Understanding the thermodynamic behavior of complex fluids in confined environments is critical for various industrial and natural processes including but not limited to polymer flooding enhanced oil recovery(EOR).In ...Understanding the thermodynamic behavior of complex fluids in confined environments is critical for various industrial and natural processes including but not limited to polymer flooding enhanced oil recovery(EOR).In this work,we develop Atif-V2.0,an extended classical density functional theory(cDFT)framework that integrates the interfacial statistical associating fluid theory(iSAFT)to model multicomponent associating fluids composed of water-soluble polymers,alkanes,and water.Building on the original theoretical framework of Atif for modeling nanoconfined inhomogeneous fluids,Atif-V2.0 embeds explicit solvent and captures additional physical interactions-hydrogen bonding,which are critical in associating fluid systems.The other key feature of Atif-V2.0 is its ability to account for polymer topology.We demonstrate its capability by predicting the equilibrium structure and thermodynamic behavior of branched hydrolyzed polyacrylamide solutions near hard walls with various branching topologies,which provides a robust theoretical tool for the rational design of EOR polymers.展开更多
Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications ofte...Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications often entail electrodes with complicated pore structures,theoretical studies are mostly restricted to EDLCs of simple geometry such as planar or slit pores ignoring the curvature effects of the electrode surface.Significant gaps exist regarding the EDLC performance and the interfacial structure.Herein the classical density functional theory(CDFT)is used to study the capacitance and interfacial behavior of spherical electric double layers within a coarse-grained model.The capacitive performance is associated with electrode curvature,surface potential,and electrolyte concentration and can be correlated with a regression-tree(RT)model.The combination of CDFT with machine-learning methods provides a promising quantitative framework useful for the computational screening of porous electrodes and novel electrolytes.展开更多
Quinones have been widely studied as a potential catholyte in water-based redox flow batteries(RFBs)due to their ability to carry both electrons and protons in aqueous solutions.The wide variety of quinones and deriva...Quinones have been widely studied as a potential catholyte in water-based redox flow batteries(RFBs)due to their ability to carry both electrons and protons in aqueous solutions.The wide variety of quinones and derivatives offers exciting opportunities to optimize the device performance while poses theoretical challenges to quantify their electrochemical behavior as required for molecular design.Computational screening of target quinones with high performance is far from satisfactory.While solvation of quinones affects their potential application in RFBs in terms of both electrochemical windows,stability,and charge transport,experimental data for the solvation structure and solvation free energies are rarely available if not incomplete.Besides,conventional thermodynamic models are mostly unreliable to estimate the properties of direct interest for electrochemical applications.Here,we analyze the hydration free energies of more than 1,400 quinones by combining the first-principles calculations and the classical density functional theory.In order to attain chemical insights and possible trends,special attention is placed on the effects of"backbones"and functional groups on the solvation behavior.The theoretical results provide a thermodynamic basis for the design,synthesis,and screening of high-performance catholytes for electrical energy storage.展开更多
An enhanced KR-fundamental measure functional （FMF） is elaborated and employed to investigate binary and ternary hard sphere fluids near a planar hard wall or confined within two planar hard walls separated by certa...An enhanced KR-fundamental measure functional （FMF） is elaborated and employed to investigate binary and ternary hard sphere fluids near a planar hard wall or confined within two planar hard walls separated by certain interval. The present enhanced KR-FMF incorporates respectively, for aim of comparison, a recent 3rd-order expansion equation of state （EOS） and a Boublfk＇s extension of Kolafa＇s EOS for HS mixtures. It is indicated that the two versions of the EOS lead to, in the framework of the enhanced KR-FMF, similar density profiles, but the 3rd-order EOS is more consistent with an exact scaled particle theory （SPT） relation than the BK EOS. Extensive comparison between the enhanced KR-FMF-3rd-order EOS predictions and corresponding density profiles produced in different periods indicates the excellent performance of the present enhanced KR-FMF-3rd-order EOS in comparison with other available density functional approximations （DFAs）. There are two anomalous situations from whose density profiles all DFAs studied deviate significantly; however, subsequent new computer simulation results for state conditions similar to the two anomalous situations are in very excellent agreement with the present enhanced KR-FMF-3rd-order EOS. The present paper indicates that （i） the validity of the ＂naive＂ substitution elaborated in the present paper and peculiar to the original KR-FMF is still in operation even if inhomogeneoas mixtures are being dealt with; （ii） the high accuracy and self-consistency of the third order EOS seem to allow for application of the KR-FMF-third order EOS to more severe state conditions; and （iii） the ＂naive＂ substitution enables very easy the combination of the original KR-FMF with future＇s more accurate but potentially more complicated EOS of hard sphere mixtures.展开更多
IN function of one complex variable, the inner function on the unit disc plays an important role in the theory of H^p functions. In the mid-1960s, W. Rudin and A. Vitushkin independently raised the question of whether...IN function of one complex variable, the inner function on the unit disc plays an important role in the theory of H^p functions. In the mid-1960s, W. Rudin and A. Vitushkin independently raised the question of whether there exist nonconstant inner functions on the unit ball B_n. Then quickly amassed considerable evidence indicated that such functions would be so pathological that they could not exist. Lately Rudin posed the conjecture on the nonexistence展开更多
We have developed efficient numerical algorithms for solving 3D steadystate Poisson-Nernst-Planck(PNP)equations with excess chemical potentials described by the classical density functional theory(cDFT).The coupled PN...We have developed efficient numerical algorithms for solving 3D steadystate Poisson-Nernst-Planck(PNP)equations with excess chemical potentials described by the classical density functional theory(cDFT).The coupled PNP equations are discretized by a finite difference scheme and solved iteratively using the Gummel method with relaxation.The Nernst-Planck equations are transformed into Laplace equations through the Slotboom transformation.Then,the algebraic multigrid method is applied to efficiently solve the Poisson equation and the transformed Nernst-Planck equations.A novel strategy for calculating excess chemical potentials through fast Fourier transforms is proposed,which reduces computational complexity from O(N2)to O(NlogN),where N is the number of grid points.Integrals involving the Dirac delta function are evaluated directly by coordinate transformation,which yields more accurate results compared to applying numerical quadrature to an approximated delta function.Numerical results for ion and electron transport in solid electrolyte for lithiumion(Li-ion)batteries are shown to be in good agreement with the experimental data and the results from previous studies.展开更多
基金financially supported by the Key Technologies R&D Program of China National Offshore Oil Corporation(No.KJGG2021-0504)。
文摘Understanding the thermodynamic behavior of complex fluids in confined environments is critical for various industrial and natural processes including but not limited to polymer flooding enhanced oil recovery(EOR).In this work,we develop Atif-V2.0,an extended classical density functional theory(cDFT)framework that integrates the interfacial statistical associating fluid theory(iSAFT)to model multicomponent associating fluids composed of water-soluble polymers,alkanes,and water.Building on the original theoretical framework of Atif for modeling nanoconfined inhomogeneous fluids,Atif-V2.0 embeds explicit solvent and captures additional physical interactions-hydrogen bonding,which are critical in associating fluid systems.The other key feature of Atif-V2.0 is its ability to account for polymer topology.We demonstrate its capability by predicting the equilibrium structure and thermodynamic behavior of branched hydrolyzed polyacrylamide solutions near hard walls with various branching topologies,which provides a robust theoretical tool for the rational design of EOR polymers.
基金sponsored by the National Natural Science Foundation of China(Nos.91834301,21908053,and 21808055)Shanghai Sailing Program(19YF1411700)financial support from the Fluid Interface Reactions,Structures and Transport(FIRST)Center,an Energy Frontier Research Center funded by the U.S.Department of Energy,Office of Basic Energy Sciences。
文摘Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications often entail electrodes with complicated pore structures,theoretical studies are mostly restricted to EDLCs of simple geometry such as planar or slit pores ignoring the curvature effects of the electrode surface.Significant gaps exist regarding the EDLC performance and the interfacial structure.Herein the classical density functional theory(CDFT)is used to study the capacitance and interfacial behavior of spherical electric double layers within a coarse-grained model.The capacitive performance is associated with electrode curvature,surface potential,and electrolyte concentration and can be correlated with a regression-tree(RT)model.The combination of CDFT with machine-learning methods provides a promising quantitative framework useful for the computational screening of porous electrodes and novel electrolytes.
基金supported by the National Natural Science Foundation of China(U1862204)the U.S.National Science Foundation(NSF-1940118)。
文摘Quinones have been widely studied as a potential catholyte in water-based redox flow batteries(RFBs)due to their ability to carry both electrons and protons in aqueous solutions.The wide variety of quinones and derivatives offers exciting opportunities to optimize the device performance while poses theoretical challenges to quantify their electrochemical behavior as required for molecular design.Computational screening of target quinones with high performance is far from satisfactory.While solvation of quinones affects their potential application in RFBs in terms of both electrochemical windows,stability,and charge transport,experimental data for the solvation structure and solvation free energies are rarely available if not incomplete.Besides,conventional thermodynamic models are mostly unreliable to estimate the properties of direct interest for electrochemical applications.Here,we analyze the hydration free energies of more than 1,400 quinones by combining the first-principles calculations and the classical density functional theory.In order to attain chemical insights and possible trends,special attention is placed on the effects of"backbones"and functional groups on the solvation behavior.The theoretical results provide a thermodynamic basis for the design,synthesis,and screening of high-performance catholytes for electrical energy storage.
基金Supported by the National Natural Science Foundation of China under Grant No.20973202
文摘An enhanced KR-fundamental measure functional （FMF） is elaborated and employed to investigate binary and ternary hard sphere fluids near a planar hard wall or confined within two planar hard walls separated by certain interval. The present enhanced KR-FMF incorporates respectively, for aim of comparison, a recent 3rd-order expansion equation of state （EOS） and a Boublfk＇s extension of Kolafa＇s EOS for HS mixtures. It is indicated that the two versions of the EOS lead to, in the framework of the enhanced KR-FMF, similar density profiles, but the 3rd-order EOS is more consistent with an exact scaled particle theory （SPT） relation than the BK EOS. Extensive comparison between the enhanced KR-FMF-3rd-order EOS predictions and corresponding density profiles produced in different periods indicates the excellent performance of the present enhanced KR-FMF-3rd-order EOS in comparison with other available density functional approximations （DFAs）. There are two anomalous situations from whose density profiles all DFAs studied deviate significantly; however, subsequent new computer simulation results for state conditions similar to the two anomalous situations are in very excellent agreement with the present enhanced KR-FMF-3rd-order EOS. The present paper indicates that （i） the validity of the ＂naive＂ substitution elaborated in the present paper and peculiar to the original KR-FMF is still in operation even if inhomogeneoas mixtures are being dealt with; （ii） the high accuracy and self-consistency of the third order EOS seem to allow for application of the KR-FMF-third order EOS to more severe state conditions; and （iii） the ＂naive＂ substitution enables very easy the combination of the original KR-FMF with future＇s more accurate but potentially more complicated EOS of hard sphere mixtures.
文摘IN function of one complex variable, the inner function on the unit disc plays an important role in the theory of H^p functions. In the mid-1960s, W. Rudin and A. Vitushkin independently raised the question of whether there exist nonconstant inner functions on the unit ball B_n. Then quickly amassed considerable evidence indicated that such functions would be so pathological that they could not exist. Lately Rudin posed the conjecture on the nonexistence
基金the Materials Synthesis and Simulation across Scales(MS3)Initiative(Laboratory Directed Research and Development(LDRD)Program)at Pacific Northwest National Laboratory(PNNL).Work by GL was supported by the U.S.Department of Energy(DOE)Office of Science’s Advanced Scientific Computing Research Applied Mathematics program and work by BZ by Early Career Award Initiative(LDRD Program)at PNNL.PNNL is operated by Battelle for the DOE under Contract DE-AC05-76RL01830.
文摘We have developed efficient numerical algorithms for solving 3D steadystate Poisson-Nernst-Planck(PNP)equations with excess chemical potentials described by the classical density functional theory(cDFT).The coupled PNP equations are discretized by a finite difference scheme and solved iteratively using the Gummel method with relaxation.The Nernst-Planck equations are transformed into Laplace equations through the Slotboom transformation.Then,the algebraic multigrid method is applied to efficiently solve the Poisson equation and the transformed Nernst-Planck equations.A novel strategy for calculating excess chemical potentials through fast Fourier transforms is proposed,which reduces computational complexity from O(N2)to O(NlogN),where N is the number of grid points.Integrals involving the Dirac delta function are evaluated directly by coordinate transformation,which yields more accurate results compared to applying numerical quadrature to an approximated delta function.Numerical results for ion and electron transport in solid electrolyte for lithiumion(Li-ion)batteries are shown to be in good agreement with the experimental data and the results from previous studies.
