Transition state and formation process of Stone–Wales defects in graphene

Stone–Wales(SW) defects are possibly formed in graphene and other two-dimensional materials, and have multiple influence on their physical and chemical properties. In this study, the transition state of SW defects in graphene is determined with the fully discrete Peierls theory. Furthermore, the atomic formation process is investigated by means of ab-initio simulations. The atomic structure change and energetics of the SW transformation are revealed. It is found that the transition state is at the SW bond rotation of 34.5°and the activation energy barrier is about 12 eV. This work provides a new method to investigate SW transformations in graphene-like materials and to explore unknown SW-type defects in other 2D materials.

Theoretical Study on the Transition State of N-nitropyrazoles Rearrangement Reaction

Theoretical studies on the rearrangement reactions of nitropyrazoles have been investigated. In order to gain a better understanding of the intermediate process of rearrangement reactions, the transition states of the rearrangement reactions were obtained by TS method at the B3 LYP/6-311 G(d, p) level of theory. The natural bond orbital charge, electrostatic potential and frontier molecular orbital of the molecules in the process of rearrangement were analyzed, and the solvent effect was also discussed. The rearrangement of nitropyrazoles involves two transition states and one intermediate, and the nitro group and hydrogen atom are two transfer groups for rearrangement reactions. The migration of these two groups leads to the change of charge distribution and molecular structure. The structural changes of the molecules in different solvents are not significant, but the dipole moment of the molecule has obvious change.

“Transition States” Testing America's Global Strategy

Elexible variety has all along been a hallmark of America’s global strategy withdifferentiated treatment for specific nations. In the new century, Washingtondivides the major world forces into four categories in light of a comprehensive crite-rion of whether they have been fused into the international system, are going to-ward democracy or benefit world stability. They include: insiders or allies (Europeand Japan), marginalized ones (some underdeveloped African nations), outsidersor "rogues" (Iraq, North Korea) and finally, travelers on the way or "transitionstates". Interpretations by U.S. strategic reports define the "transition states"

Shock Induced Chemical Reactions of Intermetallic Mixture of Nickel and Aluminum and Associated Transition States

In this paper, numerical simulation of shock-induced chemical reactions of intermetallic mixtures is discussed. Specifically, the paper focuses on intermetallic mixture of nickel and aluminum. To initiate the chemical reactions, the thermal input or the shockwave should supply the energy to take the reactants, mixture of nickel and aluminum, to the transition state. Thus, for any numerical simulation or analysis of the shock or thermally induced chemical reaction in a continuum scale or a meso scale, it is necessary to identify the transition state. The transition state for the intermetallic mixture of nickel and the aluminum is identified in this paper and a result of the numerical simulation of the shock-induced chemical reaction, in a continuum scale is presented. The numerical solutions clearly show the chemical reactions, release of heat energy, increase of the temperature and the formation of products, following the transition state and the resulting shock-induced chemical reaction of a binary intermetallic energetic mixture of nickel and aluminum. The studies also show that the collapse of porosity is a mechanism that takes the reactants to the transition state, in shock-induced chemical reactions of binary intermetallic mixtures.

Adsorption and desorption of acetone by TiO_(2) clusters:Transition state theory and sensing analysis

TiO_(2) cluster sensitivity to acetone adsorption using transition state theory is investigated.Ti_(10)O_(20) cluster is used to perform the calculations using density functional theory with dispersion corrections.Adsorption state and transition state are calculated via thermodynamic energies,i.e.,Gibbs free energy of adsorption and activation.Reaction rate,response,response time,and recovery time as a function of temperature and acetone concentration are calculated.Acetone burning in the air due to autoignition is considered using a logistic function.The results of the theory are compared with available experimental findings that revealed the quality of both theoretical and experimental results.The response time decreases with respect to acetone concentration.On the other hand,the recovery time in the desorption phase increases with acetone concentration.The temperature of maximum response is 356℃,while the maximum response value is 2.9.

8-Membered-ring Transition States of Water Assisted Reactions in Sub-and Super-critical Water

1 Results Sub-and super-critical water is an attractive reaction medium for organic transformation because of their unique properties such as low viscosity,high density,low polarity,high solubility to organic compounds,and,of course,the greenness of the medium[1-3]. We report herein some unique reactions of unsaturated compounds in sub-and super-critical water.When allylbenzene was treated in supercritical water (SCW: 380 ℃,10 min,water density=0.35 g/mL),double bond migrated to give a mixture of allylb...

Effect of Electron Correlation and Breit Interaction on Energies, Oscillator Strengths, and Transition Rates for Low-Lying States of Helium

The transition energies, E1 transitional oscillator strengths of the spin-allowed as well as the spin-forbidden and the corresponding transition rates, and complete M1, E2, M2 forbidden transition rates for 1s^(2), 1s2s, and 1s2p states of He I, are investigated using the multi-configuration Dirac–Hartree–Fock method. In the subsequent relativistic configuration interaction computations, the Breit interaction and the QED effect are considered as perturbation, separately. Our transition energies, oscillator strengths, and transition rates are in good agreement with the experimental and other theoretical results. As a result, the QED effect is not important for helium atoms, however, the effect of the Breit interaction plays a significant role in the transition energies, the oscillator strengths and transition rates.

The Natural Law of Transition of a Charged Particle into a Compound State under the Action of an Electroscalar Field

This article is the continuation of article [1] where the experimental facts of observation of the electroscalar radiation in the spectrum of the Sun have been presented [2]. This radiation comes into the world having a long wavelength, being longitudinal and extraordinarily penetrating. In accordance with the principle of least action, the Lagrangian of the electroscalar field and the tensor of energy-moment are determined using the variation the potential and coordinates. The equation of motion the charged particle in electroscalar field is determined and the energy of particle has the negative sign with respect to the mechanical energy of particle and the energy of electromagnetic field. So, this is decreasing the electrical potential of particle during the propagation. The electroscalar energy of charged particle and field’s force acting on the particle during their motion change the particle’s electrical status which, in its turn, may trigger the transition of the particle into a compound state during interaction with any object. Due to the continuity this process can lead the particle to the state which enters into a compound state with a negative energy for a different particle’s velocity. This state is the physical vacuum’s state. Analysis of the solar spectrum demonstrates that scattering and absorption of electroscalar wave go on the cavities of solids. The spreading out of electroscalar field obeys to the law of plane wave and the transfer the energy and information can occur in vacuum and any medium.

Multimodal process monitoring based on transition-constrained Gaussian mixture model

Reliable process monitoring is important for ensuring process safety and product quality.A production process is generally characterized bymultiple operation modes,and monitoring thesemultimodal processes is challenging.Most multimodal monitoring methods rely on the assumption that the modes are independent of each other,which may not be appropriate for practical application.This study proposes a transition-constrained Gaussian mixture model method for efficient multimodal process monitoring.This technique can reduce falsely and frequently occurring mode transitions by considering the time series information in the mode identification of historical and online data.This process enables the identified modes to reflect the stability of actual working conditions,improve mode identification accuracy,and enhance monitoring reliability in cases of mode overlap.Case studies on a numerical simulation example and simulation of the penicillin fermentation process are provided to verify the effectiveness of the proposed approach inmultimodal process monitoring with mode overlap.

Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Precisely quantifying transition metal(TM) redox in bulk is a key to understand the fundamental of optimizing cathode materials in secondary batteries. At present, the commonly used methods to probe TM redox are hard X-ray absorption spectroscopy(hXAS) and soft X-ray absorption spectroscopy(sXAS).However, they are both facing challenges to precisely quantify the valence states of some transition metals such as Mn. In this paper, Mn-L iPFY(inverse partial fluorescence yield) spectra extracted from Mn-L m RIXS(mapping of resonant inelastic X-ray scattering) is adopted to quantify Mn valence states. Mn-L i PFY spectra has been considered as a bulk-sensitive, non-distorted probe of TM valence states.However, the exact precision of this method is still unclear in quantifying practical battery electrodes.Herein, a series of LiMn_(2)O_(4) electrodes with different charge and discharge states are prepared. Based on their electrochemical capacity(generally considered to be very precise), the precision of Mn iPFY in quantifying bulk Mn valence state is confirmed, and the error range is unraveled. Mn-L mRIXS iPFY thus is identified as one of the best methods to quantify the bulk Mn valence state comparing with hXAS and sXAS.

Multiple steady state phenomenon in martensitic transformation

Based on the basic facts that the martensitic transformation is a physical phenomenon which occurs in non equilibrium conditions and there exists the feedback mechanism in the martensitic transformation, the dynamical processes of the isothermal and athermal martensitic transformations were analyzed by using nonlinear theory and a bifurcation theory model was established. It is shown that a multiple steady state phenomenon can take place as austenite is cooled, and the transitions of the steady state temperature between the branches of stable steady states can be considered the transformation from austenite to martensite. This model can estimate the starting temperature of the martensitic transformation and explain some experimental features of the martensitic transformation such as the effects of cooling rate, fluctuation and austenitic grain size on the martensitic transformation. [

Magnetic Field Induction and Time Intervals of the Electron Transitions Approached in a Classical and Quantum-Mechanical Way

The motion of electron wave packets of a metal is examined classically in the presence of the magnetic field with the aim to calculate the time intervals between two states lying on the same Fermi surface. A lower limiting value of the transition time equal to about 10–18 sec is estimated as an average for the case when the states are lying on the Fermi surface having a spherical shape. Simultaneously, an upper limit for the electron circular frequency in a metal has been also derived. A formal reference of the classical transition time to the time interval entering the energy-time uncertainty relations known in quantum mechanics is obtained.

A Computational Study of Microhydrated N-Acetyl-Phenylalaninylamide (NAPA): Kinetics and Thermodynamics

The formations of [NAPA-A(H2O)n (n = 1, 2, 3, 4)] complexes have been studied employing DFT/wB97XD/cc-pVTZ computational level to understand the kinetics and thermodynamics for the hydration reactions of N-acetyl-phenylalaninylamide (NAPA). Thermodynamic parameters such as reaction energy (E), enthalpy (H), Gibb’s free energy (G), specific heat capacity (Cv), entropy (S), and change of these parameters (ΔEr, ΔHr, ΔGr, ΔCr, and ΔSr) were studied using the explicit solvent model. The predicted values of H, G, C, and S increase with the sequential addition of water in NAPA-A due to the increase in the total number of vibrational modes. On the other hand, the value of ΔEr, ΔHr, and ΔGr increases (more negative to less negative) gradually for n = 1, 2, 3, and 4 that indicates an increase of hydration in NAPA-A makes exothermic to endothermic reactions. The barrier heights for the transition states (TS) of [NAPA-A(H2O)n (n = 1, 2, 3, 4)] complexes are predicted to lie at 4.41, 4.05, 3.72 and 2.26 kcal/mol respectively below the reactants. According to the calculations, the formations of [NAPA-A(H2O)1] and [NAPA-A(H2O)2] complexes are barrierless reactions because both water molecules are strongly bonded via two hydrogen bonds in the backbone of NAPA-A. On the contrary, the reactions of [NAPA-A(H2O)3] and [NAPA-A(H2O)4] complexation are endothermic and the barrier heights are predicted to stay at 6.30 and 10.54 kcal/mol respectively above the reactants. The free energy of activation (Δ‡G0) for the reaction of [NAPA-A(H2O)1], [NAPA-A(H2O)2], [NAPA-A(H2O)3], and [NAPA-A(H2O)4] complexation are 4.43, 4.28, 3.83 and 5.11 kcal/mol respectively which are very low. As well as the rates of reactions are 3.490 × 109 s-1, 4.514 × 109 s-1, 9.688 × 109 s-1, and 1.108 × 109 s-1 respectively which are very fast and spontaneous.

Regulatory dynamics of the higher-plant PSI-LHCI supercomplex during state transitions

State transition is a fundamental light acclimation mechanism of photosynthetic organisms in response to the environmental light conditions.This process rebalances the excitation energy between photosystemI(PSl)and photosystem Il through regulated reversible binding of the light-harvesting complex Il(LHCll)to PSl.However,the structural reorganization of PSI-LHCI,the dynamic binding of LHCll,and the regulatory mechanisms underlying state transitions are less understood in higher plants.In this study,using cryoelectron microscopy we resolved the structures of PSI-LHCI in both state 1(PSI-LHCI-ST1)and state 2(PSILHCI-LHCll-ST2)from Arabidopsis thaliana.Combined genetic and functional analyses revealed novel contacts between Lhcb1 and PsaK that further enhanced the binding of the LHCll trimer to the PSI core with the known interactions between phosphorylated Lhcb2 and the PsaL/PsaH/PsaO subunits.Specifically,PsaO was absent in the PSI-LHCI-ST1 supercomplex but present in the PSI-LHCI-LHCIl-ST2 supercomplex,in which the PsaL/PsaK/PsaA subunits undergo several conformational changes to strengthen the binding of PsaO in ST2.Furthermore,the PSI-LHCI module adopts a more compact configuration with shorter Mg-to-Mg distances between the chlorophylls,which may enhance the energy transfer efficiency from the peripheral antenna to the PSl core in ST2.Collectively,our work provides novel structural and functional insights into the mechanisms of light acclimation during state transitions in higher plants.

Data-driven parametric soliton-rogon state transitions for nonlinear wave equations using deep learning with Fourier neural operator

In this paper,we develop the deep learning-based Fourier neural operator(FNO)approach to find parametric mappings,which are used to approximately display abundant wave structures in the nonlinear Schr?dinger(NLS)equation,Hirota equation,and NLS equation with the generalized PT-symmetric Scarf-II potentials.Specifically,we analyze the state transitions of different types of solitons(e.g.bright solitons,breathers,peakons,rogons,and periodic waves)appearing in these complex nonlinear wave equations.By checking the absolute errors between the predicted solutions and exact solutions,we can find that the FNO with the Ge Lu activation function can perform well in all cases even though these solution parameters have strong influences on the wave structures.Moreover,we find that the approximation errors via the physics-informed neural networks(PINNs)are similar in magnitude to those of the FNO.However,the FNO can learn the entire family of solutions under a given distribution every time,while the PINNs can only learn some specific solution each time.The results obtained in this paper will be useful for exploring physical mechanisms of soliton excitations in nonlinear wave equations and applying the FNO in other nonlinear wave equations.

Midcourse correction of Earth-Moon distant retrograde orbit transfer trajectories based on high-order state transition tensors

Midcourse correction design is key to space transfers in the cislunar space.Autonomous guidance has garnered significant attention for its promise to decrease the dependence on ground control systems.This study addresses the problem of midcourse corrections for Earth-Moon transfer orbits based on high-order state transition tensors(STTs).The scenarios considered are direct Earth-Moon transfers and low-energy transfers to lunar distant retrograde orbits(DROs),where the latter involve weak stability boundary(WSB)and lunar gravity assist(LGA)techniques.Semi-analytical formulas are provided for computing the trajectory correction maneuvers(TCMs)using high-order STTs derived using the differential algebraic method.Monte Carlo simulations are performed to evaluate the effectiveness of the proposed approach.Compared with existing explicit guidance algorithms,the STT-based approach is much cheaper computationally and features fewer final position errors.These results are promising for fast and efficient orbital autonomous correction guidance approaches in the cislunar space.

Equilibrium folding and unfolding dynamics to reveal detailed free energy landscape of src SH3 protein by magnetic tweezers

Src SH3 protein domain is a typical two-state protein which has been confirmed by research of denaturant-induced unfolding dynamics.Force spectroscopy experiments by optical tweezers and atomic force microscopy have measured the force-dependent unfolding rates with different kinds of pulling geometry.However,the equilibrium folding and unfolding dynamics at constant forces has not been reported.Here,using stable magnetic tweezers,we performed equilibrium folding and unfolding dynamic measurement and force-jump measurement of src SH3 domain with tethering points at its N-and C-termini.From the obtained force-dependent transition rates,a detailed two-state free energy landscape of src SH3 protein is constructed with quantitative information of folding free energy,transition state barrier height and position,which exemplifies the capability of magnetic tweezers to study protein folding and unfolding dynamics.

Theoretical Investigation on the Abstraction Reaction of H with (CH_3)_3SiH

The abstraction reaction of H with (CH3)3SiH was investigated at the high levels of ab initio molecule orbital theory. The geometries were optimized at the MP2 level with 6-31G( d ) basis set, and G2MP2 level was used for the final energy calculations. The theoretical analysis provides the conclusive evidence that the main process is the hydrogen abstraction from the Si-H bond, leading to the formation of H2 and silyl radicals; the hydrogen abstraction from the C-H bond has a higher barrier and is difficult to react. The kinetics was calculated with canonical variational transition-state theory (CVT) over the temperature range 200-1 000 K, and the theoretical rate constants match well with the later experimental values.

Surface for methane combustion:O(^3P)+CH4→OH+CH3

Kinetic investigations including quasi-classical trajectory and canonical unified statistical theory method calculations are carried out on a potential energy surface for the hydrogen-abstraction reaction from methane by atom O(^3P).The surface is constructed using a modified Shepard interpolation method.The ab initio calculations are performed at the CCSD(T)level.Taking account of the contribution of inner core electrons to electronic correlation interaction in ab initio electronic structure calculations,modified optimized aug-cc-pCVQZ basis sets are applied to the all-electrons calculations.On this potential energy surface,the triplet oxygen atom attacks methane in a near-collinear H-CH3 direction to form a saddle point with barrier height of 13.55 kcal/mol,which plays a key role in the kinetics of the title reaction.For the temperature range of 298-2500 K,our calculated thermal rate constants for the O(^3P)+CH4→OH+CH3 reaction show good agreement with relevant experimental data.This work provides detailed mechanism of this gas-phase reaction and a theoretical guidance for methane combustion.

Reliability Analysis of Wind Energy Generation System Using Stochastic Method

Operators of renewable energy systems (RESs) must always manage uncertainty to some extent to ensure the reliability and the security of the electric power supply source. The guiding principle in this regard is to ensure service reliability and quality by balancing load variations with the variable renewable energy (VRE) sources. If the power generated by these VRE sources is not properly managed in conjunction with the varying load, the power grid may fail to achieve the required balance. To ensure its reliable operation, reliability analysis is vital for wind energy generation system (WEGS). This paper evaluated and assessed the reliability of WEGS and a proposed varying load by first using a stochastic approach to model the WEGS and the proposed varying load after which power generation indices were used to evaluate and assess the performance of the model. The WEGS and the varying load were modelled separately after which the two were combined into one model. Full availability, partial availability, the expected energy not supplied (EENS) or loss of energy expectation (LOEE), the mean or average instantaneous electric power generation and mean instantaneous generation deficiency were the indices used for the evaluation of the WEGS. The results indicated that the electric power generation will meet the power demand during most of the transition states of the WEGS with the expectation that the variation in the load will not be at fast pace and in large quantum.