In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other.This aspect is first derived in an orbital-free context.It is shown that the total Fermi potentia...In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other.This aspect is first derived in an orbital-free context.It is shown that the total Fermi potential depends on the density only,the individual parts,the Pauli kinetic energy and the exchange-correlation energy,however,are orbital dependent and as such mutually influence each other.The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy.The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the orderof a few Hartrees.For chemical purposes,however,the energetic performance as a function of the nuclear coordinates is much more important than total energies.Therefore,the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide.The data reveals that,the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances.Therefore,the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy.展开更多
Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculate...Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.展开更多
Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TM...Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TMOs)are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance.In this study,comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon(C),hydrogen(H)and oxygen(O)on TMOs was conducted.Based on density functional theory(DFT)calculations,these effects in both tetragonal structures(PtO_(2),PdO_(2))and hexagonal structures(ZnO,CdO),along with their respective transition metals were systematically explored.It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom,while face-centered cubic(FCC)and hexagonal close-packed(HCP)holes were preferred for the transition metals.Furthermore,under the influence of elastic strains,the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals.Despite these differences,the effect of elastic strains on the adsorption energies of C,H and O on TMOs mirrored those on transition metals:adsorption energies increased under compressive strains,indicating weaker adsorption,and decreased under tension strains,indicating stronger adsorption.This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom.Consequently,elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.展开更多
针对随机激励下振动系统的减振问题,提出了考虑摩擦与非线性阻尼的混联Ⅱ型惯容非线性能量阱(nonlinear energy sink,简称NES),建立了含新型NES主系统的动力学控制方程。首先,采用蒙特卡洛数值方法,研究了非线性刚度对减振性能的影响,...针对随机激励下振动系统的减振问题,提出了考虑摩擦与非线性阻尼的混联Ⅱ型惯容非线性能量阱(nonlinear energy sink,简称NES),建立了含新型NES主系统的动力学控制方程。首先,采用蒙特卡洛数值方法,研究了非线性刚度对减振性能的影响,当非线性刚度比κ_(21)逐渐增大时,主结构和混联Ⅱ型惯容NES的位移概率密度函数出现了双峰变为单峰,以及速度概率密度函数由单峰变为双峰的随机跳跃现象。主结构的位移概率密度函数对非线性刚度κ_(22)的敏感性比κ_(21)更高,κ_(22)最佳取值区间为200~1 000。其次,研究了噪声强度、阻尼比和惯质比对减振性能的影响,当噪声强度小于0.1或惯质比μ在0.1左右时,惯容NES的减振效果较好。虽然线性阻尼比λ_(1)和非线性阻尼比λ_(21)、λ_(22)增大会导致主结构和混联Ⅱ型惯容NES的概率密度函数出现分岔不稳定现象,但增大非线性阻尼比有助于改善惯容NES的减振性能。最后,采用差分进化法对惯容NES的参数进行了优化。本研究可为受随机激励的振动系统减振研究提供技术参考。展开更多
基金The project was supported by the Fund for Scientific Research in Flanders (FWO-Vlaanderen) for Research Grant G021115N.
文摘In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other.This aspect is first derived in an orbital-free context.It is shown that the total Fermi potential depends on the density only,the individual parts,the Pauli kinetic energy and the exchange-correlation energy,however,are orbital dependent and as such mutually influence each other.The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy.The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the orderof a few Hartrees.For chemical purposes,however,the energetic performance as a function of the nuclear coordinates is much more important than total energies.Therefore,the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide.The data reveals that,the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances.Therefore,the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy.
基金supported by Key Science and Technology Innovation Team of Shaanxi Province(No.2022TD-33)National Natural Science Foundation of China(Grant Nos.21373161,21504067)。
文摘Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.
基金Science and Technology Commission of Shanghai Municipality(21ZR1472900,22ZR1471600)。
文摘Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TMOs)are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance.In this study,comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon(C),hydrogen(H)and oxygen(O)on TMOs was conducted.Based on density functional theory(DFT)calculations,these effects in both tetragonal structures(PtO_(2),PdO_(2))and hexagonal structures(ZnO,CdO),along with their respective transition metals were systematically explored.It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom,while face-centered cubic(FCC)and hexagonal close-packed(HCP)holes were preferred for the transition metals.Furthermore,under the influence of elastic strains,the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals.Despite these differences,the effect of elastic strains on the adsorption energies of C,H and O on TMOs mirrored those on transition metals:adsorption energies increased under compressive strains,indicating weaker adsorption,and decreased under tension strains,indicating stronger adsorption.This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom.Consequently,elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.
文摘针对随机激励下振动系统的减振问题,提出了考虑摩擦与非线性阻尼的混联Ⅱ型惯容非线性能量阱(nonlinear energy sink,简称NES),建立了含新型NES主系统的动力学控制方程。首先,采用蒙特卡洛数值方法,研究了非线性刚度对减振性能的影响,当非线性刚度比κ_(21)逐渐增大时,主结构和混联Ⅱ型惯容NES的位移概率密度函数出现了双峰变为单峰,以及速度概率密度函数由单峰变为双峰的随机跳跃现象。主结构的位移概率密度函数对非线性刚度κ_(22)的敏感性比κ_(21)更高,κ_(22)最佳取值区间为200~1 000。其次,研究了噪声强度、阻尼比和惯质比对减振性能的影响,当噪声强度小于0.1或惯质比μ在0.1左右时,惯容NES的减振效果较好。虽然线性阻尼比λ_(1)和非线性阻尼比λ_(21)、λ_(22)增大会导致主结构和混联Ⅱ型惯容NES的概率密度函数出现分岔不稳定现象,但增大非线性阻尼比有助于改善惯容NES的减振性能。最后,采用差分进化法对惯容NES的参数进行了优化。本研究可为受随机激励的振动系统减振研究提供技术参考。
