This study presents a boundary-fitted grid (BFG) numerical model with an aim to simulate the tidal currents and diffusion of pollutants in complicated nearshore areas. To suit the general model to any curvilinear grid...This study presents a boundary-fitted grid (BFG) numerical model with an aim to simulate the tidal currents and diffusion of pollutants in complicated nearshore areas. To suit the general model to any curvilinear grids, generalized 2-D shallow sea dynamic equations and the advection diffusion equation are derived in curvilinear coordinates, and the contravariant components of the velocity vector are adopted for easily realizing boundary conditions and making the equations conservational. As the generalized equations are not limited by a speCific coordinate transformation. a self-adaptive grid generation method is then proposed conveniently to generate a boundary-fitted and varying SPacing grid.The calculation in the Yangpu Bay and the Xinying Bay shows that this is an effective model for calculating tidal currents and diffusion of pollutants in the more complicated nearshore areas.展开更多
The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane ...The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane is staler against the metal adatoms than silicene.Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene.Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed.However,the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate.Combining the adsorption energy with the diffusion energy barriers,it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage.In order to avoid forming a metal cluster,we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane.Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials.展开更多
The diffusion mechanism of boron in bcc-Fe has been studied by first-principles calculations. The diffusion coefficients of the interstitial mechanism, the B-monovacancy complex mechanism, and the B-divacancy complex ...The diffusion mechanism of boron in bcc-Fe has been studied by first-principles calculations. The diffusion coefficients of the interstitial mechanism, the B-monovacancy complex mechanism, and the B-divacancy complex mechanism have been calculated. The calculated diffusion coefficient of the interstitial mechanism is DO = 1.05 x l0-7 exp （-0.75 eV/kT） m2. s-1, while the diffusion coefficients of the B-monovacancy and the B-divacancy complex mechanisms are D1 =1.22 x 10-6fl exp （-2.27 eV/kT） mE. s-1 and D2 - 8.36 x 10-6 exp （-4.81 eV/kT） m2. s-l, re- spectively. The results indicate that the dominant diffusion mechanism in bcc-Fe is the interstitial mechanism through an octahedral interstitial site instead of the complex mechanism. The calculated diffusion coefficient is in accordance with the reported experiment results measured in Fe-3%Si-B alloy （bcc structure）. Since the non-equilibrium segregation of boron is based on the diffusion of the complexes as suggested by the theory, our calculation reasonably explains why the non-equilibrium segregation of boron is not observed in bcc-Fe in experiments.展开更多
The paper presents analysis of the performance and the internal flow behaviour in the vaned diffuser of a radial flow pump using PIV(particle image velocimetry)and pressure probe traverses.PIV measurements have alread...The paper presents analysis of the performance and the internal flow behaviour in the vaned diffuser of a radial flow pump using PIV(particle image velocimetry)and pressure probe traverses.PIV measurements have already been performed at middle height inside one diffuser channel passage for a given speed of rotation and various mass flow rates.These results have been already presented in several previous communications.New experiments have been performed using a three-hole pressure probe traverses from hub to shroud diffuser width at different radial locations between the two diffuser geometrical throats.Numerical simulations are also realized with the commercial codes Star CCM+7.02.011 and CFX.Frozen rotor and fully unsteady calculations of the whole pump have been performed.Comparisons between numerical results,previous experimental PIV results and new probe traverses one's are presented and discussed for one mass flow rate.In this respect,a first attempt to take into account fluid leakages between the rotating and fixed part of the pump has been checked since it may affects the real flow structure inside the diffuser.展开更多
Cs and I can migrate through fuel-cladding interfaces and accelerate the cladding corrosion process induced by the fuel-cladding chemical interaction.Cr coating has emerged as an important candidate for mitigating thi...Cs and I can migrate through fuel-cladding interfaces and accelerate the cladding corrosion process induced by the fuel-cladding chemical interaction.Cr coating has emerged as an important candidate for mitigating this chemical interaction.In this study,first-principles calculations were employed to investigate the diffusion behavior of Cs and I in the Cr bulk and grain boundaries to reveal the microscopic interaction mitigation mechanisms at the fuel-cladding interface.The interaction between these two fission products and the Cr coating were studied systematically,and the Cs and I temperature-dependent diffusion coefficients in Cr were obtained using Bocquet’s oversized solute-atom model and Le Claire’s nine-frequency model,respectively.The results showed that the Cs and I migration barriers were significantly lower than that of Cr,and the Cs and I diffusion coefficients were more than three orders of magnitude larger than the Cr self-diffusion coefficient within the temperature range of Generation-IV fast reactors(below 1000 K),demonstrating the strong penetration ability of Cs and I.Furthermore,Cs and I are more likely to diffuse along the grain boundary because of the generally low migration barriers,indicating that the grain boundary serves as a fast diffusion channel for Cs and I.展开更多
Density functional theory calculations in conjunction with the climbing images nudged elastic band method are conducted to study the diffusion phenomena of the Ni-based single crystal superalloys.We focus our attentio...Density functional theory calculations in conjunction with the climbing images nudged elastic band method are conducted to study the diffusion phenomena of the Ni-based single crystal superalloys.We focus our attention on the diffusion processes of the Ni and Al atoms in the γ and γ ’ phases along the direction perpendicular to the interface.The diffusion mechanisms and the expressions of the diffusion coefficients are presented.The vacancy formation energies,the migration energies,and the activation energies for the diffusing Ni and Al atoms are estimated,and these quantities display the expected and clear transition zones in the vicinity of the interface of about 3–7（002） layers.The local density-of-states profiles of atoms in each（002） layer in the γ and γ ’ phases and the partial density-of-states curves of Re and some of its nearest-neighbor atoms are also presented to explore the electronic effect of the diffusion behavior.展开更多
First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the ca...First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.展开更多
We derived revised effective diffusion energy barriers following the Boltzmann distribution assumption for impurity atoms in a bulk material under the impact of various kinds of point defects to reveal the insights of...We derived revised effective diffusion energy barriers following the Boltzmann distribution assumption for impurity atoms in a bulk material under the impact of various kinds of point defects to reveal the insights of migration mechanisms. The effective diffusion energy barriers of copper impurities in bulk zirconium were calculated through the first principle method under the presented hypothesis. Our results(?E_(||) =1.27 eV, ?E_⊥=1.31 eV) agreed well with the experimental results(?E_(||) =1.54 eV, ?E_⊥=1.60 eV), which validated bulk diffusion as the major mechanism for copper diffusion in zirconium. The effective diffusion energy barriers could be used for estimating whether the defects will accelerate the diffusion or slow them down by acting as traps of the impurity atoms. On the other hand, the first principle results of the impurity diffusion via defects could be further used as inputs of larger scale computational simulations, such as MC(Monte Carlo) or Phase Field calculations.展开更多
The partial RDF,the partial molar energy of mixing and the diffusion coefficient of,Li^(+) ,K^(+) F^(-) and Cl^(-) of LiF-KCl(1:1)system have been cal culated by computerized simulation of molecular dynamics method.Th...The partial RDF,the partial molar energy of mixing and the diffusion coefficient of,Li^(+) ,K^(+) F^(-) and Cl^(-) of LiF-KCl(1:1)system have been cal culated by computerized simulation of molecular dynamics method.The results are in agreement with the experimental values.The regularities about the local structure are discussed based on the results of calculation.展开更多
The adsorption and diffusion of F2 molecules on pristine graphene are studied by using first-principles calculations.For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on gr...The adsorption and diffusion of F2 molecules on pristine graphene are studied by using first-principles calculations.For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on graphene surface, a kinetic barrier is identified, which explains the inertness of graphene in molecular F2 at room temperature, and its reactivity with F2 at higher temperatures. Study of the diffusion of F2 molecules on graphene surface determines the energy barrier along the optimal diffusion pathway, which conduces to the understanding of the high stability of fluorographene.展开更多
A detailed first-principles study of the diffusion behaviour of point defects in the O-terminated （0001） surface in wnrtzite ZnO was performed. The 0 vacancy and interstitial are found to diffuse much more easily in...A detailed first-principles study of the diffusion behaviour of point defects in the O-terminated （0001） surface in wnrtzite ZnO was performed. The 0 vacancy and interstitial are found to diffuse much more easily in surface than in bulk. The Zn vacancy has a similar migration barrier for both bulk and surface, but has much smaller barrier for the diffuse-in process. The Zn interstitial is difficult to diffuse in the surface directly, but it can diffuse into the bulk relatively easily. Specific values of corresponding migration barriers are obtained.展开更多
The diffusion property of the intercalated species in the graphite materials is at the heart of the rate performance of graphite-based metal-ion secondary battery.Here we study the diffusion process of a AlCl_(4) mole...The diffusion property of the intercalated species in the graphite materials is at the heart of the rate performance of graphite-based metal-ion secondary battery.Here we study the diffusion process of a AlCl_(4) molecule within graphite—a key component of a recently reported aluminum ion battery with excellent performance—via molecular dynamics(MD)simulations.Both ab-initio MD(AIMD)and semiempirical tight-binding MD simulations show that the diffusion process of the intercalated AlCl_(4) molecule becomes rather inhomogeneous,when the simulation time exceeds approximately 100 picoseconds.Specifically,during its migration in between graphene layers,the intercalated AlCl_(4) molecule may become stagnant occasionally,and then recovers its normal(fast)diffusion behavior after halting for a while.When this phenomenon occurs,the linear relationship of the mean squared displacement(MSD)versus the duration time is not fulfilled.We interpret this peculiar behavior as a manifestation of inadequate sampling of rare event(the stagnation of the molecule),which does not yet appear in short-time MD simulations.We further check the influence of strains present in graphite intercalated compounds(GIC)on the diffusion properties of AlCl_(4),and find that their presence in general slows down the diffusion of the intercalated molecule,and is detrimental to the rate performance of the GIC-based battery.展开更多
The adsorption and diffusion of hydrogen atoms on Cu(001)are studied using first-principles calculations.By taking into account the contribution of zero-point energy(ZPE),the originally identical barriers are shown to...The adsorption and diffusion of hydrogen atoms on Cu(001)are studied using first-principles calculations.By taking into account the contribution of zero-point energy(ZPE),the originally identical barriers are shown to be different for H and D,which are respectively calculated to be~158 me V and~139 me V in height.Using the transfer matrix method(TMM),we are able to calculate the accurate probability of transmission across the barriers.The crucial role of quantum tunneling is clearly demonstrated at low-temperature region.By introducing a temperature-dependent attempting frequency prefactor,the rate constants and diffusion coefficients are calculated.The results are in agreement with the experimental measurements at temperatures from~50 K to 80 K.展开更多
Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into...Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.展开更多
Molecular hydrogen(H_(2))may be an important form of water in nominally anhydrous minerals in the Earth’s mantle and plays a critical role in mantle water cycle,but the transport properties of H2 remain unclear.Here,...Molecular hydrogen(H_(2))may be an important form of water in nominally anhydrous minerals in the Earth’s mantle and plays a critical role in mantle water cycle,but the transport properties of H2 remain unclear.Here,the diffusion of H2 in Fe-free olivine lattice is investigated at pressures of 1-13 GPa and temperatures of 1300-1900 K by first-principles molecular dynamics.The activation energy and activation volume for H2 diffusion in Fe-free olivine are determined to be 55±8 kJ/mol and 3.6±0.2 cm3/mol,respectively.H2 diffusion in Fe-free olivine is faster than H+by 1-4 orders of magnitude and therefore it is more favorable for hydrogen transportation under upper mantle conditions.H2 can be carried to the mantle transition zone by subducting slabs without releasing to the surrounding mantle.The upper mantle may act as a lid,preventing the releasing of H2 produced in the deep mantle to the surface.展开更多
Centrifugal compressors with parallel-wall and contracting wall vaneless diffuser are designed by using centrifugal compressor computer-aided integrated design system. The internal flow fields of the compressor are ca...Centrifugal compressors with parallel-wall and contracting wall vaneless diffuser are designed by using centrifugal compressor computer-aided integrated design system. The internal flow fields of the compressor are calculated by solving three-dimensional Navier-Stokes equation. Four aspects are investigated and calculation results show that the total efficiencies and total pressure ratios of the compressor with contracting wall vandess diffuser is higher than that of the compressor with parallel-wall. The jet and wake don＇t mix rapidly inside vandess diffuser. The outlet blade lean angle doesn＇t affect the compressor performance. The greater the mass flow rate through impeller, the more uneven the velocity distribution at impeller outlet is.展开更多
文摘This study presents a boundary-fitted grid (BFG) numerical model with an aim to simulate the tidal currents and diffusion of pollutants in complicated nearshore areas. To suit the general model to any curvilinear grids, generalized 2-D shallow sea dynamic equations and the advection diffusion equation are derived in curvilinear coordinates, and the contravariant components of the velocity vector are adopted for easily realizing boundary conditions and making the equations conservational. As the generalized equations are not limited by a speCific coordinate transformation. a self-adaptive grid generation method is then proposed conveniently to generate a boundary-fitted and varying SPacing grid.The calculation in the Yangpu Bay and the Xinying Bay shows that this is an effective model for calculating tidal currents and diffusion of pollutants in the more complicated nearshore areas.
基金Project supported by the Natural Science Foundation of Jiangxi Province,China(Grant Nos.20152ACB21014,20151BAB202006,and 20142BAB212002)the Fund from the Jiangxi Provincial Educational Committee,China(Grant No.GJJ14254)supported by the Oversea Returned Project from the Ministry of Education,China
文摘The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane is staler against the metal adatoms than silicene.Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene.Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed.However,the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate.Combining the adsorption energy with the diffusion energy barriers,it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage.In order to avoid forming a metal cluster,we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane.Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials.
基金Project supported by the National Natural Science Foundation of China(Grant No.51276016)the National Basic Research Program of China(Grant No.2012CB720406)
文摘The diffusion mechanism of boron in bcc-Fe has been studied by first-principles calculations. The diffusion coefficients of the interstitial mechanism, the B-monovacancy complex mechanism, and the B-divacancy complex mechanism have been calculated. The calculated diffusion coefficient of the interstitial mechanism is DO = 1.05 x l0-7 exp （-0.75 eV/kT） m2. s-1, while the diffusion coefficients of the B-monovacancy and the B-divacancy complex mechanisms are D1 =1.22 x 10-6fl exp （-2.27 eV/kT） mE. s-1 and D2 - 8.36 x 10-6 exp （-4.81 eV/kT） m2. s-l, re- spectively. The results indicate that the dominant diffusion mechanism in bcc-Fe is the interstitial mechanism through an octahedral interstitial site instead of the complex mechanism. The calculated diffusion coefficient is in accordance with the reported experiment results measured in Fe-3%Si-B alloy （bcc structure）. Since the non-equilibrium segregation of boron is based on the diffusion of the complexes as suggested by the theory, our calculation reasonably explains why the non-equilibrium segregation of boron is not observed in bcc-Fe in experiments.
文摘The paper presents analysis of the performance and the internal flow behaviour in the vaned diffuser of a radial flow pump using PIV(particle image velocimetry)and pressure probe traverses.PIV measurements have already been performed at middle height inside one diffuser channel passage for a given speed of rotation and various mass flow rates.These results have been already presented in several previous communications.New experiments have been performed using a three-hole pressure probe traverses from hub to shroud diffuser width at different radial locations between the two diffuser geometrical throats.Numerical simulations are also realized with the commercial codes Star CCM+7.02.011 and CFX.Frozen rotor and fully unsteady calculations of the whole pump have been performed.Comparisons between numerical results,previous experimental PIV results and new probe traverses one's are presented and discussed for one mass flow rate.In this respect,a first attempt to take into account fluid leakages between the rotating and fixed part of the pump has been checked since it may affects the real flow structure inside the diffuser.
基金the National Natural Science Foundation of China(No.12375282)the Key Laboratory of Computational Physical Sciences Project(Hehai University),Ministry of Education.
文摘Cs and I can migrate through fuel-cladding interfaces and accelerate the cladding corrosion process induced by the fuel-cladding chemical interaction.Cr coating has emerged as an important candidate for mitigating this chemical interaction.In this study,first-principles calculations were employed to investigate the diffusion behavior of Cs and I in the Cr bulk and grain boundaries to reveal the microscopic interaction mitigation mechanisms at the fuel-cladding interface.The interaction between these two fission products and the Cr coating were studied systematically,and the Cs and I temperature-dependent diffusion coefficients in Cr were obtained using Bocquet’s oversized solute-atom model and Le Claire’s nine-frequency model,respectively.The results showed that the Cs and I migration barriers were significantly lower than that of Cr,and the Cs and I diffusion coefficients were more than three orders of magnitude larger than the Cr self-diffusion coefficient within the temperature range of Generation-IV fast reactors(below 1000 K),demonstrating the strong penetration ability of Cs and I.Furthermore,Cs and I are more likely to diffuse along the grain boundary because of the generally low migration barriers,indicating that the grain boundary serves as a fast diffusion channel for Cs and I.
基金Project supported by National Basic Research Program of China(Grant No.2011CB606402)the National Natural Science Foundation of China(Grant No.51071091)
文摘Density functional theory calculations in conjunction with the climbing images nudged elastic band method are conducted to study the diffusion phenomena of the Ni-based single crystal superalloys.We focus our attention on the diffusion processes of the Ni and Al atoms in the γ and γ ’ phases along the direction perpendicular to the interface.The diffusion mechanisms and the expressions of the diffusion coefficients are presented.The vacancy formation energies,the migration energies,and the activation energies for the diffusing Ni and Al atoms are estimated,and these quantities display the expected and clear transition zones in the vicinity of the interface of about 3–7（002） layers.The local density-of-states profiles of atoms in each（002） layer in the γ and γ ’ phases and the partial density-of-states curves of Re and some of its nearest-neighbor atoms are also presented to explore the electronic effect of the diffusion behavior.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51002014,51202017,and 51372095)the Research Fund for the Doctoral Program of Higher Education of China(Grant No.20120061120039)+2 种基金the Funds from the Science and Technology Department of Jilin Province,China(Grant Nos.20120745 and 20130101029JC)the Funds from the Department of Education of Jilin Province,China(Grant No.2013279)the Youth Science Research Foundation of Liaoning University,China(Grant No.2013LDQN20)
文摘First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.
基金Funded in Part by National Natural Science Foundation of China(Nos.11575129 and 11275142)
文摘We derived revised effective diffusion energy barriers following the Boltzmann distribution assumption for impurity atoms in a bulk material under the impact of various kinds of point defects to reveal the insights of migration mechanisms. The effective diffusion energy barriers of copper impurities in bulk zirconium were calculated through the first principle method under the presented hypothesis. Our results(?E_(||) =1.27 eV, ?E_⊥=1.31 eV) agreed well with the experimental results(?E_(||) =1.54 eV, ?E_⊥=1.60 eV), which validated bulk diffusion as the major mechanism for copper diffusion in zirconium. The effective diffusion energy barriers could be used for estimating whether the defects will accelerate the diffusion or slow them down by acting as traps of the impurity atoms. On the other hand, the first principle results of the impurity diffusion via defects could be further used as inputs of larger scale computational simulations, such as MC(Monte Carlo) or Phase Field calculations.
文摘The partial RDF,the partial molar energy of mixing and the diffusion coefficient of,Li^(+) ,K^(+) F^(-) and Cl^(-) of LiF-KCl(1:1)system have been cal culated by computerized simulation of molecular dynamics method.The results are in agreement with the experimental values.The regularities about the local structure are discussed based on the results of calculation.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11664003 and 11474285)the Natural Science Foundation of Guangxi Zhuang Autonomous Region,China(Grant No.2015GXNSFAA139015)the Scientific Research and Technology Development Program of Guilin,China(Grant No.2016012002)
文摘The adsorption and diffusion of F2 molecules on pristine graphene are studied by using first-principles calculations.For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on graphene surface, a kinetic barrier is identified, which explains the inertness of graphene in molecular F2 at room temperature, and its reactivity with F2 at higher temperatures. Study of the diffusion of F2 molecules on graphene surface determines the energy barrier along the optimal diffusion pathway, which conduces to the understanding of the high stability of fluorographene.
基金Project supported by "973 Project" of Ministry of Science and Technology of China (Grant No. 2006CB605102)
文摘A detailed first-principles study of the diffusion behaviour of point defects in the O-terminated （0001） surface in wnrtzite ZnO was performed. The 0 vacancy and interstitial are found to diffuse much more easily in surface than in bulk. The Zn vacancy has a similar migration barrier for both bulk and surface, but has much smaller barrier for the diffuse-in process. The Zn interstitial is difficult to diffuse in the surface directly, but it can diffuse into the bulk relatively easily. Specific values of corresponding migration barriers are obtained.
基金supported by the National Key Research and Development Program of China(Grant No.2016YFB0201202)the National Natural Science Foundation of China(Grant Nos.11874335 and 11774327)。
文摘The diffusion property of the intercalated species in the graphite materials is at the heart of the rate performance of graphite-based metal-ion secondary battery.Here we study the diffusion process of a AlCl_(4) molecule within graphite—a key component of a recently reported aluminum ion battery with excellent performance—via molecular dynamics(MD)simulations.Both ab-initio MD(AIMD)and semiempirical tight-binding MD simulations show that the diffusion process of the intercalated AlCl_(4) molecule becomes rather inhomogeneous,when the simulation time exceeds approximately 100 picoseconds.Specifically,during its migration in between graphene layers,the intercalated AlCl_(4) molecule may become stagnant occasionally,and then recovers its normal(fast)diffusion behavior after halting for a while.When this phenomenon occurs,the linear relationship of the mean squared displacement(MSD)versus the duration time is not fulfilled.We interpret this peculiar behavior as a manifestation of inadequate sampling of rare event(the stagnation of the molecule),which does not yet appear in short-time MD simulations.We further check the influence of strains present in graphite intercalated compounds(GIC)on the diffusion properties of AlCl_(4),and find that their presence in general slows down the diffusion of the intercalated molecule,and is detrimental to the rate performance of the GIC-based battery.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11474285 and 12074382)。
文摘The adsorption and diffusion of hydrogen atoms on Cu(001)are studied using first-principles calculations.By taking into account the contribution of zero-point energy(ZPE),the originally identical barriers are shown to be different for H and D,which are respectively calculated to be~158 me V and~139 me V in height.Using the transfer matrix method(TMM),we are able to calculate the accurate probability of transmission across the barriers.The crucial role of quantum tunneling is clearly demonstrated at low-temperature region.By introducing a temperature-dependent attempting frequency prefactor,the rate constants and diffusion coefficients are calculated.The results are in agreement with the experimental measurements at temperatures from~50 K to 80 K.
基金supported financially by the National Natural Science Foundation of China (No.22075028)。
文摘Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.
基金supported by the National Natural Science Foundation of China for Distinguished Young Scholars(42325203).
文摘Molecular hydrogen(H_(2))may be an important form of water in nominally anhydrous minerals in the Earth’s mantle and plays a critical role in mantle water cycle,but the transport properties of H2 remain unclear.Here,the diffusion of H2 in Fe-free olivine lattice is investigated at pressures of 1-13 GPa and temperatures of 1300-1900 K by first-principles molecular dynamics.The activation energy and activation volume for H2 diffusion in Fe-free olivine are determined to be 55±8 kJ/mol and 3.6±0.2 cm3/mol,respectively.H2 diffusion in Fe-free olivine is faster than H+by 1-4 orders of magnitude and therefore it is more favorable for hydrogen transportation under upper mantle conditions.H2 can be carried to the mantle transition zone by subducting slabs without releasing to the surrounding mantle.The upper mantle may act as a lid,preventing the releasing of H2 produced in the deep mantle to the surface.
文摘Centrifugal compressors with parallel-wall and contracting wall vaneless diffuser are designed by using centrifugal compressor computer-aided integrated design system. The internal flow fields of the compressor are calculated by solving three-dimensional Navier-Stokes equation. Four aspects are investigated and calculation results show that the total efficiencies and total pressure ratios of the compressor with contracting wall vandess diffuser is higher than that of the compressor with parallel-wall. The jet and wake don＇t mix rapidly inside vandess diffuser. The outlet blade lean angle doesn＇t affect the compressor performance. The greater the mass flow rate through impeller, the more uneven the velocity distribution at impeller outlet is.
