In this work, a bridge density functional approximation （BDFA） （J. Chem. Phys. 112, 8079 （2000）） for a nonuniform hard-sphere fluid is extended to a non-uniform hard-core repulsive Yukawa （HCRY） fluid. It is f...In this work, a bridge density functional approximation （BDFA） （J. Chem. Phys. 112, 8079 （2000）） for a nonuniform hard-sphere fluid is extended to a non-uniform hard-core repulsive Yukawa （HCRY） fluid. It is found that the choice of a bulk bridge functional approximation is crucial for both a uniform HCRY fluid and a non-uniform HCRY fluid. A new bridge functional approximation is proposed, which can accurately predict the radial distribution function of the bulk HCRY fluid. With the new bridge functional approximation and its associated bulk second order direct correlation function as input, the BDFA can be used to well calculate the density profile of the HCRY fluid subjected to the influence of varying external fields, and the theoretical predictions are in good agreement with the corresponding simulation data. The calculated results indicate that the present BDFA captures quantitatively the phenomena such as the coexistence of solid-like high density phase and low density gas phase, and the adsorption properties of the HCRY fluid, which qualitatively differ from those of the fluids combining both hard-core repulsion and an attractive tail.展开更多
A theoretical method was proposed to extend a bridge density functional approximation （BDFA） for the non-uniform hard sphere fluid to the non-uniform Lennard-Jones （LJ） fluid. The DFT approach for LJ fluid is simp...A theoretical method was proposed to extend a bridge density functional approximation （BDFA） for the non-uniform hard sphere fluid to the non-uniform Lennard-Jones （LJ） fluid. The DFT approach for LJ fluid is simple, quantitatively accurate in a wide range of coexistence phase and external field parameters. Especially, the DFT approach only needs a second order direct correlation function （DCF） of the coexistence bulk fluid as input, and is therefore applicable to the subcritical temperature region. The present theoretical method can be regarded as a non-uniform counterpart of the thermodynamic perturbation theory, in which it is not at the level of the free energy but at the level of the second order DCF.the National Natural Science Foundation of China （No. 20546004） and the Natural Science Foundation of Education Department of Hunan Province （No.04C711）.展开更多
Density functional theory(DFT)has been established as a powerful research tool for heterogeneous catalysis research in obtaining key thermodynamic and/or kinetic parameters like adsorption energies,enthalpies of react...Density functional theory(DFT)has been established as a powerful research tool for heterogeneous catalysis research in obtaining key thermodynamic and/or kinetic parameters like adsorption energies,enthalpies of reaction,activation barriers,and rate constants.Understanding of density functional exchangecorrelation approximations is essential to reveal the mechanism and performance of a catalyst.In the present work,we reported the influence of six exchange-correlation density functionals,including PBE,RPBE,BEEF+vdW,optB86b+vdW,SCAN,and SCAN+rVV10,on the adsorption energies,reaction energies and activation barriers of carbon hydrogenation and carbon-carbon couplings during the formation of methane and ethane over Ru(0001)and Ru(1011)surfaces.We found the calculated reaction energies are strongly dependent on exchange-correlation density functionals due to the difference in coordination number between reactants and products on surfaces.The deviation of the calculated elementary reaction energies can be accumulated to a large value for chemical reaction involving multiple steps and vary considerably with different exchange-correlation density functionals calculations.The different exchange-correlation density functionals are found to influence considerably the selectivity of Ru(0001)surface for methane,ethylene,and ethane formation determined by the adsorption energies of intermediates involved.However,the influence on the barriers of the elementary surface reactions and the structural sensitivity of Ru(0001)and Ru(1011)are modest.Our work highlights the limitation of exchange-correlation density functionals on computational catalysis and the importance of choosing a proper exchange-correlation density functional in correctly evaluating the activity and selectivity of a catalyst.展开更多
Here the estimating problem of a single sinusoidal signal in the additive symmetricα-stable Gaussian(ASαSG)noise is investigated.The ASαSG noise here is expressed as the additive of a Gaussian noise and a symmetric...Here the estimating problem of a single sinusoidal signal in the additive symmetricα-stable Gaussian(ASαSG)noise is investigated.The ASαSG noise here is expressed as the additive of a Gaussian noise and a symmetricα-stable distributed variable.As the probability density function(PDF)of the ASαSG is complicated,traditional estimators cannot provide optimum estimates.Based on the Metropolis-Hastings(M-H)sampling scheme,a robust frequency estimator is proposed for ASαSG noise.Moreover,to accelerate the convergence rate of the developed algorithm,a new criterion of reconstructing the proposal covar-iance is derived,whose main idea is updating the proposal variance using several previous samples drawn in each iteration.The approximation PDF of the ASαSG noise,which is referred to the weighted sum of a Voigt function and a Gaussian PDF,is also employed to reduce the computational complexity.The computer simulations show that the performance of our method is better than the maximum likelihood and the lp-norm estimators.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant No 20673150)
文摘In this work, a bridge density functional approximation （BDFA） （J. Chem. Phys. 112, 8079 （2000）） for a nonuniform hard-sphere fluid is extended to a non-uniform hard-core repulsive Yukawa （HCRY） fluid. It is found that the choice of a bulk bridge functional approximation is crucial for both a uniform HCRY fluid and a non-uniform HCRY fluid. A new bridge functional approximation is proposed, which can accurately predict the radial distribution function of the bulk HCRY fluid. With the new bridge functional approximation and its associated bulk second order direct correlation function as input, the BDFA can be used to well calculate the density profile of the HCRY fluid subjected to the influence of varying external fields, and the theoretical predictions are in good agreement with the corresponding simulation data. The calculated results indicate that the present BDFA captures quantitatively the phenomena such as the coexistence of solid-like high density phase and low density gas phase, and the adsorption properties of the HCRY fluid, which qualitatively differ from those of the fluids combining both hard-core repulsion and an attractive tail.
文摘A theoretical method was proposed to extend a bridge density functional approximation （BDFA） for the non-uniform hard sphere fluid to the non-uniform Lennard-Jones （LJ） fluid. The DFT approach for LJ fluid is simple, quantitatively accurate in a wide range of coexistence phase and external field parameters. Especially, the DFT approach only needs a second order direct correlation function （DCF） of the coexistence bulk fluid as input, and is therefore applicable to the subcritical temperature region. The present theoretical method can be regarded as a non-uniform counterpart of the thermodynamic perturbation theory, in which it is not at the level of the free energy but at the level of the second order DCF.the National Natural Science Foundation of China （No. 20546004） and the Natural Science Foundation of Education Department of Hunan Province （No.04C711）.
基金This work was supported by the Key Technologies R&D Program of China(No.2018YFA0208603)the National Natural Science Foundation of China(No.22172150 and No.91945302)+5 种基金the Chinese Academy of Sciences Key Project(QYZDJ-SSW-SLH054)the Start-up Funds of University of Science and Technology of China(No.KY2060000171)the National Natural Science Foundation of Anhui province(No.2108085QB62)USTC Research Funds of the Double First-Class Initiative(No.YD2060002012)K.C.Wong Education(No.GJTD-2020-15)highPerformance Computational Resources provided by the University of Science and Technology of China(http://scc.ustc.edu.cn)and Hefei Advanced Computing center.
文摘Density functional theory(DFT)has been established as a powerful research tool for heterogeneous catalysis research in obtaining key thermodynamic and/or kinetic parameters like adsorption energies,enthalpies of reaction,activation barriers,and rate constants.Understanding of density functional exchangecorrelation approximations is essential to reveal the mechanism and performance of a catalyst.In the present work,we reported the influence of six exchange-correlation density functionals,including PBE,RPBE,BEEF+vdW,optB86b+vdW,SCAN,and SCAN+rVV10,on the adsorption energies,reaction energies and activation barriers of carbon hydrogenation and carbon-carbon couplings during the formation of methane and ethane over Ru(0001)and Ru(1011)surfaces.We found the calculated reaction energies are strongly dependent on exchange-correlation density functionals due to the difference in coordination number between reactants and products on surfaces.The deviation of the calculated elementary reaction energies can be accumulated to a large value for chemical reaction involving multiple steps and vary considerably with different exchange-correlation density functionals calculations.The different exchange-correlation density functionals are found to influence considerably the selectivity of Ru(0001)surface for methane,ethylene,and ethane formation determined by the adsorption energies of intermediates involved.However,the influence on the barriers of the elementary surface reactions and the structural sensitivity of Ru(0001)and Ru(1011)are modest.Our work highlights the limitation of exchange-correlation density functionals on computational catalysis and the importance of choosing a proper exchange-correlation density functional in correctly evaluating the activity and selectivity of a catalyst.
基金supported by National Key R&D Program of China(Grant No.2018YFF01012600)National Natural Science Foundation of China(Grant No.61701021)Fundamental Research Funds for the Central Universities(Grant No.FRF-TP-19-006A3).
文摘Here the estimating problem of a single sinusoidal signal in the additive symmetricα-stable Gaussian(ASαSG)noise is investigated.The ASαSG noise here is expressed as the additive of a Gaussian noise and a symmetricα-stable distributed variable.As the probability density function(PDF)of the ASαSG is complicated,traditional estimators cannot provide optimum estimates.Based on the Metropolis-Hastings(M-H)sampling scheme,a robust frequency estimator is proposed for ASαSG noise.Moreover,to accelerate the convergence rate of the developed algorithm,a new criterion of reconstructing the proposal covar-iance is derived,whose main idea is updating the proposal variance using several previous samples drawn in each iteration.The approximation PDF of the ASαSG noise,which is referred to the weighted sum of a Voigt function and a Gaussian PDF,is also employed to reduce the computational complexity.The computer simulations show that the performance of our method is better than the maximum likelihood and the lp-norm estimators.
