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国家自然科学基金(20472019)

作品数:12 被引量:61H指数:5
相关作者:曹晨忠高硕刘凤萍陈冠凡曾荣今更多>>
相关机构:湖南科技大学中南大学玉林师范学院更多>>
发文基金:国家自然科学基金湖南省自然科学基金湖南省教育厅重点项目更多>>
相关领域:理学更多>>

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Recent progress in quantifying substituent effects被引量:4
2013年
This paper summarizes significant progress in quantifying organic substituent effects in the last 20 years. The main content is as follows: (1) The principle of electronegativity equalization has gained wide acceptance, and has been used to calculate the intramolecular charge distribution and inductive effect of groups. A valence electrons equalization method was proposed to compute the molecular electronegativity on the basis of geometric mean method, harmonic mean method, and weighted mean method. This new calculation method further extended the application of the principle of electronegativity equalization. (2) A scale method was established for experimentally determining the electrophilic and nucleophilic ability of reagents, in which benzhydryliumions and quinone methides were taken as the reference compounds, and the research field was extended to the gas phase conditions, organometallic reaction and radicals system. Moreover, the nucleophilicity parameters N and electro- philicity parameters E for a series of reagents were obtained. The definition and quantitative expression of electrophilicity in- dex co and nucleophilicity index co were proposed theoretically, and the correlation between the parameters from experimental determination and the indexes from theoretical calculation was also investigated. (3) The polarizability effect parameter was initially calculated by empirical method and further developed by quantum chemistry method. Recently, the polarizability ef- fect index of alkyl (PEI) and groups (PEIx) were proposed by statistical method, and got wide applications in explaining and estimating gas-phase acidity and basicity, ionization energy, enthalpy of formation, bond energy, reaction rate, water solubility and chromatographic retention for organic compounds. (4) The excited-state substituent constant Crcc obtained directly from the UV absorption energy data of substituted benzenes, is different from the polar constants in molecular ground state and the radical spin-del
CAO ChenZhongWU YaXin
饱和链状分子中C1s电子电离能与基团拓扑电负性指数
2007年
In this paper,Topological Electronegativity Index (TEI) was developed to express the relatively power of an group in a molecule to attract electrons to itself.The charge effect,the relaxation effect and the electrostatic field effect on the C 1s core ionization energies of saturated molecules were evaluated,based on the topological electronegativity index TEI,the atomic electronegativity χP and the polarizability α.The charge effect was scaled by the topological electronegativity index discrepancy between the C and X (X is atom or group) in the C-X bond.The relaxation effect (induced dipole) was scaled by the charge on the ionized carbon atom together with the polarizabiliy of the X.The electrostatic field effect was scaled by the charges on the atoms attached directly to the ionized carbon atom.Further,the shielding effect ΔSi of the C 1s electron in the saturated molecules was expressed by the charge effect and the relaxation effect together with the electrostatic field effect.By introducing the ΔSi into the Slater model,a Slater-like model was obtained for calculating the C 1s core ionization energy E1,C of saturated molecules,whose correlation coefficient r is 0.99943 and the average absolute error between the calculated and the experimental C 1s core ionization energies is only 0.094eV for 81 saturated molecules.Also the cross-correlation was tested by the leave-one-out (LOO) cross-validation method,and the obtained model has good predictive ability and stability (the correlation coefficient rcv is 0.99928,the average absolute error between the predicted and the experimental values is only 0.105 eV).
曾荣今曹晨忠
关键词:屏蔽效应
用分子拓扑指数预测饱和酯类化合物的气相色谱保留指数被引量:12
2008年
提出修正的分子极化效应指数(MPEI_m)、烷基的极化效应指数(PEI)、奇偶指数(OEI)、均衡电负性(χ_(eq))、立体效应指数(SV_(ij))等拓扑结构参数,运用多元线性回归(MLR)方法获得了饱和酯类化合物在7种不同极性色谱柱上的结构-保留相关(QSRR)模型,模型方程为:RI=aχ_(eq)×PEI+bOEI-cSV_(ij)+dχ_(eq)×MPEI_m+f,其中a、6、c、d、f为系数,相关系数均大于0.99,以留一法(Leave-one-out)进行交互检验,相关系数R_(cv)均大于0.99,表明由上述分子结构参数得出的模型方程用于预测各饱和酯类化合物的气相色谱保留指数其稳定性和准确性俱佳,且较好地揭示了饱和酯类化合物在不同极性色谱柱上气相色谱保留指数的变化规律。
刘凤萍曹晨忠吴湘江周能
关键词:气相色谱保留指数拓扑指数多元线性回归
2,2-二对硝基苯氧基-1,3-苯并二氧噁茂的合成及其晶体结构
2008年
合成了2,2-二氯-1,3-苯并二氧噁茂(DCBZ),并用得到的DCBZ与对硝基酚反应得到2,2-二(对硝基苯氧基)-1,3-苯并二氧噁茂(DPBZ).对DPBZ用IR、1HNMR进行表征并培养出单晶,经X射线衍射法确定了其晶体结构,R=0.0414,Rw=0.1044.晶体结构表明,晶体属于单斜晶系,P2(1)/c空间群,晶胞参数:a=15.7093(4)nm,b=8.7799(2)nm,c=13.5336(3)nm,β=102.840(2)°,V=1819.96(7)nm3,Z=4.化合物通过分子间的弱氢键作用和π-π堆积形成超分子结构,分子中2个对硝基苯氧基分别处于胡椒环平面的两边.图6,表4,参16.
尹志清曹晨忠
关键词:晶体结构超分子
Effect of Excited-state Substituent Constant on the UV Spectra of 1,4-disubstituted Benzenes被引量:9
2009年
A correlation equation between the UV absorption wavenumbers of 1,4-disubstituted benzenes and the excited-state substituent constant was obtained. For 80 sorts of 1,4- disubstituted benzenes, the correlation coefficient was 0.9805, and the standard deviation was only 672.27 cm^-1. The results imply that the excited-state substituent constant can be used productively for research on UV energy of 1,4-disubstituted benzenes. The present method provides a new avenue to study the UV absorption spectra of aromatic systems with the excited-state substituent constant, and it is helpful to understand the effect of substituent electrostatic effects on the chemical and physical properties of conjugated compounds with multiple substituents in excited state.
陈冠凡曹晨忠
一维链状配位聚合物{[p-FBzlPh3P]^+[ZnCl2(NA)]^-}n的合成与晶体结构被引量:2
2008年
“模板效应”(template effect)是由Tompson等人于20世纪60年代初首先提出的。所谓模板效应是指由于配体与模板试剂配位而改变电子状态,并取得某种特定空间配置的效应。最初的模板试剂是指金属离子,20世纪80年代科学家们发现有些中性分子也具有模板效应。随着近年来超分子化学的兴起和发展。以及有机化学和无机化学更进一步的交叉,模板试剂越来越多元化,一些结构新颖的超分子聚合物被合成出来。
陈冠凡曹晨忠
关键词:锌配合物一维链状结构荧光性质
原子电负性和极化度对卤代甲烷C 1s电子电离能的影响被引量:5
2006年
以原子的电负性χP和极化度α为基本参数,估算卤代甲烷CHnY4-n-mZm(Y,Z=F,Cl,Br,I)C1s电子电离能的电荷效应和松弛效应.电荷效应由C—H和C—Y(Z)键两端原子的电负性差来度量,松弛效应由碳原子带的电荷乘上氢和卤素原子极化度来衡量,进而用电荷效应和松弛效应一起表达卤代甲烷中C1s电子电离能的静电-松弛屏蔽效应ΔSi.将ΔSi代入类-Slater模型,得到卤代甲烷中C1s电子电离能E1,C的估算方程,该方程的相关系数r=0.99987,对27个卤代甲烷的计算值与实验值之间的平均绝对误差仅为0.038eV,小于实验误差0.1eV.同时,用留一法(leave-one-out)进行交叉验证(相关系数rcv=0.99977,预测值与实验值之间的绝对平均误差只有0.049eV),结果表明所得方程具有良好的预测能力和稳定性.
曹晨忠曾荣今
关键词:卤代甲烷电负性屏蔽效应
单取代烷烃液相生成焓估算新方法被引量:6
2005年
根据烷基R和取代基X(Cl、Br、I、OH、SH、NO2、CN、NH2、CHO和COOH等)本身的电子效应,应用烷基R的极化效应指数PEI和取代基X的电负性!X定量描述单取代烷烃RX中R和X间的相互作用,再结合已提出的C—C键和C—H键的键连接矩阵的特征根,建立了一个估算单取代烷烃RX液相生成焓的方程:fH0(RX,l)=-39.5001X1CC+33.5508NCC-0.0789X1CH-25.7087NCH+0.1557Sij+0.9976H(X)-27.6642PEI(R)×X+31.5043X此方程用于估算RX的生成焓,不仅结果非常令人满意(其相关系数R达到0.9999,标准偏差SD仅为2.87kJ·mol-1),而且方程中各项参数的物理意义也非常明确,便于人们深入地理解分子结构与性能的关系.应用去一法(leave-one-out)对以上方程进行交叉验证分析表明该方程具有较好的稳定性和较强的预测能力.研究发现,著名的Luo氏方程是上述方程的一种特殊形式,上述方程是对Luo氏方程的一个较大扩展.该方法为研究更复杂体系内基团之间的相互作用提供了一种新的方法和思路.
曹晨忠高硕
关键词:特征根极化效应指数单取代烷烃生成焓
拓扑-量子指数醛酮气相色谱保留指数及沸点的定量构效关系被引量:14
2007年
通过对醛酮化合物分子结构特征及其气相色谱保留指数(RI)和沸点与分子结构间关系的研究,提出了分子极化效应指数(MPEI)、奇偶指数(OEI)、立体效应指数(SVij)、顶点度-距离指数(VDI)及键连接矩阵特征根(∑X1CH)等拓扑-量子结构参数,用多元线性回归(MLR)方法获得了醛酮类化合物的沸点及其在不同极性色谱柱上的气相色谱保留指数与这些拓扑-量子指数间良好的定量结构-性质相关(QSPR)模型,相关系数均大于0.99。5个分子结构参数具有明确的物理化学意义且易于计算和运用。与文献研究的比较结果表明:由上述分子结构参数得出的模型方程适用于各类醛酮化合物的气相色谱保留指数及沸点的预测且具有较好的稳定性和准确性。
刘凤萍梁逸曾曹晨忠
关键词:醛酮类化合物沸点定量结构-性质相关
烷烃电离能和生成焓的相关性被引量:3
2007年
根据化合物形成过程中价电子能量变化与生成焓之间的关系,推导出烷烃的生成焓和电离能之间的关系.以21个烷烃化合物为模型将实验测定的电离能与标准生成焓进行直接关联,证实了模型方程的适用性,所得回归方程的相关系数达到0.9999,估算值与实验值之间的标准偏差仅为0.03eV.同时还利用实验测定的标准生成焓对一系列烷烃的电离能作了预测.
曹晨忠刘金玲
关键词:烷烃生成焓电离能极化效应
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