefore be generated periodically from the initial state of either one of the Foek states.

Reaction视频中用户弹幕信息交互行为的情感反应生成机理研究

深入挖掘Reaction视频中弹幕信息交互行为的情感反应机理有助于理解用户弹幕创作背后的情感生成原因及情感变化过程。本文基于情感反应模型,利用定向内容分析法对哔哩哔哩网站中11个热门视频的弹幕信息资源、视频内容以及reactor反应情况展开编码研究,构建了Reaction视频中用户弹幕信息交互行为的情感反应生成机理模型。研究发现,Reaction视频弹幕信息交互行为中的情感反应生成机理总体上遵循“信息刺激-情感反应”的路径,信息刺激有时会独立唤醒情绪或特定情感态度,有时也会通过唤醒特定情感态度进而影响情绪或内化情感态度的生成。该模型有助于提升情感反应理论在计算机协助交流中的情境化探索,也将为社交媒体中用户与信息交互提供优化建议。

COS Activation by Zr^+ in the Gas Phase:A Case of Two-state Reactivity Process

To elucidate the mechanisms of Zr ＋ reacting with COS,both the quartet and doublet potential energy surfaces （PESs） for reactions of Zr ＋ （4 F,2 D） with COS in the gas phase have been investigated in detail by means of density functional method （B3LYP）.To obtain more accurate results,the coupled cluster single-point calculations （CCSD（T）） using B3LYP optimized geometries were performed.For the C-O bond activation,the calculated results indicate that both the quartet and doublet states proceed via an insertion-elimination mechanism.For the C-S bond activation,the quartet reaction has an insertion-elimination mechanism,but the doublet reaction is a direct abstraction of the sulfur atom by Zr ＋.The C-S bond activation is found to be energetically more favorable than the C-O bond activation.It is found that the reaction of the 4 F gound state of Zr ＋ to yield ZrO ＋ is spin-forbidden （Zr ＋ （4 F） ＋ COS （1 Σ） → ZrO ＋ （2） ＋ CS （1 Σ）） and the crossing points were approximately determined.All the results have been compared with the existing experimental and theoretical data.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Large Signal Modulation Characteristics in the Transition Regime for Two-State Lasing Quantum Dot Lasers

Large-signal modulation capability, as an important performance indicator, is directly related to the high-speed optical communication technology involved. We experimentally and theoretically investigate the large-signal modulation characteristics of the simultaneous ground-state （GS） and the excited-state （ES） lasing in InAs/OaAs quantum dot laser diodes. The large-signal modulation capability of total light intensity in the transition regime from OS lasing to two-state lasing is unchanged as the bias-current increases. However, GS and ES large-signal eye diagrams show obvious variations during the transition. Relaxation oscillations and large-signal eye diagrams for OS, ES, and total light intensities are numerically simulated and analyzed in detail by using a rate-equation model. The -ndings show that a complementary relationship between the light intensities for OS and ES lasing exists in both the transition regime and the two-state lasing regime, leading to a much smaller overshooting power and a shorter settling time for the total light intensity. Therefore, the eye diagrams of GS or ES lasing are diffuse whereas those of total light intensity are constant as the bias-current increases in the transition regime.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

A Deep Two-State Gated Recurrent Unit for Particulate Matter (PM_(2.5)) Concentration Forecasting

Air pollution is a significant problem in modern societies since it has a serious impact on human health and the environment.Particulate Matter(PM_(2.5))is a type of air pollution that contains of interrupted elements with a diameter less than or equal to 2.5 m.For risk assessment and epidemiological investigations,a better knowledge of the spatiotemporal variation of PM_(2.5) concentration in a constant space-time area is essential.Conventional spatiotemporal interpolation approaches commonly relying on robust presumption by limiting interpolation algorithms to those with explicit and basic mathematical expression,ignoring a plethora of hidden but crucial manipulating aspects.Many advanced deep learning approaches have been proposed to forecast Particulate Matter(PM_(2.5)).Recurrent neural network(RNN)is one of the popular deep learning architectures which is widely employed in PM_(2.5) concentration forecasting.In this research,we proposed a Two-State Gated Recurrent Unit(TS-GRU)for monitoring and estimating the PM_(2.5) concentration forecasting system.The proposed algorithm is capable of considering both spatial and temporal hidden affecting elements spontaneously.We tested our model using data from daily PM_(2.5) dimensions taken in the contactual southeast area of the United States in 2009.In the studies,three evaluation matrices were utilized to compare the overall performance of each algorithm:Mean Absolute Error(MAE),Root Mean Square Error(RMSE),and Mean Absolute Percentage Error(MAPE).The experimental results revealed that our proposed TS-GRU model outperformed compared to the other deep learning approaches in terms of forecasting performance.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Diffusion and reaction mechanism of limestone and quartz in fluxed iron ore pellet roasting process

The increase to the proportion of fluxed pellets in the blast furnace burden is a useful way to reduce the carbon emissions in the ironmaking process.In this study,the interaction between calcium carbonate and iron ore powder and the mineralization mechanism of fluxed iron ore pellet in the roasting process were investigated through diffusion couple experiments.Scanning electron microscopy with energy dispersive spectroscopy was used to study the elements’diffusion and phase transformation during the roasting process.The results indicated that limestone decomposed into calcium oxide,and magnetite was oxidized to hematite at the early stage of preheating.With the increase in roasting temperature,the diffusion rate of Fe and Ca was obviously accelerated,while the diffusion rate of Si was relatively slow.The order of magnitude of interdiffusion coefficient of Fe_(2)O_(3)-CaO diffusion couple was 10^(−10) m^(2)·s^(−1) at a roasting temperature of 1200℃for 9 h.Ca_(2)Fe_(2)O_(5) was the initial product in the Fe_(2)O_(3)-CaO-SiO_(2) diffusion interface,and then Ca_(2)Fe_(2)O_(5) continued to react with Fe_(2)O_(3) to form CaFe_(2)O_(4).With the expansion of the diffusion region,the sillico-ferrite of calcium liquid phase was produced due to the melting of SiO_(2) into CaFe_(2)O_(4),which can strengthen the consolidation of fluxed pellets.Furthermore,andradite would be formed around a small part of quartz particles,which is also conducive to the consolidation of fluxed pellets.In addition,the principle diagram of limestone and quartz diffusion reaction in the process of fluxed pellet roasting was discussed.

Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin

This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.

Measurement Problem and Two-State Vector Formalism

In this paper, I show that an interpretation of quantum mechanics using two-state vector formalism proposed by Aharonov, Bergmann, and Lebowitz, can solve one of the measurement problems formulated by Maudlin. According to this interpretation, we can simultaneously insist that the wave function of a system is complete, that the wave function is determined by the Schr?dinger equation, and that the measurement of a physical quantity always has determinate outcomes, although Maudlin in his formulation of the measurement problem states that these three claims are mutually inconsistent. Further, I show that my interpretation does not contradict the uncertainty relation and the no-go theorem.

Einstein Dilemma and Two-State Vector Formalism

In the famous EPR paper published in 1935, Einstein, Podolsky, and Rosen suggested a thought experiment, which later became known as the “EPR experiment”. Using the EPR experiment, they posited that quantum mechanics was incomplete. Einstein, however, was dissatisfied with the EPR paper and published a second work on the EPR experiment, in which he discussed the dilemma of choosing whether quantum mechanics was incomplete or nonlocal. Currently, most physicists choose the nonlocality of quantum mechanics over Einstein’s choice of the incompleteness of quantum mechanics. However, with an appropriate alternate hypothesis, both of these choices can be rejected. Herein, I demonstrate an approach to overcome the Einstein Dilemma by proposing a new interpretation invoked by a new formalism of quantum mechanics known as two-state vector formalism.