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 ligh...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"展开更多
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...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.展开更多
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 compound...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...展开更多
The structural features and three-dimensional nature of the charge density wave (CDW) state of the layered chalcogenide 1T-TaSe2-xTex (0≤x≤2.0) are characterized by Cs-corrected transmission electron microscopy ...The structural features and three-dimensional nature of the charge density wave (CDW) state of the layered chalcogenide 1T-TaSe2-xTex (0≤x≤2.0) are characterized by Cs-corrected transmission electron microscopy measurements. Notable changes of both average structure and the CDW state arising from Te substitution for Se are clearly demonstrated in samples with x〉0.3. The commensurate CDW state characterized by the known star-of-David clustering in the 1T-TaSe2 crystal becomes visibly unstable with Te substitution and vanishes when x=0.3. The 1T-TaSe2-xTex (0.3≤x≤1.3) samples generally adopt a remarkable incommensurate CDW state with monoclinic distortion, which could be fundamentally in correlation with the strong qq-dependent electron-phonon coupling-induced period-lattice-distortion as identified in TaTe22. Systematic analysis demonstrates that the occurrence of superconductivity is related to the suppression of the commensurate CDW phase and the presence of discommensuration is an evident structural feature observed in the superconducting samples.展开更多
The two possible reaction paths of producing ethane on coupling reaction of methane through plasma were theoretically investigated by B3LYP and MP2 methods with 6-311G* respectively and further compared with the previ...The two possible reaction paths of producing ethane on coupling reaction of methane through plasma were theoretically investigated by B3LYP and MP2 methods with 6-311G* respectively and further compared with the previous results calculated from B3LYP/6-31G*. The new investigated results consistently confirmed the previous conclusion. And the influences of the calculation methods and basis sets on the calculated results were also dis-cussed.展开更多
The influences of silica volume fraction, electrolyte concentration and pH value upon the stress dependence of elastic modulus G′and viscous modulus G″ were investigated. The results show that the suspension transfo...The influences of silica volume fraction, electrolyte concentration and pH value upon the stress dependence of elastic modulus G′and viscous modulus G″ were investigated. The results show that the suspension transforms from a liquid-like state to a solid-like state with increasing the volume fraction of silica. Such a solid-like state can be transformed back into a liquid-like state under the application of a larger stress. At the higher volume fraction, the larger critical stress is required to induce the transition from solid-like to liquid-like state. As the electrolyte concentration decreases or pH value increases, the inter-particle force increases, which causes the state transition to occur at a higher stress.展开更多
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), 1s...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.展开更多
Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hamper...Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.展开更多
Optimization algorithms play a pivotal role in enhancing the performance and efficiency of systems across various scientific and engineering disciplines.To enhance the performance and alleviate the limitations of the ...Optimization algorithms play a pivotal role in enhancing the performance and efficiency of systems across various scientific and engineering disciplines.To enhance the performance and alleviate the limitations of the Northern Goshawk Optimization(NGO)algorithm,particularly its tendency towards premature convergence and entrapment in local optima during function optimization processes,this study introduces an advanced Improved Northern Goshawk Optimization(INGO)algorithm.This algorithm incorporates a multifaceted enhancement strategy to boost operational efficiency.Initially,a tent chaotic map is employed in the initialization phase to generate a diverse initial population,providing high-quality feasible solutions.Subsequently,after the first phase of the NGO’s iterative process,a whale fall strategy is introduced to prevent premature convergence into local optima.This is followed by the integration of T-distributionmutation strategies and the State Transition Algorithm(STA)after the second phase of the NGO,achieving a balanced synergy between the algorithm’s exploitation and exploration.This research evaluates the performance of INGO using 23 benchmark functions alongside the IEEE CEC 2017 benchmark functions,accompanied by a statistical analysis of the results.The experimental outcomes demonstrate INGO’s superior achievements in function optimization tasks.Furthermore,its applicability in solving engineering design problems was verified through simulations on Unmanned Aerial Vehicle(UAV)trajectory planning issues,establishing INGO’s capability in addressing complex optimization challenges.展开更多
Biomass-H_(2)O gasification is a complex thermochemical reaction,including three processes of volatile removal:homogeneous/heterogeneous reforming,biochar gasification and etching.The rate-determining step is biochar-...Biomass-H_(2)O gasification is a complex thermochemical reaction,including three processes of volatile removal:homogeneous/heterogeneous reforming,biochar gasification and etching.The rate-determining step is biochar-H_(2)O gasification and etching so the DFT is carried out to see the catalytic role of different metal elements(K/Ni)in the zigzag biochar model.The calculation results show that the gasification of biochar-H_(2)O needs to go through four processes:dissociative adsorption of water,hydrogen transfer(hydrogen desorption,hydrogen atom transfer),carbon dissolution and CO desorption.The energy barrier indicated that the most significant step in reducing the activation energy of K is reflected in the hydrogen transfer step,which is reduced from 374.14 kJ/mol to 152.41 kJ/mol;the catalytic effect of Ni is mainly reflected in the carbon dissolution step,which is reduced from 122.34 kJ/mol to 84.8 kJ/mol.The existence of K causes the edge to have a stronger attraction to H and does not destroy theπbonds of biochar molecules.The destruction ofπbonds is mainly due to the role of H free radicals,while the destruction ofπbonds will lead to easier C-C bond rupture.Ni shows a strong attraction to O in OH,which forms strong Ni-O chemical bonds.Ni can also destroy the aromatic structure directly,making the gasification easier to happen.This study explored the catalytic mechanism of K/Ni on the biochar-H_(2)O gasification at the molecular level and looked forward to the potential synergy of K/Ni,laying a foundation for experimental research and catalyst design.展开更多
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 challengi...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.展开更多
The electronic structures of LiYF4:Ce^3+ and LiYF4 crystal simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consi...The electronic structures of LiYF4:Ce^3+ and LiYF4 crystal simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa (discrete variational Xa) method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3+ ion lies around the BCB (bottom of the conduction band) while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions (WFS) with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state (TS) calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3+ is larger than that of y^3+ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation (of the nearest-neighbor and next nearest-neighbor eight fluorines) has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure (including zero-phonon line) of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.展开更多
In this study, the initial perturbations that are the easiest to trigger the Kuroshio Extension (KE) transition connecting a basic weak jet state and a strong, fairly stable meandering state, are investigated using ...In this study, the initial perturbations that are the easiest to trigger the Kuroshio Extension (KE) transition connecting a basic weak jet state and a strong, fairly stable meandering state, are investigated using a reduced-gravity shallow water ocean model and the CNOP (Conditional Nonlinear Optimal Perturbation) approach. This kind of initial perturbation is called an optimal precursor (OPR). The spatial structures and evolutionary processes of the OPRs are analyzed in detail. The results show that most of the OPRs are in the form of negative sea surface height (SSH) anomalies mainly located in a narrow band region south of the KE jet, in basic agreement with altimetric observations. These negative SSH anomalies reduce the merid- ional SSH gradient within the KE, thus weakening the strength of the jet. The KE jet then becomes more convoluted, with a high-frequency and large-amplitude variability corresponding to a high eddy kinetic energy level; this gradually strengthens the KE jet through an inverse energy cascade. Eventually, the KE reaches a high-energy state characterized by two well defined and fairly stable anticyclonic meanders. Moreover, sensitivity experiments indicate that the spatial structures of the OPRs are not sensitive to the model parameters and to the optimization times used in the analysis.展开更多
Identifying state transition and determining the critical value of the Duffing oscillator are crucial to indicating external signal existence and have a great influence on detection accuracy in weak signal detection. ...Identifying state transition and determining the critical value of the Duffing oscillator are crucial to indicating external signal existence and have a great influence on detection accuracy in weak signal detection. A circular zone counting (CZC) method is proposed in this paper, by combining the Duffing oscillator's phase trajectory feature and numerical calculation for quickly and accurately identifying state transition and determining the critical value, to realize a high- efficiency weak signal detection. Detailed model analysis and method construction of the CZC method are introduced. Numerical experiments into the reliability of the proposed CZC method compared with the maximum Lyapunov exponent (MLE) method are carried out. The CZC method is demonstrated to have better detecting ability than the MLE method, and furthermore it is simpler and clearer in calculation to extend to engineering application.展开更多
The transition state between the continuous wave region and the mode-locked region in a passively mode-locked erbium-doped fibre ring laser has been experimentally observed by utilizing the nonlinear polarization rota...The transition state between the continuous wave region and the mode-locked region in a passively mode-locked erbium-doped fibre ring laser has been experimentally observed by utilizing the nonlinear polarization rotation technique. When the pump power reaches the mode-locked threshold, the metastable pulse train with a tunable repetition rate is obtained in the transition from the continuous wave state to the passive mode-locked state via proper adjustment of the polarization controller. A simpie model has been established to explain the experimental observation.展开更多
The ab initio self-consistent DV-Xa (discrete variational Xa) method was used in its relativistic and spin-polarized model to investigate the ground-state electronic structttres of the crystal YPO4 and YPO4:RE^3+ ...The ab initio self-consistent DV-Xa (discrete variational Xa) method was used in its relativistic and spin-polarized model to investigate the ground-state electronic structttres of the crystal YPO4 and YPO4:RE^3+ (RE=Ce, Pr and Sm) and f-d transition energies of the lattice. The calculation was performed on the clusters Y5P10O32 and REY4P10O32 embedded in a microcrystal containing about 1500 ions, respectively. The ground-state calculation provided the locations of the 4f and 5d crystal-field one-electron levels of RE^3+ relative to the valence and conduction bands of host, the curve of total and the partial density of states, and the corresponding occupation numbers, etc. Especially, the transition-state calculation was performed to obtain the 4f→5d transition energies of RE^3+ in comparison to the experimental observations. The lattice relaxation caused by the dopant ion RE3+ was discussed based on the total energy calculation and the transition-state calculation of the f-d transition energies.展开更多
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...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.展开更多
Theoretical studies on the rearrangement reactions of nitropyrazoles have beeninvestigated. In order to gain a better understanding of the intermediate process of rearrangementreactions, the transition states of the r...Theoretical studies on the rearrangement reactions of nitropyrazoles have beeninvestigated. In order to gain a better understanding of the intermediate process of rearrangementreactions, the transition states of the rearrangement reactions were obtained by TS method at theB3LYP/6-311G(d, p) level of theory. The natural bond orbital charge, electrostatic potential andfrontier molecular orbital of the molecules in the process of rearrangement were analyzed, and thesolvent effect was also discussed. The rearrangement of nitropyrazoles involves two transitionstates and one intermediate, and the nitro group and hydrogen atom are two transfer groups forrearrangement reactions. The migration of these two groups leads to the change of chargedistribution and molecular structure. The structural changes of the molecules in different solventsare not significant, but the dipole moment of the molecule has obvious change.展开更多
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 ...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.展开更多
The electronic structures of LiYF4:Ce^3+ and LiYF4 crystal simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consi...The electronic structures of LiYF4:Ce^3+ and LiYF4 crystal simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa (discrete variational Xa) method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3+ ion lies around the BCB (bottom of the conduction band) while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions (WFS) with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state (TS) calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3+ is larger than that of y^3+ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation (of the nearest-neighbor and next nearest-neighbor eight fluorines) has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure (including zero-phonon line) of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.展开更多
文摘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"
文摘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.
文摘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...
基金Supported by the National Basic Research Program of China under Grant Nos 2015CB921300 and 2012CB821404the National Key Research and Development Program of China under Grant Nos 2016YFA0300300 and 2016YFA0300404+1 种基金the National Natural Science Foundation of China under Grant Nos 11474323,11604372,11274368,91221102,11190022,11674326 and 91422303the Strategic Priority Research Program(B)of the Chinese Academy of Sciences under Grant No XDB07020000
文摘The structural features and three-dimensional nature of the charge density wave (CDW) state of the layered chalcogenide 1T-TaSe2-xTex (0≤x≤2.0) are characterized by Cs-corrected transmission electron microscopy measurements. Notable changes of both average structure and the CDW state arising from Te substitution for Se are clearly demonstrated in samples with x〉0.3. The commensurate CDW state characterized by the known star-of-David clustering in the 1T-TaSe2 crystal becomes visibly unstable with Te substitution and vanishes when x=0.3. The 1T-TaSe2-xTex (0.3≤x≤1.3) samples generally adopt a remarkable incommensurate CDW state with monoclinic distortion, which could be fundamentally in correlation with the strong qq-dependent electron-phonon coupling-induced period-lattice-distortion as identified in TaTe22. Systematic analysis demonstrates that the occurrence of superconductivity is related to the suppression of the commensurate CDW phase and the presence of discommensuration is an evident structural feature observed in the superconducting samples.
基金Project supported by the Natural Science Foundation of Tianjin Education Commission (No. 20020902) and the Youth Fund Project of Tianjin Nor-mal University (No. 52LE31).
文摘The two possible reaction paths of producing ethane on coupling reaction of methane through plasma were theoretically investigated by B3LYP and MP2 methods with 6-311G* respectively and further compared with the previous results calculated from B3LYP/6-31G*. The new investigated results consistently confirmed the previous conclusion. And the influences of the calculation methods and basis sets on the calculated results were also dis-cussed.
基金the National Natural Science Foundation of China(No.2 0 2 4 30 0 2 )
文摘The influences of silica volume fraction, electrolyte concentration and pH value upon the stress dependence of elastic modulus G′and viscous modulus G″ were investigated. The results show that the suspension transforms from a liquid-like state to a solid-like state with increasing the volume fraction of silica. Such a solid-like state can be transformed back into a liquid-like state under the application of a larger stress. At the higher volume fraction, the larger critical stress is required to induce the transition from solid-like to liquid-like state. As the electrolyte concentration decreases or pH value increases, the inter-particle force increases, which causes the state transition to occur at a higher stress.
基金Supported by the National Key Research and Development Program of China (Grant No. 2017YFA0402300)the National Natural Science Foundation of China (Grant Nos. 11774344 and 11474033)。
文摘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.
基金supported by the National Key Research and Development Program of China (2022YFB4002100)the development project of Zhejiang Province's "Jianbing" and "Lingyan" (2023C01226)+4 种基金the National Natural Science Foundation of China (22278364, U22A20432, 22238008, 22211530045, and 22178308)the Fundamental Research Funds for the Central Universities (226-2022-00044 and 226-2022-00055)the Science Foundation of Donghai Laboratory (DH-2022ZY0009)the Startup Foundation for Hundred-Talent Program of Zhejiang UniversityScientific Research Fund of Zhejiang Provincial Education Department.
文摘Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.
基金supported by theKey Research and Development Project of Hubei Province(No.2023BAB094)the Key Project of Science and Technology Research Program of Hubei Educational Committee(No.D20211402)the Open Foundation of HubeiKey Laboratory for High-Efficiency Utilization of Solar Energy and Operation Control of Energy Storage System(No.HBSEES202309).
文摘Optimization algorithms play a pivotal role in enhancing the performance and efficiency of systems across various scientific and engineering disciplines.To enhance the performance and alleviate the limitations of the Northern Goshawk Optimization(NGO)algorithm,particularly its tendency towards premature convergence and entrapment in local optima during function optimization processes,this study introduces an advanced Improved Northern Goshawk Optimization(INGO)algorithm.This algorithm incorporates a multifaceted enhancement strategy to boost operational efficiency.Initially,a tent chaotic map is employed in the initialization phase to generate a diverse initial population,providing high-quality feasible solutions.Subsequently,after the first phase of the NGO’s iterative process,a whale fall strategy is introduced to prevent premature convergence into local optima.This is followed by the integration of T-distributionmutation strategies and the State Transition Algorithm(STA)after the second phase of the NGO,achieving a balanced synergy between the algorithm’s exploitation and exploration.This research evaluates the performance of INGO using 23 benchmark functions alongside the IEEE CEC 2017 benchmark functions,accompanied by a statistical analysis of the results.The experimental outcomes demonstrate INGO’s superior achievements in function optimization tasks.Furthermore,its applicability in solving engineering design problems was verified through simulations on Unmanned Aerial Vehicle(UAV)trajectory planning issues,establishing INGO’s capability in addressing complex optimization challenges.
基金Sponsored by the National Natural Science Foundation of China(Grant No.52276180)the Natural Science Foundation of Heilongjiang Province(Grant No.YQ2022E026).
文摘Biomass-H_(2)O gasification is a complex thermochemical reaction,including three processes of volatile removal:homogeneous/heterogeneous reforming,biochar gasification and etching.The rate-determining step is biochar-H_(2)O gasification and etching so the DFT is carried out to see the catalytic role of different metal elements(K/Ni)in the zigzag biochar model.The calculation results show that the gasification of biochar-H_(2)O needs to go through four processes:dissociative adsorption of water,hydrogen transfer(hydrogen desorption,hydrogen atom transfer),carbon dissolution and CO desorption.The energy barrier indicated that the most significant step in reducing the activation energy of K is reflected in the hydrogen transfer step,which is reduced from 374.14 kJ/mol to 152.41 kJ/mol;the catalytic effect of Ni is mainly reflected in the carbon dissolution step,which is reduced from 122.34 kJ/mol to 84.8 kJ/mol.The existence of K causes the edge to have a stronger attraction to H and does not destroy theπbonds of biochar molecules.The destruction ofπbonds is mainly due to the role of H free radicals,while the destruction ofπbonds will lead to easier C-C bond rupture.Ni shows a strong attraction to O in OH,which forms strong Ni-O chemical bonds.Ni can also destroy the aromatic structure directly,making the gasification easier to happen.This study explored the catalytic mechanism of K/Ni on the biochar-H_(2)O gasification at the molecular level and looked forward to the potential synergy of K/Ni,laying a foundation for experimental research and catalyst design.
基金supported in part by National Natural Science Foundation of China under Grants 61973119 and 61603138in part by Shanghai Rising-Star Program under Grant 20QA1402600+1 种基金in part by the Open Funding from Shandong Key Laboratory of Big-data Driven Safety Control Technology for Complex Systems under Grant SKDN202001in part by the Programme of Introducing Talents of Discipline to Universities(the 111 Project)under Grant B17017.
文摘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.
文摘The electronic structures of LiYF4:Ce^3+ and LiYF4 crystal simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa (discrete variational Xa) method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3+ ion lies around the BCB (bottom of the conduction band) while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions (WFS) with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state (TS) calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3+ is larger than that of y^3+ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation (of the nearest-neighbor and next nearest-neighbor eight fluorines) has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure (including zero-phonon line) of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.
基金supported by the National Natural Science Foundation of China (Grant Nos. 41576015, 41306023, 41490644 and 41490640)the Natural Science Foundation Of China (NSFC) Innovative Group (Grant No. 41421005)+1 种基金the NSFC–Shandong Joint Fund for Marine Science Research Centers (Grant No. U1406401)support from the University of Naples Parthenope (Grant No. DSTE315)
文摘In this study, the initial perturbations that are the easiest to trigger the Kuroshio Extension (KE) transition connecting a basic weak jet state and a strong, fairly stable meandering state, are investigated using a reduced-gravity shallow water ocean model and the CNOP (Conditional Nonlinear Optimal Perturbation) approach. This kind of initial perturbation is called an optimal precursor (OPR). The spatial structures and evolutionary processes of the OPRs are analyzed in detail. The results show that most of the OPRs are in the form of negative sea surface height (SSH) anomalies mainly located in a narrow band region south of the KE jet, in basic agreement with altimetric observations. These negative SSH anomalies reduce the merid- ional SSH gradient within the KE, thus weakening the strength of the jet. The KE jet then becomes more convoluted, with a high-frequency and large-amplitude variability corresponding to a high eddy kinetic energy level; this gradually strengthens the KE jet through an inverse energy cascade. Eventually, the KE reaches a high-energy state characterized by two well defined and fairly stable anticyclonic meanders. Moreover, sensitivity experiments indicate that the spatial structures of the OPRs are not sensitive to the model parameters and to the optimization times used in the analysis.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61172047 and 61071025)
文摘Identifying state transition and determining the critical value of the Duffing oscillator are crucial to indicating external signal existence and have a great influence on detection accuracy in weak signal detection. A circular zone counting (CZC) method is proposed in this paper, by combining the Duffing oscillator's phase trajectory feature and numerical calculation for quickly and accurately identifying state transition and determining the critical value, to realize a high- efficiency weak signal detection. Detailed model analysis and method construction of the CZC method are introduced. Numerical experiments into the reliability of the proposed CZC method compared with the maximum Lyapunov exponent (MLE) method are carried out. The CZC method is demonstrated to have better detecting ability than the MLE method, and furthermore it is simpler and clearer in calculation to extend to engineering application.
基金Project supported by the National Natural Science Foundation of China(Grant No.11074078)the Specialized Research Fund for the Doctoral Program of Higher Education,China(Grant No.20094407110002)+1 种基金the Key Program for Scientific and Technological Innovations of Higher Education Institutes in Guangdong Province,China(Grant No.cxzd1011)the Foundation for Distinguished Young Talents in Higher Education of Guangdong,China(Grant No.C10183)
文摘The transition state between the continuous wave region and the mode-locked region in a passively mode-locked erbium-doped fibre ring laser has been experimentally observed by utilizing the nonlinear polarization rotation technique. When the pump power reaches the mode-locked threshold, the metastable pulse train with a tunable repetition rate is obtained in the transition from the continuous wave state to the passive mode-locked state via proper adjustment of the polarization controller. A simpie model has been established to explain the experimental observation.
基金the National Natural Science Foundation of China (50332050 and 10474092)Specialized Research Fund for the Doc-toral Program of Higher Education (20060358054)
文摘The ab initio self-consistent DV-Xa (discrete variational Xa) method was used in its relativistic and spin-polarized model to investigate the ground-state electronic structttres of the crystal YPO4 and YPO4:RE^3+ (RE=Ce, Pr and Sm) and f-d transition energies of the lattice. The calculation was performed on the clusters Y5P10O32 and REY4P10O32 embedded in a microcrystal containing about 1500 ions, respectively. The ground-state calculation provided the locations of the 4f and 5d crystal-field one-electron levels of RE^3+ relative to the valence and conduction bands of host, the curve of total and the partial density of states, and the corresponding occupation numbers, etc. Especially, the transition-state calculation was performed to obtain the 4f→5d transition energies of RE^3+ in comparison to the experimental observations. The lattice relaxation caused by the dopant ion RE3+ was discussed based on the total energy calculation and the transition-state calculation of the f-d transition energies.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11847089)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (Grant No. 20KJB430002)GuiZhou Provincial Department of Science and Technology, China (Grant No. QKHJC[2019]1167)。
文摘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.
文摘Theoretical studies on the rearrangement reactions of nitropyrazoles have beeninvestigated. In order to gain a better understanding of the intermediate process of rearrangementreactions, the transition states of the rearrangement reactions were obtained by TS method at theB3LYP/6-311G(d, p) level of theory. The natural bond orbital charge, electrostatic potential andfrontier molecular orbital of the molecules in the process of rearrangement were analyzed, and thesolvent effect was also discussed. The rearrangement of nitropyrazoles involves two transitionstates and one intermediate, and the nitro group and hydrogen atom are two transfer groups forrearrangement reactions. The migration of these two groups leads to the change of chargedistribution and molecular structure. The structural changes of the molecules in different solventsare not significant, but the dipole moment of the molecule has obvious change.
基金the support from the key research and development and promotion of special projects (scientific and technological research) of Henan province (212102210188)the National Natural Science Foundation of China (51604244)the Energy Storage Materials and Processes Key Laboratory of Henan Province Open Fund (2021003)。
文摘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.
文摘The electronic structures of LiYF4:Ce^3+ and LiYF4 crystal simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa (discrete variational Xa) method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3+ ion lies around the BCB (bottom of the conduction band) while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions (WFS) with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state (TS) calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3+ is larger than that of y^3+ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation (of the nearest-neighbor and next nearest-neighbor eight fluorines) has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure (including zero-phonon line) of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.