The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the...The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.展开更多
The algebraic energy method （AEM） is applied to the study of molecular dissociation energy De for 11 heteronuclear diatomic electronic states： a^3∑＋ state of NaK, X^2∑＋ state of XeBr, X^2∑＋ state of HgI, X^1...The algebraic energy method （AEM） is applied to the study of molecular dissociation energy De for 11 heteronuclear diatomic electronic states： a^3∑＋ state of NaK, X^2∑＋ state of XeBr, X^2∑＋ state of HgI, X^1∑＋ state of LiH, A3∏（1） state of IC1, X^1∑＋ state of CsH, A（3∏1） and B0＋（3∏） states of CIF, 21∏ state of KRb, X^1∑＋ state of CO, and c^3∑＋ state of NaK molecule. The results show that the values of De computed by using the AEM are satisfactorily accurate compared with experimental ones. The AEM can serve as an economic and useful tool to generate a reliable De within an allowed experimental error for the electronic states whose molecular dissociation energies are unavailable from the existing literature展开更多
Vanadium battery has fast and large capacity charge and discharge characteristics, and the concentration and stability of the battery electrolyte are the key to the electrolyte performance. In actual, with higher acid...Vanadium battery has fast and large capacity charge and discharge characteristics, and the concentration and stability of the battery electrolyte are the key to the electrolyte performance. In actual, with higher acidity and higher concentration of the vanadium battery electrolyte, the ion-pair is dominant. The ion-pair dissociation constant is one of the important thermodynamic data related to battery performance. The vanadyl sulfate conductivity in aqueous solution was determined using the conductance method at 298.15K. Using the origin data fitting, the limiting molar conductance is obtained, and then by the improved Ostwald dilution law and the Davies equation, the activity coefficient is solved so as to obtain the ionic strength of the true solution. Using the Fuoss method, the dissociation constant of vanadyl sulfate ion-pair was calculated. At last, the vanadyl sulfate limiting molar conductance (Λ <sub> 0 </sub>) is 174.8251748 S·dm<sup>2</sup>·mol<sup>?1</sup>, and the vanadyl sulfate ion-pair dissociation constant K <sub>d</sub> is 0.002636367, and then other thermodynamic properties can be studied.展开更多
The numerical simulation and analysis of natural gas hydrates with heat and mass transfer are essential for identifying and predicting reservoir states during dissociation and seepage processes.In specific cases,the t...The numerical simulation and analysis of natural gas hydrates with heat and mass transfer are essential for identifying and predicting reservoir states during dissociation and seepage processes.In specific cases,the transported substance may undergo phase transitions between solid,liquid,or gas states during dissociation and hydration processes.To effectively predict hydrate dissociation performance influenced by multi-field coupling processes,this study proposes a novel bond-based peridynamic coupled finite difference model that accounts for gas-liquid two-phase seepage behavior.The developed peridynamic(PD)model simulates hydrate dissociation reactions accompanied by gas-liquid seepage,mass transfer,and heat transfer phenomena.The formulation demonstrates strong agreement with established analytical solutions for one-dimensional problems and finite element transient solutions for two-dimensional problems in the literature,validating the accuracy and reliability of the newly constructed model.This research presents an innovative approach to simulate heat transport and multiphase flow phenomena associated with hydrate dissociation.展开更多
In this paper,a composite numerical scheme is proposed to solve the threedimensional Darcy-Forchheimer miscible displacement problem with positive semi-definite assumptions.A mixed finite element is used for the fow e...In this paper,a composite numerical scheme is proposed to solve the threedimensional Darcy-Forchheimer miscible displacement problem with positive semi-definite assumptions.A mixed finite element is used for the fow equation.The velocity and pressure are computed simultaneously.The accuracy of velocity is improved one order.The concentration equation is solved by using mixed finite element,multi-step difference and upwind approximation.A multi-step method is used to approximate time derivative for improving the accuracy.The upwind approximation and an expanded mixed finite element are adopted to solve the convection and diffusion,respectively.The composite method could compute the diffusion flux and its gradient.It possibly becomes an eficient tool for solving convection-dominated diffusion problems.Firstly,the conservation of mass holds.Secondly,the multi-step method has high accuracy.Thirdly,the upwind approximation could avoid numerical dispersion.Using numerical analysis of a priori estimates and special techniques of differential equations,we give an error estimates for a positive definite problem.Numerical experiments illustrate its computational efficiency and feasibility of application.展开更多
The work considers the problem of gas hydrate dissociation in a porous medium using the two-term Forchheimer law,corresponding to high flow rates of reservoir fluids.Such rates can arise during the decomposition of ga...The work considers the problem of gas hydrate dissociation in a porous medium using the two-term Forchheimer law,corresponding to high flow rates of reservoir fluids.Such rates can arise during the decomposition of gas hydrates,since a large amount of gas is released.Intensive emissions of gases from the earth’s interior are observed on the ocean floor.They are also associated with a large number of subvertical geological structures under the ocean floor,coming to the surface in the formof local ring funnels(pockmarks).Many similar objects have also been found on land.Particular interest in this problemis caused by climate threats associated with the release of greenhouse gases.The movement of gas released fromthe hydrate to the breakthrough channel is similar to the gas inflow to the well(without hydrate),which is usually described by a two-term filtration law.In this work,a mathematical model of gas hydrate dissociation with a nonlinear Forchheimer-type law ofmotion is developed.The systemis split in two blocks by physical processes,taking into account the quadratic correction to the velocity in the filtration law.The first block is responsible for the convective transfer of saturation parameters in the model,water,gas and hydrate saturations are taken into account.The second block corresponds to the equation of dissipative piezoconductivity with a different number of thermodynamic degrees of freedom,taking into account heat and mass transfer in a porous medium.The performed splitting allows using explicit-implicit difference schemes when solving problems and avoiding strong refinement of the step in time and space.For numerical modeling,the support operator method is used,which makes it possible to discretize partial differential equations on irregular grids,which allows taking into account the complex geometry and lithology of the reservoir.A difference scheme based on the support operator method is developed,which,due to the mutually consistent approximation of vector analysis operations(divergence and gradient),allows to take into account the various flux laws between adjacent grid cells,including quadratic corrections to the velocity.Based on the developed numerical algorithms and their program implementations,calculations of gas hydrate dissociation are performed both in a reservoir of simple geometric structure and in a heterogeneous reservoir of complex configuration.The results obtained correspond to the physics of the processes under consideration.展开更多
Life science has a need for detection methods that are label-free and real-time. In this paper, we have selected staphylococcal protein A （SPA） and swine immunoglobulin G （IgG）, and monitor the bindings between SP...Life science has a need for detection methods that are label-free and real-time. In this paper, we have selected staphylococcal protein A （SPA） and swine immunoglobulin G （IgG）, and monitor the bindings between SPA and swine IgG with different concentrations, as well as the dissociations of SPA-swine IgG complex in different pH values of phosphate buffer by oblique-incidence reflectivity difference （OIRD） in a label-free and real-time fashion. We obtain the ON and OFF reaction dynamic curves corresponding to the bindings and dissociations of SPA and swine IgG. Through our analysis of the experimental results, we have been able to obtain the damping coefficients and the dissociation time of SPA and swine IgG for different pH values of the phosphate buffer. The results prove that the OIRD technique is a competing method for monitoring the dynamic processes of biomolecule interaction and achieving the quantitative information of reaction kinetics.展开更多
Two methods, rapidly depressurizing to 0.1 MPa at a constant temperature and rising temperature under equilibrium P, T conditions, were used to study the dissociation of pure CH4 hydrate formed below the ice point. At...Two methods, rapidly depressurizing to 0.1 MPa at a constant temperature and rising temperature under equilibrium P, T conditions, were used to study the dissociation of pure CH4 hydrate formed below the ice point. At a constant temperature with rapidly depressurizing to 0.1 MPa, CH4 hydrate dissociated rapidly at initial dissociation and then the dissociation rate gradually decreased. However, the dissociation of CH4 hydrate at temperatures of 261 to 266 K was much faster than that at temperatures of 269 to 272 K, indicating its anomalous preservation. Under an equilibrium P, T conditions, rising temperature had extensively controlling impact on dissociation of CH4 hydrate at equilibrium pressures of 2.31, 2.16 and 1.96 MPa. In this study, we report the effect of pressure on CH4 hydrate dissociation, especially the effect of equilibrium pressure on dissociation at various melting temperatures. And we find that the ice particles size of CH4 hydrate formed may dominant the CH4 hydrate dissociation. Dissociation of CH4 hydrate formed from ice particles of smaller than 250 μm may not have an anomalous preservation below the ice point, while particles larger than 250 μm may have more extensive anomalous preservation.展开更多
On basis of bond dissociation energies （BDEs） for BH2, B（OH）2, BCl2, and BCl, the diffusion Monte Carlo （DMC） method is applied to explore the BDEs of HB-H, HOB-OH, ClB-Cl, and B-Cl. The effect of the choice of ...On basis of bond dissociation energies （BDEs） for BH2, B（OH）2, BCl2, and BCl, the diffusion Monte Carlo （DMC） method is applied to explore the BDEs of HB-H, HOB-OH, ClB-Cl, and B-Cl. The effect of the choice of orbitals, as well as the backflow transformation, is studied. The Slater-Jastrow DMC algorithm gives BDEs of 359.1±0.12 kJ/mol for HB-H, 410.5±0.50 kJ/mol for HOB-OH, 357.8±1.46 kJ/mol for ClB-Cl, and 504.5±0.96 kJ/mol for B-Cl using B3PW91 orbitals and similar BDEs when B3LYP orbitals are used. DMC with backflow corrections （BF-DMC） gives a HB-H BDE of 369.9±0.12 kJ/mol which is close to one of the available experimental value （375.8 kJ/mol）. In the case of HOB-OH BDE, the BF-DMC calculation is 446.04-1.84 k J/mol that is closer to the experimental BDE. The BF-DMC BDE for ClB-Cl is 343.2±2.34 kJ/mol and the BF-DMC B-Cl BDE is 523.3±0.33 kJ/mol, which are close to the experimental BDEs, 341.9 and 530.0 kJ/mol, respectively.展开更多
This paper studies full vibrational spectra {Ev} and molecular dissociation energies De by using conventional least-squares （LS） fitting and an algebraic method （AM） proposed recently for 10 diatomic electronic st...This paper studies full vibrational spectra {Ev} and molecular dissociation energies De by using conventional least-squares （LS） fitting and an algebraic method （AM） proposed recently for 10 diatomic electronic states of ^7Li2, Na2, NaK and NaLi molecules based on some known experimental vibrational energies in a subset [Ev^expt] respectively. Studies show that： （1） although both the full AM spectrum {Ev^AM} and the LS spectrum {Ev^LS} can reproduce the known experimental energies in [Ev^expt], the {EAM} is superior to the {Ev^LS} in that the high-lying AM vibrational energies which may not be available experimentally have better or much better accuracy than those LS counterparts in {Ev^LS}, and so is the AM dissociation energy De^AM; （2） the main source of the errors in the data obtained by using the LS fitting is that the fitting which is just a pure mathematical process does not use any physical criteria that must be satisfied by the full vibrational spectrum, while the AM method does. This study suggests that when fitting or solving a physical equation using a set of source data, it is important not only to apply a proper mathematical tool, but also to use correct physical criteria which measure the physical properties of the data, kick out those data having bigger errors, and impose conditional convergence on the numerical process.展开更多
Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies（BDEs） for 15 acids.These compounds are studied by utilizing the hybrid density func...Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies（BDEs） for 15 acids.These compounds are studied by utilizing the hybrid density functional theory（DFT）（B3LYP,B3PW91,B3P86,PBE1PBE） and the complete basis set（CBS-Q） method in conjunction with the 6311G^＊＊ basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.展开更多
In this study, a reliable algorithm to develop approximate solutions for the problem of fluid flow over a stretching or shrinking sheet is proposed. It is depicted that the differential transform method (DTM) solution...In this study, a reliable algorithm to develop approximate solutions for the problem of fluid flow over a stretching or shrinking sheet is proposed. It is depicted that the differential transform method (DTM) solutions are only valid for small values of the independent variable. The DTM solutions diverge for some differential equations that extremely have nonlinear behaviors or have boundary-conditions at infinity. For this reason the governing boundary-layer equations are solved by the Multi-step Differential Transform Method (MDTM). The main advantage of this method is that it can be applied directly to nonlinear differential equations without requiring linearization, discretization, or perturbation. It is a semi analytical-numerical technique that formulizes Taylor series in a very different manner. By applying the MDTM the interval of convergence for the series solution is increased. The MDTM is treated as an algorithm in a sequence of intervals for finding accurate approximate solutions for systems of differential equations. It is predicted that the MDTM can be applied to a wide range of engineering applications.展开更多
This paper is aimed at solving the nonlinear time-fractional partial differential equation with two small parameters arising from option pricing model in financial economics.The traditional reproducing kernel(RK)metho...This paper is aimed at solving the nonlinear time-fractional partial differential equation with two small parameters arising from option pricing model in financial economics.The traditional reproducing kernel(RK)method which deals with this problem is very troublesome.This paper proposes a new method by adaptive multi-step piecewise interpolation reproducing kernel(AMPIRK)method for the first time.This method has three obvious advantages which are as follows.Firstly,the piecewise number is reduced.Secondly,the calculation accuracy is improved.Finally,the waste time caused by too many fragments is avoided.Then four numerical examples show that this new method has a higher precision and it is a more timesaving numerical method than the others.The research in this paper provides a powerful mathematical tool for solving time-fractional option pricing model which will play an important role in financial economics.展开更多
The dynamics of the double-channel dissociation of the NaCs molecule is investigated by using the time-dependent wave packet （TDWP） method with the ＂split operator-Fourier transform＂ scheme. At a given wavelength ...The dynamics of the double-channel dissociation of the NaCs molecule is investigated by using the time-dependent wave packet （TDWP） method with the ＂split operator-Fourier transform＂ scheme. At a given wavelength and intensity of laser pulse, the population of each state changing with time is obtained. The photo-absorption spectra and kinetic- energy distribution of the dissociation fragments, which exhibit vibration-level structure and dispersion of the wave packet, respectively, are also obtained. The results show that by increasing the laser intensity, one can find not only the band center shift of the photo-absorption spectrum, but also the change of the fragment energy. The appearance of the diffusive band in the photo-absorption spectrum and the multiple peaks in the kinetic-energy spectrum can be attributed to the effects of the predissoeiation limit and the external field.展开更多
This paper obtains accurate vibrational spectroscopic constants and full vibrational energy spectrum by the al- gebraic method （AM） for some electronic states of halogen diatomic molecules. Motivated by the recent s...This paper obtains accurate vibrational spectroscopic constants and full vibrational energy spectrum by the al- gebraic method （AM） for some electronic states of halogen diatomic molecules. Motivated by the recent success of obtaining the dissociation energies of Li2 molecule by using a new analytical formula, it further extends the formula to study the dissociation energies of halogen diatomic molecules. The results show that the AM spectrum and the theoretical dissociation energies agree well with RKR data and experimental data respectively.展开更多
The photo-dissociation dynamics of LiF is investigated with newly constructed accurate ab initio potential energy curves （PECs） using the time-dependent quantum wave packet method. The oscillations and decay of the ...The photo-dissociation dynamics of LiF is investigated with newly constructed accurate ab initio potential energy curves （PECs） using the time-dependent quantum wave packet method. The oscillations and decay of the wave packet on the adiabats as a function of time are given, which can be compared with the femtosecond transition-state （FTS） spectroscopy. The photo-absorption spectra and the kinetic-energy distribution of the dissociation fragments, which can exhibit the vibration-level structure and the dispersion of the wave packet, respectively, are also obtained. The investigation shows a blue shift of the band center for the photo-absorption spectrum and multiple peaks in the kinetic-energy spectrum with increasing laser intensity, which can be attributed to external field effects. By analyzing the oscillations of the wave packet evolving on the upper adiabat, an approximate inversion scheme is devised to roughly deduce its shape.展开更多
Within an extended Su–Schrieffer–Heeger model including impurity interactions,the dynamical process of exciton dissociation in the presence of an external electric field is investigated by using a non-adiabatic evol...Within an extended Su–Schrieffer–Heeger model including impurity interactions,the dynamical process of exciton dissociation in the presence of an external electric field is investigated by using a non-adiabatic evolution method.Under the action of impurities,the stability as well as the effective mass of the exciton is reduced.Our results show that the field required to dissociate the excitons depends sensitively on the strength of the impurity potential.As the impurity potential strength increases,the dissociation field decreases effectively.The theoretical results are expected to provide useful predictions concerning which polymers with properly impurity-assisted interactions are likely to be more suitable for use in organic solar cells.展开更多
The activation and dissociation of hydrogen molecules(H_(2))on the Cu(001)surface are studied theoretically.Using first-principles calculations,the activation barrier for the dissociation of H_(2) on Cu(001)is determi...The activation and dissociation of hydrogen molecules(H_(2))on the Cu(001)surface are studied theoretically.Using first-principles calculations,the activation barrier for the dissociation of H_(2) on Cu(001)is determined to be~0.59 eV in height.It is found that the electron transfer from the copper substrate to H_(2) plays a key role in the activation and breaking of the H–H bond,and the formation of the Cu–H bonds.Two stationary states are identified at around the critical height of bond breaking,corresponding to the molecular and the dissociative states,respectively.Using the transfer matrix method,we also investigate the role of quantum tunneling in the dissociation process along the minimum energy pathway(MEP),which is found to be significant at or below room temperature.At a given temperature,the tunneling contributions due to the translational and the vibrational motions of H_(2) are quantified for the dissociation process.Within a wide range of temperature,the effects of quantum tunneling on the effective barriers of dissociation and the rate constants are observed.The deduced energetic parameters associated with the thermal equilibrium and non-equilibrium(molecular beam)conditions are comparable to experimental data.In the low-temperature region,the crossover from classical to quantum regime is identified.展开更多
This paper employs a multi-parameter multi-step chaos control method, which is built up on the OGY method, to stabilize desirable UPOs of a gear system with elastomeric web as a high-dimensional and non-hyperbolic cha...This paper employs a multi-parameter multi-step chaos control method, which is built up on the OGY method, to stabilize desirable UPOs of a gear system with elastomeric web as a high-dimensional and non-hyperbolic chaotic system, and the analyses are carried out. Three types of relations between components of a certain control parameter combination are defined in a certain control process. Special emphasis is put on the comparison of control efficiencies of the multi-parameter multi-step method and single-parameter multi-step method. The numerical experiments show the ability to switch between different orbits and the method can be a good chaos control alternative since it provides a more effective UPOs stabilization of high-dimensional and non-hyperbolic chaotic systems than the single-parameter chaos control, and according to the relation between components of each parameter combination, the best combination for chaos control in a certain UPO stabilization process are obtained.展开更多
In this paper, we studied the process of dissociation unimolecular of the evaporation of H+2n+1 hydrogen clusters according to size, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constants k(E) were ...In this paper, we studied the process of dissociation unimolecular of the evaporation of H+2n+1 hydrogen clusters according to size, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constants k(E) were determined with the use of statistical theory of unimolecular reactions using various approximations. In our work, we used the products frequencies instead of transitions frequencies in the calculation of unimolecular dissociation rates obtained by three models RRKM. The agreement between the experimental cross section ratio and calculated rate ratio with direct count approximation seems to be reasonable.展开更多
文摘The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.
基金Project supported by the Science Foundation of China West Normal University （Grant No 05B016） and the Science Foundation of Sichuan province Educational Bureau of China （Grant No 2006A080）.
文摘The algebraic energy method （AEM） is applied to the study of molecular dissociation energy De for 11 heteronuclear diatomic electronic states： a^3∑＋ state of NaK, X^2∑＋ state of XeBr, X^2∑＋ state of HgI, X^1∑＋ state of LiH, A3∏（1） state of IC1, X^1∑＋ state of CsH, A（3∏1） and B0＋（3∏） states of CIF, 21∏ state of KRb, X^1∑＋ state of CO, and c^3∑＋ state of NaK molecule. The results show that the values of De computed by using the AEM are satisfactorily accurate compared with experimental ones. The AEM can serve as an economic and useful tool to generate a reliable De within an allowed experimental error for the electronic states whose molecular dissociation energies are unavailable from the existing literature
基金financially supported by the National Natural Science Foundation of China(No.21273152)
文摘Vanadium battery has fast and large capacity charge and discharge characteristics, and the concentration and stability of the battery electrolyte are the key to the electrolyte performance. In actual, with higher acidity and higher concentration of the vanadium battery electrolyte, the ion-pair is dominant. The ion-pair dissociation constant is one of the important thermodynamic data related to battery performance. The vanadyl sulfate conductivity in aqueous solution was determined using the conductance method at 298.15K. Using the origin data fitting, the limiting molar conductance is obtained, and then by the improved Ostwald dilution law and the Davies equation, the activity coefficient is solved so as to obtain the ionic strength of the true solution. Using the Fuoss method, the dissociation constant of vanadyl sulfate ion-pair was calculated. At last, the vanadyl sulfate limiting molar conductance (Λ <sub> 0 </sub>) is 174.8251748 S·dm<sup>2</sup>·mol<sup>?1</sup>, and the vanadyl sulfate ion-pair dissociation constant K <sub>d</sub> is 0.002636367, and then other thermodynamic properties can be studied.
基金financially supported by the National Natural Science Foundation of China(General Program,Grant No.52374011)the Research and Innovation Fund for Graduate Students of Southwest Petroleum University(Grant No.2021CXYB04)the Sichuan Province Science and Technology Support Program(Grant No.2023NSFSC1980)。
文摘The numerical simulation and analysis of natural gas hydrates with heat and mass transfer are essential for identifying and predicting reservoir states during dissociation and seepage processes.In specific cases,the transported substance may undergo phase transitions between solid,liquid,or gas states during dissociation and hydration processes.To effectively predict hydrate dissociation performance influenced by multi-field coupling processes,this study proposes a novel bond-based peridynamic coupled finite difference model that accounts for gas-liquid two-phase seepage behavior.The developed peridynamic(PD)model simulates hydrate dissociation reactions accompanied by gas-liquid seepage,mass transfer,and heat transfer phenomena.The formulation demonstrates strong agreement with established analytical solutions for one-dimensional problems and finite element transient solutions for two-dimensional problems in the literature,validating the accuracy and reliability of the newly constructed model.This research presents an innovative approach to simulate heat transport and multiphase flow phenomena associated with hydrate dissociation.
基金supported by the Natural Science Foundation of Shandong Province(ZR2021MA019)the National Natural Science Foundation of China(11871312)。
文摘In this paper,a composite numerical scheme is proposed to solve the threedimensional Darcy-Forchheimer miscible displacement problem with positive semi-definite assumptions.A mixed finite element is used for the fow equation.The velocity and pressure are computed simultaneously.The accuracy of velocity is improved one order.The concentration equation is solved by using mixed finite element,multi-step difference and upwind approximation.A multi-step method is used to approximate time derivative for improving the accuracy.The upwind approximation and an expanded mixed finite element are adopted to solve the convection and diffusion,respectively.The composite method could compute the diffusion flux and its gradient.It possibly becomes an eficient tool for solving convection-dominated diffusion problems.Firstly,the conservation of mass holds.Secondly,the multi-step method has high accuracy.Thirdly,the upwind approximation could avoid numerical dispersion.Using numerical analysis of a priori estimates and special techniques of differential equations,we give an error estimates for a positive definite problem.Numerical experiments illustrate its computational efficiency and feasibility of application.
基金the framework of the state assignment of Keldysh Institute of Applied Mathematics of RAS(Project No.125020701776-0)the Ministry of Education and Science of Russia for IO RAS(Project No.FMWE-2024-0018).
文摘The work considers the problem of gas hydrate dissociation in a porous medium using the two-term Forchheimer law,corresponding to high flow rates of reservoir fluids.Such rates can arise during the decomposition of gas hydrates,since a large amount of gas is released.Intensive emissions of gases from the earth’s interior are observed on the ocean floor.They are also associated with a large number of subvertical geological structures under the ocean floor,coming to the surface in the formof local ring funnels(pockmarks).Many similar objects have also been found on land.Particular interest in this problemis caused by climate threats associated with the release of greenhouse gases.The movement of gas released fromthe hydrate to the breakthrough channel is similar to the gas inflow to the well(without hydrate),which is usually described by a two-term filtration law.In this work,a mathematical model of gas hydrate dissociation with a nonlinear Forchheimer-type law ofmotion is developed.The systemis split in two blocks by physical processes,taking into account the quadratic correction to the velocity in the filtration law.The first block is responsible for the convective transfer of saturation parameters in the model,water,gas and hydrate saturations are taken into account.The second block corresponds to the equation of dissipative piezoconductivity with a different number of thermodynamic degrees of freedom,taking into account heat and mass transfer in a porous medium.The performed splitting allows using explicit-implicit difference schemes when solving problems and avoiding strong refinement of the step in time and space.For numerical modeling,the support operator method is used,which makes it possible to discretize partial differential equations on irregular grids,which allows taking into account the complex geometry and lithology of the reservoir.A difference scheme based on the support operator method is developed,which,due to the mutually consistent approximation of vector analysis operations(divergence and gradient),allows to take into account the various flux laws between adjacent grid cells,including quadratic corrections to the velocity.Based on the developed numerical algorithms and their program implementations,calculations of gas hydrate dissociation are performed both in a reservoir of simple geometric structure and in a heterogeneous reservoir of complex configuration.The results obtained correspond to the physics of the processes under consideration.
基金Supported by the Key Research Program of Chinese Academy of Sciences
文摘Life science has a need for detection methods that are label-free and real-time. In this paper, we have selected staphylococcal protein A （SPA） and swine immunoglobulin G （IgG）, and monitor the bindings between SPA and swine IgG with different concentrations, as well as the dissociations of SPA-swine IgG complex in different pH values of phosphate buffer by oblique-incidence reflectivity difference （OIRD） in a label-free and real-time fashion. We obtain the ON and OFF reaction dynamic curves corresponding to the bindings and dissociations of SPA and swine IgG. Through our analysis of the experimental results, we have been able to obtain the damping coefficients and the dissociation time of SPA and swine IgG for different pH values of the phosphate buffer. The results prove that the OIRD technique is a competing method for monitoring the dynamic processes of biomolecule interaction and achieving the quantitative information of reaction kinetics.
基金supported by the Key Projector of Chinese Academy of Science (No. KZCX-YW-330)the National Science Fund Fostering Talents in Basic Research to Glaciology and Geocryology (Grant No. J0630966)
文摘Two methods, rapidly depressurizing to 0.1 MPa at a constant temperature and rising temperature under equilibrium P, T conditions, were used to study the dissociation of pure CH4 hydrate formed below the ice point. At a constant temperature with rapidly depressurizing to 0.1 MPa, CH4 hydrate dissociated rapidly at initial dissociation and then the dissociation rate gradually decreased. However, the dissociation of CH4 hydrate at temperatures of 261 to 266 K was much faster than that at temperatures of 269 to 272 K, indicating its anomalous preservation. Under an equilibrium P, T conditions, rising temperature had extensively controlling impact on dissociation of CH4 hydrate at equilibrium pressures of 2.31, 2.16 and 1.96 MPa. In this study, we report the effect of pressure on CH4 hydrate dissociation, especially the effect of equilibrium pressure on dissociation at various melting temperatures. And we find that the ice particles size of CH4 hydrate formed may dominant the CH4 hydrate dissociation. Dissociation of CH4 hydrate formed from ice particles of smaller than 250 μm may not have an anomalous preservation below the ice point, while particles larger than 250 μm may have more extensive anomalous preservation.
文摘On basis of bond dissociation energies （BDEs） for BH2, B（OH）2, BCl2, and BCl, the diffusion Monte Carlo （DMC） method is applied to explore the BDEs of HB-H, HOB-OH, ClB-Cl, and B-Cl. The effect of the choice of orbitals, as well as the backflow transformation, is studied. The Slater-Jastrow DMC algorithm gives BDEs of 359.1±0.12 kJ/mol for HB-H, 410.5±0.50 kJ/mol for HOB-OH, 357.8±1.46 kJ/mol for ClB-Cl, and 504.5±0.96 kJ/mol for B-Cl using B3PW91 orbitals and similar BDEs when B3LYP orbitals are used. DMC with backflow corrections （BF-DMC） gives a HB-H BDE of 369.9±0.12 kJ/mol which is close to one of the available experimental value （375.8 kJ/mol）. In the case of HOB-OH BDE, the BF-DMC calculation is 446.04-1.84 k J/mol that is closer to the experimental BDE. The BF-DMC BDE for ClB-Cl is 343.2±2.34 kJ/mol and the BF-DMC B-Cl BDE is 523.3±0.33 kJ/mol, which are close to the experimental BDEs, 341.9 and 530.0 kJ/mol, respectively.
基金Project supported by the National Natural Science Foundation of China (Grant No 10774105)the Science Foundation of the Chinese Educational Ministry
文摘This paper studies full vibrational spectra {Ev} and molecular dissociation energies De by using conventional least-squares （LS） fitting and an algebraic method （AM） proposed recently for 10 diatomic electronic states of ^7Li2, Na2, NaK and NaLi molecules based on some known experimental vibrational energies in a subset [Ev^expt] respectively. Studies show that： （1） although both the full AM spectrum {Ev^AM} and the LS spectrum {Ev^LS} can reproduce the known experimental energies in [Ev^expt], the {EAM} is superior to the {Ev^LS} in that the high-lying AM vibrational energies which may not be available experimentally have better or much better accuracy than those LS counterparts in {Ev^LS}, and so is the AM dissociation energy De^AM; （2） the main source of the errors in the data obtained by using the LS fitting is that the fitting which is just a pure mathematical process does not use any physical criteria that must be satisfied by the full vibrational spectrum, while the AM method does. This study suggests that when fitting or solving a physical equation using a set of source data, it is important not only to apply a proper mathematical tool, but also to use correct physical criteria which measure the physical properties of the data, kick out those data having bigger errors, and impose conditional convergence on the numerical process.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11047176)the Research Foundation of Education Bureau of Hubei Province,China (Grant Nos. Q20111305,B20101303,T201204,B20111304,and Q20091215)
文摘Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies（BDEs） for 15 acids.These compounds are studied by utilizing the hybrid density functional theory（DFT）（B3LYP,B3PW91,B3P86,PBE1PBE） and the complete basis set（CBS-Q） method in conjunction with the 6311G^＊＊ basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.
文摘In this study, a reliable algorithm to develop approximate solutions for the problem of fluid flow over a stretching or shrinking sheet is proposed. It is depicted that the differential transform method (DTM) solutions are only valid for small values of the independent variable. The DTM solutions diverge for some differential equations that extremely have nonlinear behaviors or have boundary-conditions at infinity. For this reason the governing boundary-layer equations are solved by the Multi-step Differential Transform Method (MDTM). The main advantage of this method is that it can be applied directly to nonlinear differential equations without requiring linearization, discretization, or perturbation. It is a semi analytical-numerical technique that formulizes Taylor series in a very different manner. By applying the MDTM the interval of convergence for the series solution is increased. The MDTM is treated as an algorithm in a sequence of intervals for finding accurate approximate solutions for systems of differential equations. It is predicted that the MDTM can be applied to a wide range of engineering applications.
基金the National Natural Science Foundation of China(Grant Nos.71961022,11902163,12265020,and 12262024)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(Grant Nos.2019BS01011 and 2022MS01003)+5 种基金2022 Inner Mongolia Autonomous Region Grassland Talents Project-Young Innovative and Entrepreneurial Talents(Mingjing Du)2022 Talent Development Foundation of Inner Mongolia Autonomous Region of China(Ming-Jing Du)the Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region Program(Grant No.NJYT-20-B18)the Key Project of High-quality Economic Development Research Base of Yellow River Basin in 2022(Grant No.21HZD03)2022 Inner Mongolia Autonomous Region International Science and Technology Cooperation High-end Foreign Experts Introduction Project(Ge Kai)MOE(Ministry of Education in China)Humanities and Social Sciences Foundation(Grants No.20YJC860005).
文摘This paper is aimed at solving the nonlinear time-fractional partial differential equation with two small parameters arising from option pricing model in financial economics.The traditional reproducing kernel(RK)method which deals with this problem is very troublesome.This paper proposes a new method by adaptive multi-step piecewise interpolation reproducing kernel(AMPIRK)method for the first time.This method has three obvious advantages which are as follows.Firstly,the piecewise number is reduced.Secondly,the calculation accuracy is improved.Finally,the waste time caused by too many fragments is avoided.Then four numerical examples show that this new method has a higher precision and it is a more timesaving numerical method than the others.The research in this paper provides a powerful mathematical tool for solving time-fractional option pricing model which will play an important role in financial economics.
基金Project supported by the National Natural Science Foundation of China(Grant No.11074151)the Doctoral Program Foundation of Institutions of Higher Education of China(Grant No.20123704110002)
文摘The dynamics of the double-channel dissociation of the NaCs molecule is investigated by using the time-dependent wave packet （TDWP） method with the ＂split operator-Fourier transform＂ scheme. At a given wavelength and intensity of laser pulse, the population of each state changing with time is obtained. The photo-absorption spectra and kinetic- energy distribution of the dissociation fragments, which exhibit vibration-level structure and dispersion of the wave packet, respectively, are also obtained. The results show that by increasing the laser intensity, one can find not only the band center shift of the photo-absorption spectrum, but also the change of the fragment energy. The appearance of the diffusive band in the photo-absorption spectrum and the multiple peaks in the kinetic-energy spectrum can be attributed to the effects of the predissoeiation limit and the external field.
基金supported by the National Natural Science Foundation of China (Grant No. 51071131)the Science Foundation of Educational Bureau of Sichuan Province of China (Grant No. 09ZA124)
文摘This paper obtains accurate vibrational spectroscopic constants and full vibrational energy spectrum by the al- gebraic method （AM） for some electronic states of halogen diatomic molecules. Motivated by the recent success of obtaining the dissociation energies of Li2 molecule by using a new analytical formula, it further extends the formula to study the dissociation energies of halogen diatomic molecules. The results show that the AM spectrum and the theoretical dissociation energies agree well with RKR data and experimental data respectively.
基金the International Cooperation Program for Excellent Lectures of 2008 by Shandong Provincial Education Department,Chinathe National Natural Science Foundation of China(Grant No.11074151)Fundao para a Ciência e a Tecnologia,Portugal
文摘The photo-dissociation dynamics of LiF is investigated with newly constructed accurate ab initio potential energy curves （PECs） using the time-dependent quantum wave packet method. The oscillations and decay of the wave packet on the adiabats as a function of time are given, which can be compared with the femtosecond transition-state （FTS） spectroscopy. The photo-absorption spectra and the kinetic-energy distribution of the dissociation fragments, which can exhibit the vibration-level structure and the dispersion of the wave packet, respectively, are also obtained. The investigation shows a blue shift of the band center for the photo-absorption spectrum and multiple peaks in the kinetic-energy spectrum with increasing laser intensity, which can be attributed to external field effects. By analyzing the oscillations of the wave packet evolving on the upper adiabat, an approximate inversion scheme is devised to roughly deduce its shape.
基金by the National Natural Science Foundation of China.
文摘Within an extended Su–Schrieffer–Heeger model including impurity interactions,the dynamical process of exciton dissociation in the presence of an external electric field is investigated by using a non-adiabatic evolution method.Under the action of impurities,the stability as well as the effective mass of the exciton is reduced.Our results show that the field required to dissociate the excitons depends sensitively on the strength of the impurity potential.As the impurity potential strength increases,the dissociation field decreases effectively.The theoretical results are expected to provide useful predictions concerning which polymers with properly impurity-assisted interactions are likely to be more suitable for use in organic solar cells.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11474285 and 12074382)。
文摘The activation and dissociation of hydrogen molecules(H_(2))on the Cu(001)surface are studied theoretically.Using first-principles calculations,the activation barrier for the dissociation of H_(2) on Cu(001)is determined to be~0.59 eV in height.It is found that the electron transfer from the copper substrate to H_(2) plays a key role in the activation and breaking of the H–H bond,and the formation of the Cu–H bonds.Two stationary states are identified at around the critical height of bond breaking,corresponding to the molecular and the dissociative states,respectively.Using the transfer matrix method,we also investigate the role of quantum tunneling in the dissociation process along the minimum energy pathway(MEP),which is found to be significant at or below room temperature.At a given temperature,the tunneling contributions due to the translational and the vibrational motions of H_(2) are quantified for the dissociation process.Within a wide range of temperature,the effects of quantum tunneling on the effective barriers of dissociation and the rate constants are observed.The deduced energetic parameters associated with the thermal equilibrium and non-equilibrium(molecular beam)conditions are comparable to experimental data.In the low-temperature region,the crossover from classical to quantum regime is identified.
基金Sponsored by the National High Technology Research and Development Program of China(Grant No.2009AA04Z404)
文摘This paper employs a multi-parameter multi-step chaos control method, which is built up on the OGY method, to stabilize desirable UPOs of a gear system with elastomeric web as a high-dimensional and non-hyperbolic chaotic system, and the analyses are carried out. Three types of relations between components of a certain control parameter combination are defined in a certain control process. Special emphasis is put on the comparison of control efficiencies of the multi-parameter multi-step method and single-parameter multi-step method. The numerical experiments show the ability to switch between different orbits and the method can be a good chaos control alternative since it provides a more effective UPOs stabilization of high-dimensional and non-hyperbolic chaotic systems than the single-parameter chaos control, and according to the relation between components of each parameter combination, the best combination for chaos control in a certain UPO stabilization process are obtained.
文摘In this paper, we studied the process of dissociation unimolecular of the evaporation of H+2n+1 hydrogen clusters according to size, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constants k(E) were determined with the use of statistical theory of unimolecular reactions using various approximations. In our work, we used the products frequencies instead of transitions frequencies in the calculation of unimolecular dissociation rates obtained by three models RRKM. The agreement between the experimental cross section ratio and calculated rate ratio with direct count approximation seems to be reasonable.
