The exact equation of state (EOS) for the fission gas Xe is necessary for the accurate prediction of the fission gas behavior in uranium dioxide nuclear fuel, However, the comparison with the experimental data indic...The exact equation of state (EOS) for the fission gas Xe is necessary for the accurate prediction of the fission gas behavior in uranium dioxide nuclear fuel, However, the comparison with the experimental data indicates that the applicable pressure ranges of existing EOS for Xe published in the literature cannot cover the overpressure of the rim fission gas bubble at the typical UO2 fuel pellet rim structure. Based on the interatomic potential of Xe, the pressure-volume-temperature data are calculated by the molecular dynamics (MD) simulation. The results indicate that the data of MD simulation with Ross and McMahan's potential [M. Ross and A. K. McMahan 1980 Phys. Rev. B 21 1658] are in good agreement with the experimental data. A preferable EOS for Xe is proposed based on the MD simulation. The comparison with the MD simulation data shows that the proposed EOS can be applied at pressures up to 550 MPa and 3 GPa and temperatures 900 K and 1373 K respectively. The applicable pressure range of this EOS is wider than those of the other existing EOS for Xe published in the literature.展开更多
The quantum molecular dynamics based on the density functional theory has been adopted to simulate the equation of state for the shock compressed lithium. In contrary to some earlier experimental measurement and theor...The quantum molecular dynamics based on the density functional theory has been adopted to simulate the equation of state for the shock compressed lithium. In contrary to some earlier experimental measurement and theoretical simulation,there is not any evidence of the ‘kink' in the Hugoniot curve in our accurate simulation. Throughout the shock compression process, only a simple solid-to-liquid melting behavior is demonstrated, instead of complicated solid–solid phase transitions. Moreover, the x-ray absorption near-edge spectroscopy has been predicted as a feasible way to diagnose the structural evolution of warm dense lithium in this density region.展开更多
The shell-model molecular dynamics method was applied to simulate the melting temper- atures of SrF2 and BaF2 at elevated temperatures and high pressures. The same method was used to calculate the equations of state f...The shell-model molecular dynamics method was applied to simulate the melting temper- atures of SrF2 and BaF2 at elevated temperatures and high pressures. The same method was used to calculate the equations of state for SrF2 and BaF2 over the pressure range of 0.1 MPa-3 GPa and 0.1 MPa-7 GPa. Compared with previous results for equations of state, the maximum errors are 0.3% and 2.2%, respectively. Considering the pre-melting in the fluorite-type crystals, we made the necessary corrections for the simulated melting temper- atures of SrF2 and BaF2. Consequently, the melting temperatures of SrF2 and BaF2 were obtained for high pressures. The melting temperatures of SrF2 and BaF2 that were obtained by the simulation are in good agreement with available experimental data.展开更多
In this paper, the Martin-Hou equation of state is derived by using a power series representation of radial distribution function and an analytic representation of multi-section potential based on the Barker-Henderso...In this paper, the Martin-Hou equation of state is derived by using a power series representation of radial distribution function and an analytic representation of multi-section potential based on the Barker-Henderson hard-particle perturbation theory including high-order terms. In the derivation, a theoretical form of Martin-Hou equation was obtained. It had a similar form and the same capability to predict P-V-T properties as the Martin-Hou equation and no additional data were required for evaluating the constants. The characteristic constants of the theoretical expression have certain relationships with the molecular parameters.展开更多
The equation of state of MgSiO3 perovskite under high pressure and high temperature is simulated using the molecular dynamics method. It was found that the molecular dynamics simulation is very successful in accuratel...The equation of state of MgSiO3 perovskite under high pressure and high temperature is simulated using the molecular dynamics method. It was found that the molecular dynamics simulation is very successful in accurately reproducing the measured molar volumes of MgSiO3 perovskite over a wide range of temperatures and pressures. The simulated equation of state of MgSiO3 perovskite matched experimental data at up to 140GPa at 300K, as well as the fitting data of others and results from the first-principles simulation based on the local density approximation. The simulated equations of state of MgSiO3 perovskite at higher temperatures and higher pressures also correspond to the other calculations. In addition, the volume compression data of MgSiO3 perovskite is simulated up to 120 GPa at 300, 900, 2000 and 3000 K, respectively.展开更多
With the statistical mechanical theory for square-well-chain fluids as the basic princi-ples,a molecular thermodynamic model including expressions for the Helmholtz function and thecompressibility factor for associate...With the statistical mechanical theory for square-well-chain fluids as the basic princi-ples,a molecular thermodynamic model including expressions for the Helmholtz function and thecompressibility factor for associated square-well-chain fluids has been developed.Employment ofthe shield-sticky concept enables the corporation of association bonds between in the model.Good agreement with computer-simulation results for dimer-linear quadrimer systems is obtained.Satisfactory correlation for vapor pressures and saturated liquid volumes of pure substances con-taining associated molecules(such as carboxylic acids,alcohols,amines,water,etc.)with four mo-lecular parameters indicates the applicability of the model.展开更多
In this paper, the pressure state of the helium bubble in titanium is simulated by a molecular dynamics (MD) method. First, the possible helium/vacancy ratio is determined according to therelation between the bubble...In this paper, the pressure state of the helium bubble in titanium is simulated by a molecular dynamics (MD) method. First, the possible helium/vacancy ratio is determined according to therelation between the bubble pressure and helium/vacancy ratio; then the dependences of the helium bubble pressure on the bubble radius at different temperatures are studied. It is shown that the product of the bubble pressure and the radius is approximately a constant, a result justifying the pressure-radius relation predicted by thermodynamics-based theory for gas bubble. Furthermore, a state equation of the helium bubble is established based on the MD calculations. Comparison between the results obtained by the state equation and corresponding experimental data shows that the state equation can describe reasonably the state of helium bubble and thus could be used for Monte Carlo simulations of the evolution of helium bubble in metals.展开更多
The classical molecular dynamics simulation has been used to study the equation of state of gas H<SUB>2</SUB>, D<SUB>2</SUB> and T<SUB>2</SUB>. It has also been investigated that th...The classical molecular dynamics simulation has been used to study the equation of state of gas H<SUB>2</SUB>, D<SUB>2</SUB> and T<SUB>2</SUB>. It has also been investigated that the isotope mass affects on the accuracy of equation of state. Our calculated results show that the classical effect is principal and the isotope mass effects on the equation of state are obvious for the much light gases. At the same time, some useful theoretical data of equation of state for these gases have been provided. It is found that the classical simulation is still effective to the quantum gas. However, the quantum mechanics simulation and the improvement of intermolecular interaction potential are necessary if more accurate computational results are expected.展开更多
The existence of confining walls limits the prediction accuracy of nanoconfined fluids using macroscopic equations of state(EOSs);moreover,appropriate EOSs for multicomponent mixture fluids in nanoconfined spaces are ...The existence of confining walls limits the prediction accuracy of nanoconfined fluids using macroscopic equations of state(EOSs);moreover,appropriate EOSs for multicomponent mixture fluids in nanoconfined spaces are missing.Here,we derive the EOS of multicomponent mixture fluids confined in nanospaces at high temperatures and pressures,mainly considering the nanoconfinement effect and the competitive adsorption effect between different components.Then,the EOSs are validated through comparison with the molecular dynamics-simulated Pv T data of CO_(2)/H_(2)O mixtures in graphite nanoslits.To consider the above effects,we derive two EOSs via two modeling methods:EOS I is obtained through modification of the actual component occupation volume in the Peng-Robinson equation of state(PR EOS)by fitting the binary component interaction coefficient and the number of adsorbed molecules according to a selectivity coefficient,while EOS II is obtained by considering the decreased pressure of the fluids in PR EOS by adding an attractive term between components and walls.With the simulation results as a benchmark,the two EOSs exhibited good prediction accuracies under low CO_(2) concentrations,and generally,EOS II was more accurate than EOS I.This study fills the gap in the EOSs of nanoconfined mixture fluids,and the obtained equations can help to further describe the thermodynamic properties of confined mixture fluids.展开更多
With unique physical and chemical properties, aqueous solutions in the mantle may play important roles for a number of geochemical and geodynamical processes. However, since experimental data available are very limite...With unique physical and chemical properties, aqueous solutions in the mantle may play important roles for a number of geochemical and geodynamical processes. However, since experimental data available are very limited, people still know little about the aqueous solutions and their interactions with surrounding rocks and melts. From the perspective of thermodynamics, equation of state(EOS) is the key to push forward the modeling of aqueous solutions. Nevertheless, up to now accurate EOSs suitable for the mantle conditions are still in shortage. With discussions over several recognized EOSs, we summarize several ways to enhance the predictability of EOS: utilizing high quality data from molecular simulations, choosing functions with sound physical background, and improving the regression procedures for the empirical parameters. In the meantime, we find that the ion-bearing systems are still the focus of challenges in this area. New developments of experiments and computer simulations effectively deal with these challenges and in-depth understandings of aqueous solutions in the mantle are expected in the near future.展开更多
A new equation of state is derived from the Barker-Henderson hard-sphere perturbation theory. It has the form similar to the Martin-Hou equation of state. The numerical values of the characteristic constants in the eq...A new equation of state is derived from the Barker-Henderson hard-sphere perturbation theory. It has the form similar to the Martin-Hou equation of state. The numerical values of the characteristic constants in the equation can be calculatrd by the method of Martin and Hou. The equation can he used to predictP-V-T properties accurately for fluids when the critical parameters (Tc,Pc, and Vc) and one point on the vapor pressure cure are given. By using the functional relationships between the characteristic constants and the microscopic parameters, the molecular microscopic parameters of the substance can be obtained.展开更多
This project aims to attack the frontiers of electronic structure calculations on the excited states of large molecules and molecular aggregates by developing novel theoretical and computational methods. The methodolo...This project aims to attack the frontiers of electronic structure calculations on the excited states of large molecules and molecular aggregates by developing novel theoretical and computational methods. The methodology development is especially based on the time-dependent density functional theory (TDDFT) and valence bond (VB) theory, and is expected to be computationally effective and accurate as well. Research works on the following related subjects will be performed: (1) The analytical energy-derivative approaches for electronically excited state within TDDFT will be developed to reduce bypass the computational costs in the calculation of molecular excited-state properties. (2) The ab initio methods for electronically excited state based on VB theory and hybrid TDDFT-VB method will be developed to overcome the limitations of current TDDFT in simulating photophysics and photochemistry. (3) For larger aggregates, neither ab initio methods nor TDDFT is applicable. We intend to build the effective model Hamiltonian by developing novel theoretical and computational methods to calculate the involved microscopic physical parameters from the first-principles methods. The constructed effective Hamiltonian is then used to describe the excitonic states and excitonic dynamics of the natural or artificial photosynthesized systems, organic or inorganic photovoltaic cell. (4) The condensed phase environment is taken into account by combining the developed theories and algorithms based on TDDFT and VB with the polarizable continuum solvent models (PCM), molecular mechanism (MM), classical electrodynamics (ED) or molecular dynamics (MD) theory. (5) Highly efficient software packages will be designed and developed.展开更多
An accurate knowledge about phase behaviors of CH4, CO2 and their binary mixture is crucial in fields of natural gas liquefaction and refrigeration applications. In this work, two all-atom force fields of TraPPE-EH an...An accurate knowledge about phase behaviors of CH4, CO2 and their binary mixture is crucial in fields of natural gas liquefaction and refrigeration applications. In this work, two all-atom force fields of TraPPE-EH and EMP2 were used for the components CH4 and CO〉 respectively. Then the vapor-liquid equilibria (VLE) of CH4, CO2 and their binary system were calculated via the NVT- and NpT Gibbs Ensemble Monte Carlo Simulations. Meanwhile the traditional method using Equation of State (EoS) to correlate the VLE properties was also investigated. The EoSs considered in this work were three classic cubic RK, SRK, PR and another advanced molecular-based PC-SAFT equations. For pure components, both molecular simulations and the PC-SAFT EoS could obtain satisfactory predictions for all the saturated properties. However, the saturated liquid densities calculated by the cubic EoSs were not so good. It was also observed that the TraPPE-EH force field had a good representation for CH4 molecule, while the EMP2 force field was not enough accurate to represent CO2 molecules. For the mixture CH4 + CO2, SRK and PR showed the best predictions for the saturated pressure-component property, while good results were also obtained via molecular simulations and PC-SAFT EoS. It was suggested that special combining rules or binary interaction parameters were important to obtain enough accurate prediction of the mixed phase behavior. Compared with the cubic EoS, the PC-SAFT and molecular simulation method showed better adaptabilities for both the pure and mixture systems. Besides, the accurate molecular parameters used in the PC-SAFT and molecular simulations could bring about direct and deep understanding about the molecular characteristics.展开更多
This contribution provides a summary of proposed theoretical and computational studies on excited state dynamics in molecular aggregates, as an important part of the National Natural Science Foundation (NNSF) Major Pr...This contribution provides a summary of proposed theoretical and computational studies on excited state dynamics in molecular aggregates, as an important part of the National Natural Science Foundation (NNSF) Major Project entitled "Theoretical study of the low-lying electronic excited state for molecular aggregates". This study will focus on developments of novel methods to simulate excited state dynamics of molecular aggregates, with the aim of understanding several important chemical physics processes, and providing a solid foundation for predicting the opto-electronic properties of organic functional materials and devices. The contents of this study include: (1) The quantum chemical methods for electronic excited state and electronic couplings targeted for dynamics in molecular aggregates; (2) Methods to construct effective Hamiltonian models, and to solve their dynamics using system-bath approaches; (3) Non-adiabatic mixed quantum-classic methods targeted for molecular aggregates; (4) Theoretical studies of charge and energy transfer, and related spectroscopic phenomena in molecular aggregates.展开更多
High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice co...High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice constants and mass density of the MgSiO3 crystal as functions of pressure are computed, and the corresponding bulk modulus and bulk velocity are evaluated. Our theoretical results agree well with the high-pressure experimental data. A thermodynamic method is introduced to correct the temperature effect on the O-K first-principles results of bulk wave velocity, bulk modulus and mass density in lower mantle PIT range. Taking into account the temperature corrections, the corrected mass density, bulk modulus and bulk wave velocity of MgSiO3-perovskite are estimated from the first-principles results to be 2%, 4%, and 1% lower than the preliminary reference Earth model (PREM) profile, respectively, supporting the possibility of a pure perovskite lower mantle model.展开更多
The microscopic structure of black holes remains a challenging subject. In this paper, based on the well-accepted fact that black holes can be mapped to thermodynamic systems, we make a preliminary exploration of the ...The microscopic structure of black holes remains a challenging subject. In this paper, based on the well-accepted fact that black holes can be mapped to thermodynamic systems, we make a preliminary exploration of the microscopic structure of the thermodynamically stable Schwarzschild anti-de-Sitter(SAdS) black hole. In accordance with the number density and thermodynamic scalar curvature, we give the interaction potential among the molecules of thermodynamically stable SAdS black holes and analyze its effectiveness. Moreover, we derive the thermo-correction to the equation of state for such black holes that arises from interactions among black-hole molecules using virial coefficients.展开更多
Quantum molecular dynamic (QMD) simulations have been applied to study the thermophysical properties of liquid xenon under dynamic compressions. The equation of state (EOS) obtained from QMD calculations are corrected...Quantum molecular dynamic (QMD) simulations have been applied to study the thermophysical properties of liquid xenon under dynamic compressions. The equation of state (EOS) obtained from QMD calculations are corrected according to Saha equation, and contributions from atomic ionization, which are of predominance in determining the EOS at high temperature and pressure, are considered. For the pressures below 160 GPa, the necessity in accounting for the atomic ionization has been demonstrated by the Hugoniot curve, which shows excellent agreement with previous experimental measurements, and three levels of ionization have been proved to be sufficient at this stage.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant No.11205146)
文摘The exact equation of state (EOS) for the fission gas Xe is necessary for the accurate prediction of the fission gas behavior in uranium dioxide nuclear fuel, However, the comparison with the experimental data indicates that the applicable pressure ranges of existing EOS for Xe published in the literature cannot cover the overpressure of the rim fission gas bubble at the typical UO2 fuel pellet rim structure. Based on the interatomic potential of Xe, the pressure-volume-temperature data are calculated by the molecular dynamics (MD) simulation. The results indicate that the data of MD simulation with Ross and McMahan's potential [M. Ross and A. K. McMahan 1980 Phys. Rev. B 21 1658] are in good agreement with the experimental data. A preferable EOS for Xe is proposed based on the MD simulation. The comparison with the MD simulation data shows that the proposed EOS can be applied at pressures up to 550 MPa and 3 GPa and temperatures 900 K and 1373 K respectively. The applicable pressure range of this EOS is wider than those of the other existing EOS for Xe published in the literature.
基金supported by the National Natural Science Foundation of China(Grant Nos.11474034 and 11675024)the Foundation for Development of Science and Technology of China Academy of Engineering Physics(Grant Nos.2015B0102020 and 2015B0102022)the Science Challenge Project(Grant No.TZ2016005)
文摘The quantum molecular dynamics based on the density functional theory has been adopted to simulate the equation of state for the shock compressed lithium. In contrary to some earlier experimental measurement and theoretical simulation,there is not any evidence of the ‘kink' in the Hugoniot curve in our accurate simulation. Throughout the shock compression process, only a simple solid-to-liquid melting behavior is demonstrated, instead of complicated solid–solid phase transitions. Moreover, the x-ray absorption near-edge spectroscopy has been predicted as a feasible way to diagnose the structural evolution of warm dense lithium in this density region.
基金This work was supported by the National Natural Science Foundation of China (No.10676025) and Research Center of Laser Fusion, China Academy of Engineering Physics.
文摘The shell-model molecular dynamics method was applied to simulate the melting temper- atures of SrF2 and BaF2 at elevated temperatures and high pressures. The same method was used to calculate the equations of state for SrF2 and BaF2 over the pressure range of 0.1 MPa-3 GPa and 0.1 MPa-7 GPa. Compared with previous results for equations of state, the maximum errors are 0.3% and 2.2%, respectively. Considering the pre-melting in the fluorite-type crystals, we made the necessary corrections for the simulated melting temper- atures of SrF2 and BaF2. Consequently, the melting temperatures of SrF2 and BaF2 were obtained for high pressures. The melting temperatures of SrF2 and BaF2 that were obtained by the simulation are in good agreement with available experimental data.
基金Zhejiang Provincial Natural Science Foundation of China!(No. 298013)
文摘In this paper, the Martin-Hou equation of state is derived by using a power series representation of radial distribution function and an analytic representation of multi-section potential based on the Barker-Henderson hard-particle perturbation theory including high-order terms. In the derivation, a theoretical form of Martin-Hou equation was obtained. It had a similar form and the same capability to predict P-V-T properties as the Martin-Hou equation and no additional data were required for evaluating the constants. The characteristic constants of the theoretical expression have certain relationships with the molecular parameters.
基金This work was supported by the National Natural Sci- ence Foundation of China, (NSFC No. 10274055), the Natural Science Foundation of Gansu Province of China (No. 3ZS051-A25-027) and the Natural Science Foundation of Education Department of Gansu Province of China (No. 0410-01).
文摘The equation of state of MgSiO3 perovskite under high pressure and high temperature is simulated using the molecular dynamics method. It was found that the molecular dynamics simulation is very successful in accurately reproducing the measured molar volumes of MgSiO3 perovskite over a wide range of temperatures and pressures. The simulated equation of state of MgSiO3 perovskite matched experimental data at up to 140GPa at 300K, as well as the fitting data of others and results from the first-principles simulation based on the local density approximation. The simulated equations of state of MgSiO3 perovskite at higher temperatures and higher pressures also correspond to the other calculations. In addition, the volume compression data of MgSiO3 perovskite is simulated up to 120 GPa at 300, 900, 2000 and 3000 K, respectively.
基金Supported by the National Natural Science Foundation of China and the Doctorate Research Foundation sponsored by the National Education Commission of China.
文摘With the statistical mechanical theory for square-well-chain fluids as the basic princi-ples,a molecular thermodynamic model including expressions for the Helmholtz function and thecompressibility factor for associated square-well-chain fluids has been developed.Employment ofthe shield-sticky concept enables the corporation of association bonds between in the model.Good agreement with computer-simulation results for dimer-linear quadrimer systems is obtained.Satisfactory correlation for vapor pressures and saturated liquid volumes of pure substances con-taining associated molecules(such as carboxylic acids,alcohols,amines,water,etc.)with four mo-lecular parameters indicates the applicability of the model.
基金supported by the National Natural Science Foundation of China (Grant No. 10775101)National Magnetic Confinement Fusion Program of China (Grant No. 2009GB106004)
文摘In this paper, the pressure state of the helium bubble in titanium is simulated by a molecular dynamics (MD) method. First, the possible helium/vacancy ratio is determined according to therelation between the bubble pressure and helium/vacancy ratio; then the dependences of the helium bubble pressure on the bubble radius at different temperatures are studied. It is shown that the product of the bubble pressure and the radius is approximately a constant, a result justifying the pressure-radius relation predicted by thermodynamics-based theory for gas bubble. Furthermore, a state equation of the helium bubble is established based on the MD calculations. Comparison between the results obtained by the state equation and corresponding experimental data shows that the state equation can describe reasonably the state of helium bubble and thus could be used for Monte Carlo simulations of the evolution of helium bubble in metals.
文摘The classical molecular dynamics simulation has been used to study the equation of state of gas H<SUB>2</SUB>, D<SUB>2</SUB> and T<SUB>2</SUB>. It has also been investigated that the isotope mass affects on the accuracy of equation of state. Our calculated results show that the classical effect is principal and the isotope mass effects on the equation of state are obvious for the much light gases. At the same time, some useful theoretical data of equation of state for these gases have been provided. It is found that the classical simulation is still effective to the quantum gas. However, the quantum mechanics simulation and the improvement of intermolecular interaction potential are necessary if more accurate computational results are expected.
基金supported by the National Natural Science Foundation of China for the Basic Science Center Program for Ordered Energy Conversion(Grant Nos.51888103,and 52222606)。
文摘The existence of confining walls limits the prediction accuracy of nanoconfined fluids using macroscopic equations of state(EOSs);moreover,appropriate EOSs for multicomponent mixture fluids in nanoconfined spaces are missing.Here,we derive the EOS of multicomponent mixture fluids confined in nanospaces at high temperatures and pressures,mainly considering the nanoconfinement effect and the competitive adsorption effect between different components.Then,the EOSs are validated through comparison with the molecular dynamics-simulated Pv T data of CO_(2)/H_(2)O mixtures in graphite nanoslits.To consider the above effects,we derive two EOSs via two modeling methods:EOS I is obtained through modification of the actual component occupation volume in the Peng-Robinson equation of state(PR EOS)by fitting the binary component interaction coefficient and the number of adsorbed molecules according to a selectivity coefficient,while EOS II is obtained by considering the decreased pressure of the fluids in PR EOS by adding an attractive term between components and walls.With the simulation results as a benchmark,the two EOSs exhibited good prediction accuracies under low CO_(2) concentrations,and generally,EOS II was more accurate than EOS I.This study fills the gap in the EOSs of nanoconfined mixture fluids,and the obtained equations can help to further describe the thermodynamic properties of confined mixture fluids.
基金supported by the National Natural Science Foundation of China (Grant Nos. 41590620 & 41473060)
文摘With unique physical and chemical properties, aqueous solutions in the mantle may play important roles for a number of geochemical and geodynamical processes. However, since experimental data available are very limited, people still know little about the aqueous solutions and their interactions with surrounding rocks and melts. From the perspective of thermodynamics, equation of state(EOS) is the key to push forward the modeling of aqueous solutions. Nevertheless, up to now accurate EOSs suitable for the mantle conditions are still in shortage. With discussions over several recognized EOSs, we summarize several ways to enhance the predictability of EOS: utilizing high quality data from molecular simulations, choosing functions with sound physical background, and improving the regression procedures for the empirical parameters. In the meantime, we find that the ion-bearing systems are still the focus of challenges in this area. New developments of experiments and computer simulations effectively deal with these challenges and in-depth understandings of aqueous solutions in the mantle are expected in the near future.
基金Project supported by the Natural Science Foundation of Zhejiang Province (Grant No. 292051)
文摘A new equation of state is derived from the Barker-Henderson hard-sphere perturbation theory. It has the form similar to the Martin-Hou equation of state. The numerical values of the characteristic constants in the equation can be calculatrd by the method of Martin and Hou. The equation can he used to predictP-V-T properties accurately for fluids when the critical parameters (Tc,Pc, and Vc) and one point on the vapor pressure cure are given. By using the functional relationships between the characteristic constants and the microscopic parameters, the molecular microscopic parameters of the substance can be obtained.
基金the National Natrual Science Foundation of China (21290193)
文摘This project aims to attack the frontiers of electronic structure calculations on the excited states of large molecules and molecular aggregates by developing novel theoretical and computational methods. The methodology development is especially based on the time-dependent density functional theory (TDDFT) and valence bond (VB) theory, and is expected to be computationally effective and accurate as well. Research works on the following related subjects will be performed: (1) The analytical energy-derivative approaches for electronically excited state within TDDFT will be developed to reduce bypass the computational costs in the calculation of molecular excited-state properties. (2) The ab initio methods for electronically excited state based on VB theory and hybrid TDDFT-VB method will be developed to overcome the limitations of current TDDFT in simulating photophysics and photochemistry. (3) For larger aggregates, neither ab initio methods nor TDDFT is applicable. We intend to build the effective model Hamiltonian by developing novel theoretical and computational methods to calculate the involved microscopic physical parameters from the first-principles methods. The constructed effective Hamiltonian is then used to describe the excitonic states and excitonic dynamics of the natural or artificial photosynthesized systems, organic or inorganic photovoltaic cell. (4) The condensed phase environment is taken into account by combining the developed theories and algorithms based on TDDFT and VB with the polarizable continuum solvent models (PCM), molecular mechanism (MM), classical electrodynamics (ED) or molecular dynamics (MD) theory. (5) Highly efficient software packages will be designed and developed.
基金The National Natural Science Foundation of China(Grant No.51376188)The National Basic Research Program of China("973"Project)(Grant No.2011CB710701)
文摘An accurate knowledge about phase behaviors of CH4, CO2 and their binary mixture is crucial in fields of natural gas liquefaction and refrigeration applications. In this work, two all-atom force fields of TraPPE-EH and EMP2 were used for the components CH4 and CO〉 respectively. Then the vapor-liquid equilibria (VLE) of CH4, CO2 and their binary system were calculated via the NVT- and NpT Gibbs Ensemble Monte Carlo Simulations. Meanwhile the traditional method using Equation of State (EoS) to correlate the VLE properties was also investigated. The EoSs considered in this work were three classic cubic RK, SRK, PR and another advanced molecular-based PC-SAFT equations. For pure components, both molecular simulations and the PC-SAFT EoS could obtain satisfactory predictions for all the saturated properties. However, the saturated liquid densities calculated by the cubic EoSs were not so good. It was also observed that the TraPPE-EH force field had a good representation for CH4 molecule, while the EMP2 force field was not enough accurate to represent CO2 molecules. For the mixture CH4 + CO2, SRK and PR showed the best predictions for the saturated pressure-component property, while good results were also obtained via molecular simulations and PC-SAFT EoS. It was suggested that special combining rules or binary interaction parameters were important to obtain enough accurate prediction of the mixed phase behavior. Compared with the cubic EoS, the PC-SAFT and molecular simulation method showed better adaptabilities for both the pure and mixture systems. Besides, the accurate molecular parameters used in the PC-SAFT and molecular simulations could bring about direct and deep understanding about the molecular characteristics.
基金the National Natural Science Foundation of China (21290194)
文摘This contribution provides a summary of proposed theoretical and computational studies on excited state dynamics in molecular aggregates, as an important part of the National Natural Science Foundation (NNSF) Major Project entitled "Theoretical study of the low-lying electronic excited state for molecular aggregates". This study will focus on developments of novel methods to simulate excited state dynamics of molecular aggregates, with the aim of understanding several important chemical physics processes, and providing a solid foundation for predicting the opto-electronic properties of organic functional materials and devices. The contents of this study include: (1) The quantum chemical methods for electronic excited state and electronic couplings targeted for dynamics in molecular aggregates; (2) Methods to construct effective Hamiltonian models, and to solve their dynamics using system-bath approaches; (3) Non-adiabatic mixed quantum-classic methods targeted for molecular aggregates; (4) Theoretical studies of charge and energy transfer, and related spectroscopic phenomena in molecular aggregates.
基金Supported by the National Natural Science Foundation of China under Grant Nos 40474033 and 10376024, and the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No 20050613017.
文摘High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice constants and mass density of the MgSiO3 crystal as functions of pressure are computed, and the corresponding bulk modulus and bulk velocity are evaluated. Our theoretical results agree well with the high-pressure experimental data. A thermodynamic method is introduced to correct the temperature effect on the O-K first-principles results of bulk wave velocity, bulk modulus and mass density in lower mantle PIT range. Taking into account the temperature corrections, the corrected mass density, bulk modulus and bulk wave velocity of MgSiO3-perovskite are estimated from the first-principles results to be 2%, 4%, and 1% lower than the preliminary reference Earth model (PREM) profile, respectively, supporting the possibility of a pure perovskite lower mantle model.
基金supported by the National Natural Science Foundation of China(Grant No.11675081)
文摘The microscopic structure of black holes remains a challenging subject. In this paper, based on the well-accepted fact that black holes can be mapped to thermodynamic systems, we make a preliminary exploration of the microscopic structure of the thermodynamically stable Schwarzschild anti-de-Sitter(SAdS) black hole. In accordance with the number density and thermodynamic scalar curvature, we give the interaction potential among the molecules of thermodynamically stable SAdS black holes and analyze its effectiveness. Moreover, we derive the thermo-correction to the equation of state for such black holes that arises from interactions among black-hole molecules using virial coefficients.
基金Supported by the Foundation for Development of Science and Technology of China Academy of Engineering Physics under Grant No.2009B0301037
文摘Quantum molecular dynamic (QMD) simulations have been applied to study the thermophysical properties of liquid xenon under dynamic compressions. The equation of state (EOS) obtained from QMD calculations are corrected according to Saha equation, and contributions from atomic ionization, which are of predominance in determining the EOS at high temperature and pressure, are considered. For the pressures below 160 GPa, the necessity in accounting for the atomic ionization has been demonstrated by the Hugoniot curve, which shows excellent agreement with previous experimental measurements, and three levels of ionization have been proved to be sufficient at this stage.