To investigate the effect of void defects on the shock response of hexanitrohexaazaisowurtzitane(CL-20)co-crystals,shock responses of CL-20 co-crystals with energetic materials ligands trinitrotoluene(TNT),1,3-dinitro...To investigate the effect of void defects on the shock response of hexanitrohexaazaisowurtzitane(CL-20)co-crystals,shock responses of CL-20 co-crystals with energetic materials ligands trinitrotoluene(TNT),1,3-dinitrobenzene(DNB),solvents ligands dimethyl carbonate(DMC) and gamma-butyrolactone(GBL)with void were simulated,using molecular dynamics method and reactive force field.It is found that the CL-20 co-crystals with void defects will form hot spots when impacted,significantly affecting the decomposition of molecules around the void.The degree of molecular fragmentation is relatively low under the reflection velocity of 2 km/s,and the main reactions are the formation of dimer and the shedding of nitro groups.The existence of voids reduces the safety of CL-20 co-crystals,which induced the sensitivity of energetic co-crystals CL-20/TNT and CL-20/DNB to increase more significantly.Detonation has occurred under the reflection velocity of 4 km/s,energetic co-crystals are easier to polymerize than solvent co-crystals,and are not obviously affected by voids.The results show that the energy of the wave decreases after sweeping over the void,which reduces the chemical reaction frequency downstream of the void and affects the detonation performance,especially the solvent co-crystals.展开更多
We investigate the Hugoniot curve, shock-particle velocity relations, and Chapman-Jouguet conditions of the hot dense system through molecular dynamics (MD) simulations. The detailed pathways from crystal nitrometha...We investigate the Hugoniot curve, shock-particle velocity relations, and Chapman-Jouguet conditions of the hot dense system through molecular dynamics (MD) simulations. The detailed pathways from crystal nitromethane to reacted state by shock compression are simulated. The phase transition of N2 and CO mixture is found at about 10 GPa, and the main reason is that the dissociation of the C-O bond and the formation of C-C bond start at 10.0-11.0 GPa. The unreacted state simulations of nitromethane are consistent with shock Hugoniot data. The complete pathway from unreacted to reacted state is discussed. Through chemical species analysis, we find that the C-N bond breaking is the main event of the shock-induced nitromethane decomposition.展开更多
Molecular dynamics simulations of liquid water were performed at 258 K and density of 1.0 g/cm^3 under different strengths of an external electric field, ranging from 0 to 8.0×10^9V/m, to investigate the influenc...Molecular dynamics simulations of liquid water were performed at 258 K and density of 1.0 g/cm^3 under different strengths of an external electric field, ranging from 0 to 8.0×10^9V/m, to investigate the influence of an external field on structural and dynamic properties of water. The flexible simple point charge model is used for water molecules. An enhancement of the water hydrogen bond structure with increasing strength of the electric field has been deduced from the radial distribution functions and the analysis of hydrogen bond structure. With increasing field strength, water system has a more perfect structure, which is shnilar to ice structure. However, the electrofreezing phenomenon of liquid water has not been detected because of a too large self-diffusion coefficient. The self-diffusion coefficient decreases remarkably with increasing strength of electric field, and the self-diffusion coefficient is anisotropic.展开更多
A deep understanding of explosive sensitivities and their factors is important for safe and reliable applications.However,quantitative prediction of the sensitivities is difficult.Here,reactive molecular dynamics simu...A deep understanding of explosive sensitivities and their factors is important for safe and reliable applications.However,quantitative prediction of the sensitivities is difficult.Here,reactive molecular dynamics simulation models for high-speed piston impacts on explosive supercells were established.Simulations were also performed to investigate shock-induced reactions of various high-energy explosives.The fraction of reacted explosive molecules in an initial supercell changed linearly with the propagation distance of the shock-wave front.The corresponding slope could be used as a reaction rate for a specific shock-loading velocity.Reaction rates that varied with the shock-loading pressure exhibited two-stage linearities with different slopes.The two inflection points corresponded to the initial and accelerated reactions,which respectively correlated to the thresholds of shock-induced ignition and detonation.Therefore,the ignition and detonation critical pressures could be determined.The sensitivity could then be a quantitative prediction of the critical pressure.The accuracies of the quantitative shock sensitivity predictions were verified by comparing the impact and shock sensitivities of common explosives and the characteristics of anisotropic shock-induced reactions.Molecular dynamics simulations quantitatively predict and rank shock sensitivities by using only crystal structures of the explosives.Overall,this method will enable the design and safe use of explosives.展开更多
Understanding of metal oxidation is very critical to corrosion control,catalysis synthesis,and advanced materials engineering.Metal oxidation is a very complex phenomenon,with many different processes which are couple...Understanding of metal oxidation is very critical to corrosion control,catalysis synthesis,and advanced materials engineering.Metal oxidation is a very complex phenomenon,with many different processes which are coupled and involved from the onset of reaction.In this work,the initial stage of oxidation on titanium surface was investigated in atomic scale by molecular dynamics(MD)simulations using a reactive force field(ReaxFF).We show that oxygen transport is the dominant process during the initial oxidation.Our simulation also demonstrate that a compressive stress was generated in the oxide layer which blocked the oxygen transport perpendicular to the Titanium(0001)surface and further prevented oxidation in the deeper layers.The mechanism of initial oxidation observed in this work can be also applicable to other self-limiting oxidation.展开更多
Two-state folding and down-hill folding are two kinds of protein folding dynamics for small single domain proteins.Here we apply molecular dynamics(MD)simulation to the two-state protein GB1 and down-hill folding prot...Two-state folding and down-hill folding are two kinds of protein folding dynamics for small single domain proteins.Here we apply molecular dynamics(MD)simulation to the two-state protein GB1 and down-hill folding protein gpW to reveal the relationship of their free energy landscape and folding/unfolding dynamics.Results from the steered MD simulations show that gpW is much less mechanical resistant than GB1,and the unfolding process of gpW has more variability than that of GB1 according to their force-extension curves.The potential of mean force(PMF)of GB1 and gpW obtained by the umbrella sampling simulations shows apparent difference:PMF of GB1 along the coordinate of extension exhibits a kink transition point where the slope of PMF drops suddenly,while PMF of gpW increases with extension smoothly,which are consistent with two-state folding dynamics of GB1 and downhill folding dynamics of gpW,respectively.Our results provide insight to understand the fundamental mechanism of different folding dynamics of twostate proteins and downhill folding proteins.展开更多
Molecular dynamics simulation was carried out to study the behavior of liquid 1,2-dichloroethane molecules under external electric fields including direct current field, alternating current field and positive-half-per...Molecular dynamics simulation was carried out to study the behavior of liquid 1,2-dichloroethane molecules under external electric fields including direct current field, alternating current field and positive-half-period cosin field. The maximum applied field strength was 10^8 V/m , the maximum frequency of the alternating current field and that of the positive-half-period cosine field was 10^12 Hz . The simulation revealed that the field type and field strength act on the population of the molecular configuration. In the strong direct current field, all trans forms converted completely into gauche forms. Order parameter and the correlation of the system torsion angle were also investigated. The results suggested that these two dynamical parameters depended also on the field type and the field strength. The maximum of order parameter was found to be at 0.6in the strong direct current field.展开更多
The short-range repulsive interactions of any force field must be modified to be applicable for high energy atomic collisions because of extremely far from equilibrium state when used in molecular dynamics(MD)simulati...The short-range repulsive interactions of any force field must be modified to be applicable for high energy atomic collisions because of extremely far from equilibrium state when used in molecular dynamics(MD)simulations.In this work,the short-range repulsive interaction of a reactive force field(ReaxFF),describing Fe-Ni-Al alloy system,is well modified by adding a tabulated function form based on Ziegler-Biersack-Littmark(ZBL)potential.The modified interaction covers three ranges,including short range,smooth range,and primordial range.The short range is totally predominated by ZBL potential.The primordial range means the interactions in this range is the as-is ReaxFF with no changes.The smooth range links the short-range ZBL and primordial-range ReaxFF potentials with a taper function.Both energies and forces are guaranteed to be continuous,and qualified to the consistent requirement in LAMMPS.This modified force field is applicable for simulations of energetic particle bombardments and reproducing point defects'booming and recombination effectively.展开更多
The behavior of saturated aqueous Na Cl solutions under a constant external electric field(E) was studied by molecular dynamics(MD) simulation. Our dynamic MD simulations indicated that the irreversible nucleation...The behavior of saturated aqueous Na Cl solutions under a constant external electric field(E) was studied by molecular dynamics(MD) simulation. Our dynamic MD simulations indicated that the irreversible nucleation process towards crystallization is accelerated by a moderate E but retarded or even prohibited under a stronger E, which can be understood by the competition between self-diffusion and drift motion. The former increases with E, thereby accelerating the nucleation process, whereas the latter pulls oppositely charged ions apart under a stronger E, thereby decelerating nucleation.Additionally, our steady-state MD simulations indicated that a first-order phase transition occurs in saturated solutions at a certain threshold Ec. The magnitude of Ec increases with concentration because larger clusters form more easily when the solution is more concentrated and require a stronger E to dissociate.展开更多
Sorption isotherms of hydrocarbon and carbon dioxide (CO2) provide crucial information for designing processes to sequester CO2 and recover natural gas from unmineable coal beds. Methane (CH4), ethane (C2H6), an...Sorption isotherms of hydrocarbon and carbon dioxide (CO2) provide crucial information for designing processes to sequester CO2 and recover natural gas from unmineable coal beds. Methane (CH4), ethane (C2H6), and CO2 adsorption isotherms on dry coal and the temperature effect on their maximum sorption capacity have been studied by performing combined Monte Carlo (MC) and molecular dynamics (MD) simulations at temperatures of 308 and 370 K (35 and 97 ~C) and at pressures up to 10 MPa. Simulation results demonstrate that absolute sorption (expressed as a mass basis) divided by bulk gas density has negligible temperature effect on CH4, C2H6, and CO2 sorption on dry coal when pressure is over 6 MPa. CO2 is more closely packed due to stronger interaction with coal and the stronger interaction between CO2 mole- cules compared, respectively, with the interactions between hydrocarbons and coal and between hydrocarbons. The results of this work suggest that the "a" constant (pro- portional to TcPc) in the Peng-Robinson equation of state is an important factor affecting the sorption behavior of hydrocarbons. CO2 injection pressures of lower than 8 MPa may be desirable for CH4 recovery and CO2 sequestration. This study provides a quantitative under- standing of the effects of temperature on coal sorptioncapacity for CH4, C2H6, and CO2 from a microscopic perspective.展开更多
Thermodynamic properties of complex systems play an essential role in developing chemical engineering processes.It remains a challenge to predict the thermodynamic properties of complex systems in a wide range and des...Thermodynamic properties of complex systems play an essential role in developing chemical engineering processes.It remains a challenge to predict the thermodynamic properties of complex systems in a wide range and describe the behavior of ions and molecules in complex systems.Machine learning emerges as a powerful tool to resolve this issue because it can describe complex relationships beyond the capacity of traditional mathematical functions.This minireview will summarize some fundamental concepts of machine learning methods and their applications in three aspects of the molecular thermodynamics using several examples.The first aspect is to apply machine learning methods to predict the thermodynamic properties of a broad spectrum of systems based on known data.The second aspect is to integer machine learning and molecular simulations to accelerate the discovery of materials.The third aspect is to develop machine learning force field that can eliminate the barrier between quantum mechanics and all-atom molecular dynamics simulations.The applications in these three aspects illustrate the potential of machine learning in molecular thermodynamics of chemical engineering.We will also discuss the perspective of the broad applications of machine learning in chemical engineering.展开更多
Carbon nanotubes (CNTs) have long been expected to be excellent nanochannels for use in desalination membranes and other bio-inspired human-made channels owing to their experimentally confirmed ultrafast water flow ...Carbon nanotubes (CNTs) have long been expected to be excellent nanochannels for use in desalination membranes and other bio-inspired human-made channels owing to their experimentally confirmed ultrafast water flow and theoretically predicted ion rejection. The correct classical force field potential for the interactions between cations and CNTs plays a cru- cial role in understanding the transport behaviors of ions near and inside the CNT, which is key to these expectations. Here, using density functional theory calculations, we provide classical force field potentials for the interactions of Na+/hydrated Na+ with (7,7), (8,8), (9,9), and (10,10)-type CNTs. These potentials can be directly used in current popular classical soft- ware such as nanoscale molecular dynamics (NAMD) by employing the tclBC interface. By incorporating the potential of hydrated cation-g interactions to classical all-atom force fields, we show that the ions will move inside the CNT and accu- mulate, which will block the water flow in wide CNTs. This blockage of water flow in wide CNTs is consistent with recent experimental observations. These results will be helpful for the understanding and design of desalination membranes, new types of nanofluidic channels, nanosensors, and nanoreactors based on CNT platforms.展开更多
A protein may exist as an ensem-ble of di erent conformations in solution,which cannot be repre-sented by a single static structure.Molecular dy-namics(MD)simulation has become a useful tool for sampling protein confo...A protein may exist as an ensem-ble of di erent conformations in solution,which cannot be repre-sented by a single static structure.Molecular dy-namics(MD)simulation has become a useful tool for sampling protein conformations in solution,but force elds and water models are important issues.This work presents a case study of the bacteriophage T4 lysozyme(T4L).We have found that MD simulations using a classic AMBER99SB force eld and TIP4P water model cannot well describe hinge-bending domain motion of the wild-type T4L at the timescale of one microsecond.Other combinations,such as a residue-speci c force eld called RSFF2+and a dispersion-corrected water model TIP4P-D,are able to sample reasonable solution conformations of T4L,which are in good agreement with experimental data.This primary study may provide candidates of force elds and water models for further investigating conformational transition of T4L.展开更多
Nuclear magnetic resonance spectroscopy offers a powerful method for validation of molecular dynamics simulations as it provides information on the molecular structure and dynamics in solution. We performed 10 ns MD s...Nuclear magnetic resonance spectroscopy offers a powerful method for validation of molecular dynamics simulations as it provides information on the molecular structure and dynamics in solution. We performed 10 ns MD simulations using the CHARMM27 force field of four palindromic oligonucleotides and compared the results with experimental NOESY data using the full relaxation matrix formalism. The correlation coefficients between theoretical and experimental data for the four molecular species under study ranged from 0.82 to 0.98 confirming the high quality of the selected force field and providing a valid basis for the identification of force field imperfections. Hence, we observed an unsatisfactory treatment of deoxyribose conformational equilibrium, which resulted in the overrepresentation of the energetically favorable C3'-endo conformation in the MD trajectory. Our developed approach for force field validation based on NMR NOESY spectral data is applicable to a wide range of molecular systems and appropriate force fields.展开更多
疏水力作为胶体物理化学及生物大分子体系中重要作用力,具有典型的多尺度作用程特征,其中亚稳态液膜空化气泡桥接诱发长程疏水力和固液界面水分子重排熵效应诱导短程疏水力假说占据着当前学术主流,但仍缺少系统理论研究.为进一步阐明基...疏水力作为胶体物理化学及生物大分子体系中重要作用力,具有典型的多尺度作用程特征,其中亚稳态液膜空化气泡桥接诱发长程疏水力和固液界面水分子重排熵效应诱导短程疏水力假说占据着当前学术主流,但仍缺少系统理论研究.为进一步阐明基于亚稳态液膜空化的长程疏水力作用机制,借助原子力显微镜(AFM)及分子动力学模拟对全氟辛基三氯硅烷疏水化颗粒与表面间长程疏水力进行了系统研究.AFM力测试结果表明:长程疏水力作用程随接近次数增加而逐渐增大并逐渐趋于稳定,第十次接触时进针曲线跳入黏附距离达到502.01 nm,退针曲线中观察到了预示空化气泡毛细桥断裂的台阶.此外,发现经典毛细力数学模型可以较好地拟合进针曲线,通过计算得到毛细桥体积约为0.30μm^(3),从理论角度直接验证了亚稳态液膜空化气泡毛细桥的存在.进一步借助GROM ACS(GROningen M A chine for Chemical Simulations)大尺度牵引分子动力学模拟从分子尺度探索疏水颗粒分离过程中空化气泡毛细桥产生、演化过程与力学行为的内在关联机制,结果表明:疏水颗粒从基板表面跳出分离瞬间,产生的局部压降吸引氮气分子向液膜内部扩散从而形成空化气泡毛细桥,同时,在毛细桥断裂时刻在计算弹簧势力曲线中观察到了力跳跃行为.最后研究了溶液气体含量对长程疏水力的影响规律,发现气体分子含量和空化气泡毛细桥体积增长速率与毛细桥拉伸断裂长度呈现正相关关系,进一步表明了长程疏水力的气体浓度依赖效应.基于亚稳态液膜空化的长程疏水力作用机制的揭示有助于进一步完善胶体物理化学及生物大分子间相互作用理论体系,同时对调控实际矿物浮选过程具有重要指导意义.展开更多
基金supported by the National Natural Science Foundation of China (22275018)the Project of State Key Laboratory of Explosion Science and Technology (Beijing Institute of Technology)(Grant No.QNKT20-04)。
文摘To investigate the effect of void defects on the shock response of hexanitrohexaazaisowurtzitane(CL-20)co-crystals,shock responses of CL-20 co-crystals with energetic materials ligands trinitrotoluene(TNT),1,3-dinitrobenzene(DNB),solvents ligands dimethyl carbonate(DMC) and gamma-butyrolactone(GBL)with void were simulated,using molecular dynamics method and reactive force field.It is found that the CL-20 co-crystals with void defects will form hot spots when impacted,significantly affecting the decomposition of molecules around the void.The degree of molecular fragmentation is relatively low under the reflection velocity of 2 km/s,and the main reactions are the formation of dimer and the shedding of nitro groups.The existence of voids reduces the safety of CL-20 co-crystals,which induced the sensitivity of energetic co-crystals CL-20/TNT and CL-20/DNB to increase more significantly.Detonation has occurred under the reflection velocity of 4 km/s,energetic co-crystals are easier to polymerize than solvent co-crystals,and are not obviously affected by voids.The results show that the energy of the wave decreases after sweeping over the void,which reduces the chemical reaction frequency downstream of the void and affects the detonation performance,especially the solvent co-crystals.
基金supported by the National Natural Science Foundation of China(Grant No.11374217)the Shandong Provincial Natural Science Foundation,China(Grant No.ZR2014BQ008)
文摘We investigate the Hugoniot curve, shock-particle velocity relations, and Chapman-Jouguet conditions of the hot dense system through molecular dynamics (MD) simulations. The detailed pathways from crystal nitromethane to reacted state by shock compression are simulated. The phase transition of N2 and CO mixture is found at about 10 GPa, and the main reason is that the dissociation of the C-O bond and the formation of C-C bond start at 10.0-11.0 GPa. The unreacted state simulations of nitromethane are consistent with shock Hugoniot data. The complete pathway from unreacted to reacted state is discussed. Through chemical species analysis, we find that the C-N bond breaking is the main event of the shock-induced nitromethane decomposition.
基金Project supported by National Natural Science Foundation of China(Grant No. 20276055)
文摘Molecular dynamics simulations of liquid water were performed at 258 K and density of 1.0 g/cm^3 under different strengths of an external electric field, ranging from 0 to 8.0×10^9V/m, to investigate the influence of an external field on structural and dynamic properties of water. The flexible simple point charge model is used for water molecules. An enhancement of the water hydrogen bond structure with increasing strength of the electric field has been deduced from the radial distribution functions and the analysis of hydrogen bond structure. With increasing field strength, water system has a more perfect structure, which is shnilar to ice structure. However, the electrofreezing phenomenon of liquid water has not been detected because of a too large self-diffusion coefficient. The self-diffusion coefficient decreases remarkably with increasing strength of electric field, and the self-diffusion coefficient is anisotropic.
基金supported by the National Natural Science Foundation of China(Grant No.11832006).
文摘A deep understanding of explosive sensitivities and their factors is important for safe and reliable applications.However,quantitative prediction of the sensitivities is difficult.Here,reactive molecular dynamics simulation models for high-speed piston impacts on explosive supercells were established.Simulations were also performed to investigate shock-induced reactions of various high-energy explosives.The fraction of reacted explosive molecules in an initial supercell changed linearly with the propagation distance of the shock-wave front.The corresponding slope could be used as a reaction rate for a specific shock-loading velocity.Reaction rates that varied with the shock-loading pressure exhibited two-stage linearities with different slopes.The two inflection points corresponded to the initial and accelerated reactions,which respectively correlated to the thresholds of shock-induced ignition and detonation.Therefore,the ignition and detonation critical pressures could be determined.The sensitivity could then be a quantitative prediction of the critical pressure.The accuracies of the quantitative shock sensitivity predictions were verified by comparing the impact and shock sensitivities of common explosives and the characteristics of anisotropic shock-induced reactions.Molecular dynamics simulations quantitatively predict and rank shock sensitivities by using only crystal structures of the explosives.Overall,this method will enable the design and safe use of explosives.
基金Support of this work from the National Natural Science Foundation of China(Grant No.51361009)Work at Ames Laboratory was supported by the US Department of Energy,Basic Energy Sciences,Division of Materials Science and Engineering under Contract No.DE-AC02-07CH11358,including a grant of computer time at the National Energy Research Scientific Computing Centre(NERSC)in Berkeley,CA.
文摘Understanding of metal oxidation is very critical to corrosion control,catalysis synthesis,and advanced materials engineering.Metal oxidation is a very complex phenomenon,with many different processes which are coupled and involved from the onset of reaction.In this work,the initial stage of oxidation on titanium surface was investigated in atomic scale by molecular dynamics(MD)simulations using a reactive force field(ReaxFF).We show that oxygen transport is the dominant process during the initial oxidation.Our simulation also demonstrate that a compressive stress was generated in the oxide layer which blocked the oxygen transport perpendicular to the Titanium(0001)surface and further prevented oxidation in the deeper layers.The mechanism of initial oxidation observed in this work can be also applicable to other self-limiting oxidation.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11874309,11474237,and 11574310)the 111 Project,China(Grant No.B16029).
文摘Two-state folding and down-hill folding are two kinds of protein folding dynamics for small single domain proteins.Here we apply molecular dynamics(MD)simulation to the two-state protein GB1 and down-hill folding protein gpW to reveal the relationship of their free energy landscape and folding/unfolding dynamics.Results from the steered MD simulations show that gpW is much less mechanical resistant than GB1,and the unfolding process of gpW has more variability than that of GB1 according to their force-extension curves.The potential of mean force(PMF)of GB1 and gpW obtained by the umbrella sampling simulations shows apparent difference:PMF of GB1 along the coordinate of extension exhibits a kink transition point where the slope of PMF drops suddenly,while PMF of gpW increases with extension smoothly,which are consistent with two-state folding dynamics of GB1 and downhill folding dynamics of gpW,respectively.Our results provide insight to understand the fundamental mechanism of different folding dynamics of twostate proteins and downhill folding proteins.
文摘Molecular dynamics simulation was carried out to study the behavior of liquid 1,2-dichloroethane molecules under external electric fields including direct current field, alternating current field and positive-half-period cosin field. The maximum applied field strength was 10^8 V/m , the maximum frequency of the alternating current field and that of the positive-half-period cosine field was 10^12 Hz . The simulation revealed that the field type and field strength act on the population of the molecular configuration. In the strong direct current field, all trans forms converted completely into gauche forms. Order parameter and the correlation of the system torsion angle were also investigated. The results suggested that these two dynamical parameters depended also on the field type and the field strength. The maximum of order parameter was found to be at 0.6in the strong direct current field.
基金Project supported by the National Magnetic Confinement Fusion Energy Research Project(Grant Nos.2019YFE03120003,2018YFE0307100,and 2017YFE0302500)the National Natural Science Foundation of China(Grant Nos.11975034,11921006,12004010,and U20B2025).
文摘The short-range repulsive interactions of any force field must be modified to be applicable for high energy atomic collisions because of extremely far from equilibrium state when used in molecular dynamics(MD)simulations.In this work,the short-range repulsive interaction of a reactive force field(ReaxFF),describing Fe-Ni-Al alloy system,is well modified by adding a tabulated function form based on Ziegler-Biersack-Littmark(ZBL)potential.The modified interaction covers three ranges,including short range,smooth range,and primordial range.The short range is totally predominated by ZBL potential.The primordial range means the interactions in this range is the as-is ReaxFF with no changes.The smooth range links the short-range ZBL and primordial-range ReaxFF potentials with a taper function.Both energies and forces are guaranteed to be continuous,and qualified to the consistent requirement in LAMMPS.This modified force field is applicable for simulations of energetic particle bombardments and reproducing point defects'booming and recombination effectively.
基金Project supported by the National Basic Research Program of China(Grant No.2013CB932804)the National Natural Science Foundation of China(Grant Nos.91227115+1 种基金11274319and 11421063)
文摘The behavior of saturated aqueous Na Cl solutions under a constant external electric field(E) was studied by molecular dynamics(MD) simulation. Our dynamic MD simulations indicated that the irreversible nucleation process towards crystallization is accelerated by a moderate E but retarded or even prohibited under a stronger E, which can be understood by the competition between self-diffusion and drift motion. The former increases with E, thereby accelerating the nucleation process, whereas the latter pulls oppositely charged ions apart under a stronger E, thereby decelerating nucleation.Additionally, our steady-state MD simulations indicated that a first-order phase transition occurs in saturated solutions at a certain threshold Ec. The magnitude of Ec increases with concentration because larger clusters form more easily when the solution is more concentrated and require a stronger E to dissociate.
基金supported by the National Basic Research Program of China (2014CB239004)the ‘‘Element and Process Constraint Petroleum System Modeling’’ project (No. 2011A-0207) under the Petro China Science Innovation program
文摘Sorption isotherms of hydrocarbon and carbon dioxide (CO2) provide crucial information for designing processes to sequester CO2 and recover natural gas from unmineable coal beds. Methane (CH4), ethane (C2H6), and CO2 adsorption isotherms on dry coal and the temperature effect on their maximum sorption capacity have been studied by performing combined Monte Carlo (MC) and molecular dynamics (MD) simulations at temperatures of 308 and 370 K (35 and 97 ~C) and at pressures up to 10 MPa. Simulation results demonstrate that absolute sorption (expressed as a mass basis) divided by bulk gas density has negligible temperature effect on CH4, C2H6, and CO2 sorption on dry coal when pressure is over 6 MPa. CO2 is more closely packed due to stronger interaction with coal and the stronger interaction between CO2 mole- cules compared, respectively, with the interactions between hydrocarbons and coal and between hydrocarbons. The results of this work suggest that the "a" constant (pro- portional to TcPc) in the Peng-Robinson equation of state is an important factor affecting the sorption behavior of hydrocarbons. CO2 injection pressures of lower than 8 MPa may be desirable for CH4 recovery and CO2 sequestration. This study provides a quantitative under- standing of the effects of temperature on coal sorptioncapacity for CH4, C2H6, and CO2 from a microscopic perspective.
基金financial supports from the National Natural Science Foundation of China(21676245 and 51933009)the National Key Research and Development Program of China(2017YFB0702502)+1 种基金the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)financial support provided by the Startup Funds of the University of Kentucky。
文摘Thermodynamic properties of complex systems play an essential role in developing chemical engineering processes.It remains a challenge to predict the thermodynamic properties of complex systems in a wide range and describe the behavior of ions and molecules in complex systems.Machine learning emerges as a powerful tool to resolve this issue because it can describe complex relationships beyond the capacity of traditional mathematical functions.This minireview will summarize some fundamental concepts of machine learning methods and their applications in three aspects of the molecular thermodynamics using several examples.The first aspect is to apply machine learning methods to predict the thermodynamic properties of a broad spectrum of systems based on known data.The second aspect is to integer machine learning and molecular simulations to accelerate the discovery of materials.The third aspect is to develop machine learning force field that can eliminate the barrier between quantum mechanics and all-atom molecular dynamics simulations.The applications in these three aspects illustrate the potential of machine learning in molecular thermodynamics of chemical engineering.We will also discuss the perspective of the broad applications of machine learning in chemical engineering.
基金Project supported by the National Science Fund for Outstanding Young Scholars of China(Grant No.11722548)the National Natural Science Foundation of China(Grant Nos.11574339 and 11404361)
文摘Carbon nanotubes (CNTs) have long been expected to be excellent nanochannels for use in desalination membranes and other bio-inspired human-made channels owing to their experimentally confirmed ultrafast water flow and theoretically predicted ion rejection. The correct classical force field potential for the interactions between cations and CNTs plays a cru- cial role in understanding the transport behaviors of ions near and inside the CNT, which is key to these expectations. Here, using density functional theory calculations, we provide classical force field potentials for the interactions of Na+/hydrated Na+ with (7,7), (8,8), (9,9), and (10,10)-type CNTs. These potentials can be directly used in current popular classical soft- ware such as nanoscale molecular dynamics (NAMD) by employing the tclBC interface. By incorporating the potential of hydrated cation-g interactions to classical all-atom force fields, we show that the ions will move inside the CNT and accu- mulate, which will block the water flow in wide CNTs. This blockage of water flow in wide CNTs is consistent with recent experimental observations. These results will be helpful for the understanding and design of desalination membranes, new types of nanofluidic channels, nanosensors, and nanoreactors based on CNT platforms.
基金This work was supported by the National Natu-ral Science Foundation of China(No.91953101 and No.21573205)the Strategic Priority Research Program of the Chinese Academy of Science(XDB37040202),the Hefei National Science Center Pilot Project Funds,and the New Concept Medical Research Fund of USTC.
文摘A protein may exist as an ensem-ble of di erent conformations in solution,which cannot be repre-sented by a single static structure.Molecular dy-namics(MD)simulation has become a useful tool for sampling protein conformations in solution,but force elds and water models are important issues.This work presents a case study of the bacteriophage T4 lysozyme(T4L).We have found that MD simulations using a classic AMBER99SB force eld and TIP4P water model cannot well describe hinge-bending domain motion of the wild-type T4L at the timescale of one microsecond.Other combinations,such as a residue-speci c force eld called RSFF2+and a dispersion-corrected water model TIP4P-D,are able to sample reasonable solution conformations of T4L,which are in good agreement with experimental data.This primary study may provide candidates of force elds and water models for further investigating conformational transition of T4L.
文摘Nuclear magnetic resonance spectroscopy offers a powerful method for validation of molecular dynamics simulations as it provides information on the molecular structure and dynamics in solution. We performed 10 ns MD simulations using the CHARMM27 force field of four palindromic oligonucleotides and compared the results with experimental NOESY data using the full relaxation matrix formalism. The correlation coefficients between theoretical and experimental data for the four molecular species under study ranged from 0.82 to 0.98 confirming the high quality of the selected force field and providing a valid basis for the identification of force field imperfections. Hence, we observed an unsatisfactory treatment of deoxyribose conformational equilibrium, which resulted in the overrepresentation of the energetically favorable C3'-endo conformation in the MD trajectory. Our developed approach for force field validation based on NMR NOESY spectral data is applicable to a wide range of molecular systems and appropriate force fields.
文摘疏水力作为胶体物理化学及生物大分子体系中重要作用力,具有典型的多尺度作用程特征,其中亚稳态液膜空化气泡桥接诱发长程疏水力和固液界面水分子重排熵效应诱导短程疏水力假说占据着当前学术主流,但仍缺少系统理论研究.为进一步阐明基于亚稳态液膜空化的长程疏水力作用机制,借助原子力显微镜(AFM)及分子动力学模拟对全氟辛基三氯硅烷疏水化颗粒与表面间长程疏水力进行了系统研究.AFM力测试结果表明:长程疏水力作用程随接近次数增加而逐渐增大并逐渐趋于稳定,第十次接触时进针曲线跳入黏附距离达到502.01 nm,退针曲线中观察到了预示空化气泡毛细桥断裂的台阶.此外,发现经典毛细力数学模型可以较好地拟合进针曲线,通过计算得到毛细桥体积约为0.30μm^(3),从理论角度直接验证了亚稳态液膜空化气泡毛细桥的存在.进一步借助GROM ACS(GROningen M A chine for Chemical Simulations)大尺度牵引分子动力学模拟从分子尺度探索疏水颗粒分离过程中空化气泡毛细桥产生、演化过程与力学行为的内在关联机制,结果表明:疏水颗粒从基板表面跳出分离瞬间,产生的局部压降吸引氮气分子向液膜内部扩散从而形成空化气泡毛细桥,同时,在毛细桥断裂时刻在计算弹簧势力曲线中观察到了力跳跃行为.最后研究了溶液气体含量对长程疏水力的影响规律,发现气体分子含量和空化气泡毛细桥体积增长速率与毛细桥拉伸断裂长度呈现正相关关系,进一步表明了长程疏水力的气体浓度依赖效应.基于亚稳态液膜空化的长程疏水力作用机制的揭示有助于进一步完善胶体物理化学及生物大分子间相互作用理论体系,同时对调控实际矿物浮选过程具有重要指导意义.