Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedra...Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.展开更多
Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR pr...Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.展开更多
Using our recently published electron’s charge electromagnetic flux manifold fiber model of the electron, described by analytical method and numerical simulations, we show how the fine structure constant is embedded ...Using our recently published electron’s charge electromagnetic flux manifold fiber model of the electron, described by analytical method and numerical simulations, we show how the fine structure constant is embedded as a geometrical proportionality constant in three dimensional space of its charge manifold and how this dictates the first QED term one-loop contribution of its anomalous magnetic moment making for the first time a connection of its intrinsic characteristics with physical geometrical dimensions and therefore demonstrating that the physical electron charge cannot be dimensionless. We show that the fine structure constant (FSC) α, and anomalous magnetic moment α<sub>μ</sub> of the electron is related to the sphericity of its charge distribution which is not perfectly spherical and thus has a shape, and therefore its self-confined charge possesses measurable physical dimensions. We also explain why these are not yet able to be measured by past and current experiments and how possible we could succeed.展开更多
The non-spherical lowest-lying Lin(n=15–17)isomers were found with high symmetric compact structures,of which the stability was not rationalized in a previous report(J.Chem.Phys.1199444(2003)).Based on the newly prop...The non-spherical lowest-lying Lin(n=15–17)isomers were found with high symmetric compact structures,of which the stability was not rationalized in a previous report(J.Chem.Phys.1199444(2003)).Based on the newly proposed super-valence bond model,the three prolate lithium clusters can be viewed as magnetic superatomic molecules,which are composed by sharing valence electron pairs and nuclei between two superatom units,namely,Li10 or Li11,and thus their stability can be given a good understanding.Molecular orbital and chemical bonding analysis clearly reveal that the Lin(n=15–17)clusters with prolate shapes are magnetic superatomic molecules.Our work may aid in the developments of the cluster-assembled materials or superatom-bonds.展开更多
The geometries of molecules H_3AXAH_3(X=O,S,Se and A=C,Si)have been optimized using STO-3G ab initio calculations and gradient method and the results are in good agreement with reported experimental values.From the ST...The geometries of molecules H_3AXAH_3(X=O,S,Se and A=C,Si)have been optimized using STO-3G ab initio calculations and gradient method and the results are in good agreement with reported experimental values.From the STO-3G optimized geometries,we have also calculated the electronic structures of these molecules using 4-31G and 6-31G basis sets to obtain the MO energies. atomic net charges and dipole moments.The ionization potentials calculated by 6-31G basis set are in good agreement with experimental values.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11864040,11964037,and 11664038)。
文摘Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.
基金financial supports from the National Natural Science Foundation of China(52201237)the Talent Introduction Project of Chinese Academy of Sciences(E344011)+4 种基金the Shenzhen High Level Talent Team Project(KQTD2022110109364705)the Joint Research Project of China Merchants Group and SIAT(E2Z1521)the Cross Institute Joint Research Youth Team Project of SIAT(E25427)National Natural Science Foundation of China(52402136)the China Postdoctoral Science Foundation(E325281005)。
文摘Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.
文摘Using our recently published electron’s charge electromagnetic flux manifold fiber model of the electron, described by analytical method and numerical simulations, we show how the fine structure constant is embedded as a geometrical proportionality constant in three dimensional space of its charge manifold and how this dictates the first QED term one-loop contribution of its anomalous magnetic moment making for the first time a connection of its intrinsic characteristics with physical geometrical dimensions and therefore demonstrating that the physical electron charge cannot be dimensionless. We show that the fine structure constant (FSC) α, and anomalous magnetic moment α<sub>μ</sub> of the electron is related to the sphericity of its charge distribution which is not perfectly spherical and thus has a shape, and therefore its self-confined charge possesses measurable physical dimensions. We also explain why these are not yet able to be measured by past and current experiments and how possible we could succeed.
基金Project supported by the PhD Starting Fund of Guangdong Ocean University(Grant No.120702/R17077)the National Natural Science Foundation of China(Grant No.11704080).
文摘The non-spherical lowest-lying Lin(n=15–17)isomers were found with high symmetric compact structures,of which the stability was not rationalized in a previous report(J.Chem.Phys.1199444(2003)).Based on the newly proposed super-valence bond model,the three prolate lithium clusters can be viewed as magnetic superatomic molecules,which are composed by sharing valence electron pairs and nuclei between two superatom units,namely,Li10 or Li11,and thus their stability can be given a good understanding.Molecular orbital and chemical bonding analysis clearly reveal that the Lin(n=15–17)clusters with prolate shapes are magnetic superatomic molecules.Our work may aid in the developments of the cluster-assembled materials or superatom-bonds.
基金Work supported by the National Natural Science Foundation of China.
文摘The geometries of molecules H_3AXAH_3(X=O,S,Se and A=C,Si)have been optimized using STO-3G ab initio calculations and gradient method and the results are in good agreement with reported experimental values.From the STO-3G optimized geometries,we have also calculated the electronic structures of these molecules using 4-31G and 6-31G basis sets to obtain the MO energies. atomic net charges and dipole moments.The ionization potentials calculated by 6-31G basis set are in good agreement with experimental values.
