A global and local charge transfer partitioning model,based on the cornerstone theory developed by Robert G.Parr and Robert G.Pearson,which introduces two charge transfer channels(one for accepting electrons(electroph...A global and local charge transfer partitioning model,based on the cornerstone theory developed by Robert G.Parr and Robert G.Pearson,which introduces two charge transfer channels(one for accepting electrons(electrophilic) and another for donating(nucleophilic)),is applied to the reaction of a set of indoles with 4,6-dinitrobenzofuroxan.The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles,i.e.,the indoles under consideration transfer electrons to 4,6-dinitrobenzofuroxan.Evaluating the reactivity descriptorswith exchange-correlation functionals including exact exchange(global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals;however,the trends are preserved.Comparing the trend obtained with the number of electrons donated by the indoles,and predicted by the partitioning model,with that observed experimentally based on the measured rate constants,we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4,6-dinitrobenzofuroxan.This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species;therefore,it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting.The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions,and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve,reaching an optimal correlation,which in the present case indicates keeping three atoms from the indoles and two from 4,6-dinitrobenzofuroxan.The atoms selected by this procedure provide valuable information about the local reactivity of the indoles.We further show that this information about the most reactive atoms on each reactant,combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants,allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.展开更多
Oil-paper compound insulation has been widely used in power transformers for quite a long time because of its good performances. The insulation gradually degrades under combined thermal, electrical and chemical stress...Oil-paper compound insulation has been widely used in power transformers for quite a long time because of its good performances. The insulation gradually degrades under combined thermal, electrical and chemical stresses during routine operations, mainly because of space charges inside. This work investigated the space charge characteristics in oil-paper insulation under oil aging circumstance. New trans- former oil samples are thermally aged to obtain different aging states, and their physical and chemical properties are analyzed. New Kraft papers are dried in vacuum and fully immersed in these different aged oil samples, and three kinds of oil-paper samples are obtained. We use the pulsed electro-acoustic (PEA) method to measure space charge under both DC voltage-on and voltage-off conditions at room temperature. The effect of oil aging state on characteristics of space charge injection, accumulation, and decay is analyzed and discussed. The results show that comparing with the DC voltage-off condition, more charges are injected into samples at the interface of electrode and dielectric when DC voltage is on. When the oil-aged state gets worse, more charges are induced at both cathode and anode, more space charges are accumulated in the bulk, the area of negative charges is larger, and local electric field is distorted more seriously. Moreover, for the voltage-off condition, aged oil is good for space charge decay, and trapped positive space charges decay faster than trapped negative charges.展开更多
The addition of electrons to form gas-phase multiply charged anions(MCAs)normally requires sophisticated experiments or calculations.In this work,the factors stabilizing the MCAs,the maximum electron uptake of gas-pha...The addition of electrons to form gas-phase multiply charged anions(MCAs)normally requires sophisticated experiments or calculations.In this work,the factors stabilizing the MCAs,the maximum electron uptake of gas-phase molecules,X,and the electronic stability of MCAs X^(Q-),are discussed.The drawbacks encountered when applying computational and/or conceptual density functional theory(DFT)to MCAs are highlighted.We develop and test a different model based on the valence-state concept.As in DFT,the electronic energy,E(N,v_(ex)),is a continuous function of the average electron number,N,and the external potential,v_(ex),of the nuclei.The valence-state-parabola is a second-order polynomial that allows extending E(N,v_(ex))to dianions and higher MCAs.The model expresses the maximum electron acceptance,Q_(max),and the higher electron affinities,A_Q,as simple functions of the firstelectron affinity,A_1,and the ionization energy,I,of the"ancestor"system.Thus,the maximum electron acceptance is Q_(max,calc)=1+12A_1/7(I-A_1).The ground-state parabola model of the conceptual DFT yields approximately half of this value,and it is termed Q_(max,GS)=?+A_1/(I-A_1).A large variety of molecules are evaluated including fullerenes,metal clusters,super-pnictogens,super-halogens(OF_3),super-alkali species(OLi_3),and neutral or charged transition-metal complexes,AB_(m )L_n^(0/+/-).The calculated second electron affinity A_(2,calc)=A_1-(7/12)(I-A_1)is linearly correlated to the literature references A_(2,lit) with a correlation coefficient R=0.998.A_2 or A_3 values are predicted for further 24 species.The appearance sizes,n_(ap)^(3-),of triply charged anionic clusters and fullerenes are calculated in agreement with the literature.展开更多
在孤岛直流微电网系统中,线路阻抗不匹配会影响各线路的电流分配精度和荷电状态(state of charge,SOC)均衡效果。同时,由于采用下垂控制,虚拟阻抗的存在也会导致直流母线电压下降。针对以上问题,提出了一种基于自适应虚拟阻抗的SOC均衡...在孤岛直流微电网系统中,线路阻抗不匹配会影响各线路的电流分配精度和荷电状态(state of charge,SOC)均衡效果。同时,由于采用下垂控制,虚拟阻抗的存在也会导致直流母线电压下降。针对以上问题,提出了一种基于自适应虚拟阻抗的SOC均衡控制策略。该策略考虑了不同容量的分布式储能单元(distributed energy storage units,DESUs),并设计了交互DESUs邻居单元SOC均衡差异信息的收敛因子,以加快SOC均衡速度。利用结合多种系统状态信息的状态因子,通过单补偿环节即可实现输出电流的精准分配以及母线电压的恢复。使用改进后的动态平均一致性算法获取系统全局平均状态信息估计值。最后,在Matlab/Simulink仿真软件中搭建了4种工况模型,验证了所提控制策略的有效性和可靠性。展开更多
针对微电网多储能单元因荷电状态、额定容量和线路阻抗差异导致部分储能单元过充过放,影响其使用寿命进而使微网稳定性调节能力变差的问题,提出一种基于变调节因子的多储能荷电状态(state of charge,SoC)均衡策略,通过反余切函数将下垂...针对微电网多储能单元因荷电状态、额定容量和线路阻抗差异导致部分储能单元过充过放,影响其使用寿命进而使微网稳定性调节能力变差的问题,提出一种基于变调节因子的多储能荷电状态(state of charge,SoC)均衡策略,通过反余切函数将下垂系数与SoC、额定容量关联,并引入虚拟压降补偿环节,实现多组储能单元间SoC均衡。在此基础上设计变调节因子,提高SoC均衡速度。仿真结果验证了所提策略能实现多组储能单元间SoC均衡,有效提升SoC均衡速度,并消除线路阻抗对SoC均衡及电流分配精度的影响。展开更多
基金UOV was supported in part by Conacyt through a doctoral fellowship. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867.
文摘A global and local charge transfer partitioning model,based on the cornerstone theory developed by Robert G.Parr and Robert G.Pearson,which introduces two charge transfer channels(one for accepting electrons(electrophilic) and another for donating(nucleophilic)),is applied to the reaction of a set of indoles with 4,6-dinitrobenzofuroxan.The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles,i.e.,the indoles under consideration transfer electrons to 4,6-dinitrobenzofuroxan.Evaluating the reactivity descriptorswith exchange-correlation functionals including exact exchange(global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals;however,the trends are preserved.Comparing the trend obtained with the number of electrons donated by the indoles,and predicted by the partitioning model,with that observed experimentally based on the measured rate constants,we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4,6-dinitrobenzofuroxan.This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species;therefore,it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting.The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions,and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve,reaching an optimal correlation,which in the present case indicates keeping three atoms from the indoles and two from 4,6-dinitrobenzofuroxan.The atoms selected by this procedure provide valuable information about the local reactivity of the indoles.We further show that this information about the most reactive atoms on each reactant,combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants,allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.
基金Project supported by China National Fund for Distinguished Young Scientists (51125029)National High-tech Research and Development Program of China (863 Program) (2007AA04Z411)
文摘Oil-paper compound insulation has been widely used in power transformers for quite a long time because of its good performances. The insulation gradually degrades under combined thermal, electrical and chemical stresses during routine operations, mainly because of space charges inside. This work investigated the space charge characteristics in oil-paper insulation under oil aging circumstance. New trans- former oil samples are thermally aged to obtain different aging states, and their physical and chemical properties are analyzed. New Kraft papers are dried in vacuum and fully immersed in these different aged oil samples, and three kinds of oil-paper samples are obtained. We use the pulsed electro-acoustic (PEA) method to measure space charge under both DC voltage-on and voltage-off conditions at room temperature. The effect of oil aging state on characteristics of space charge injection, accumulation, and decay is analyzed and discussed. The results show that comparing with the DC voltage-off condition, more charges are injected into samples at the interface of electrode and dielectric when DC voltage is on. When the oil-aged state gets worse, more charges are induced at both cathode and anode, more space charges are accumulated in the bulk, the area of negative charges is larger, and local electric field is distorted more seriously. Moreover, for the voltage-off condition, aged oil is good for space charge decay, and trapped positive space charges decay faster than trapped negative charges.
文摘The addition of electrons to form gas-phase multiply charged anions(MCAs)normally requires sophisticated experiments or calculations.In this work,the factors stabilizing the MCAs,the maximum electron uptake of gas-phase molecules,X,and the electronic stability of MCAs X^(Q-),are discussed.The drawbacks encountered when applying computational and/or conceptual density functional theory(DFT)to MCAs are highlighted.We develop and test a different model based on the valence-state concept.As in DFT,the electronic energy,E(N,v_(ex)),is a continuous function of the average electron number,N,and the external potential,v_(ex),of the nuclei.The valence-state-parabola is a second-order polynomial that allows extending E(N,v_(ex))to dianions and higher MCAs.The model expresses the maximum electron acceptance,Q_(max),and the higher electron affinities,A_Q,as simple functions of the firstelectron affinity,A_1,and the ionization energy,I,of the"ancestor"system.Thus,the maximum electron acceptance is Q_(max,calc)=1+12A_1/7(I-A_1).The ground-state parabola model of the conceptual DFT yields approximately half of this value,and it is termed Q_(max,GS)=?+A_1/(I-A_1).A large variety of molecules are evaluated including fullerenes,metal clusters,super-pnictogens,super-halogens(OF_3),super-alkali species(OLi_3),and neutral or charged transition-metal complexes,AB_(m )L_n^(0/+/-).The calculated second electron affinity A_(2,calc)=A_1-(7/12)(I-A_1)is linearly correlated to the literature references A_(2,lit) with a correlation coefficient R=0.998.A_2 or A_3 values are predicted for further 24 species.The appearance sizes,n_(ap)^(3-),of triply charged anionic clusters and fullerenes are calculated in agreement with the literature.
文摘在孤岛直流微电网系统中,线路阻抗不匹配会影响各线路的电流分配精度和荷电状态(state of charge,SOC)均衡效果。同时,由于采用下垂控制,虚拟阻抗的存在也会导致直流母线电压下降。针对以上问题,提出了一种基于自适应虚拟阻抗的SOC均衡控制策略。该策略考虑了不同容量的分布式储能单元(distributed energy storage units,DESUs),并设计了交互DESUs邻居单元SOC均衡差异信息的收敛因子,以加快SOC均衡速度。利用结合多种系统状态信息的状态因子,通过单补偿环节即可实现输出电流的精准分配以及母线电压的恢复。使用改进后的动态平均一致性算法获取系统全局平均状态信息估计值。最后,在Matlab/Simulink仿真软件中搭建了4种工况模型,验证了所提控制策略的有效性和可靠性。
文摘针对微电网多储能单元因荷电状态、额定容量和线路阻抗差异导致部分储能单元过充过放,影响其使用寿命进而使微网稳定性调节能力变差的问题,提出一种基于变调节因子的多储能荷电状态(state of charge,SoC)均衡策略,通过反余切函数将下垂系数与SoC、额定容量关联,并引入虚拟压降补偿环节,实现多组储能单元间SoC均衡。在此基础上设计变调节因子,提高SoC均衡速度。仿真结果验证了所提策略能实现多组储能单元间SoC均衡,有效提升SoC均衡速度,并消除线路阻抗对SoC均衡及电流分配精度的影响。
