共查询到18条相似文献，搜索用时 312 毫秒
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Cs+水合结构的密度泛函理论计算研究 总被引：1，自引：1，他引：0
基于密度泛函理论在ωB97XD/gen def2-tzvp基组水平上对[Cs(H_2O)n]~+(n=1～15)水合团簇结构的振动光谱进行了研究。研究表明,随着水分子数的增加,在气相和液相中,八配位的Cs~+水合团簇是最稳定的;随着水分子数的增加,Cs-O键长增大,Cs~+上的电荷密度减小。当水分子数大于11时,Cs-O键长和Cs~+上的电荷密度变化很小。O(H_2O)-O(H_2O)距离、∠O(H_2O)-Cs-O(H_2O)°统计结果表明,15个水分子足以形成Cs~+的近似饱和水合层。此外,红外光谱显示[Cs(H_2O)n]~+水合团簇中O-H伸缩振动随着水分子数的增加而发生变化,由此可以作为鉴别水合层位置的一种参考方法。 相似文献
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本文用密度泛函理论在WB97XD/gen def2-tzvp基组水平上对[Cs(H2O) n] +(n=1-15)水合团簇结构的振动光谱进行了研究。研究表明,随着水分子数的增加,在气相和液相中,8配位的Cs+ 水合团簇是最稳定的;随着水分子数的增加,Cs-O键长增大,Cs+上的电荷密度减小。当水分子数大于11时,Cs-O键长和Cs+上的电荷密度变化很小。O(H2O)-O(H2O)距离、∠O(H2O)-Cs-O(H2O)°统计结果表明,15个水分子足以形成Cs+的近似饱和水合层。此外,红外光谱显示[Cs(H2O)n]+水合团簇中O-H伸缩振动随着水分子数的增加而发生变化,由此可以作为鉴别水合层位置的一种参考方法。 相似文献
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结合密度泛函理论,运用B3LYP/aug-cc-pVDZ方法对[Li(H2O)n]+(n=1~10)水合团簇的结构进行了研究。研究结果表明,在气相和液相中,四配位结构的[Li(H2O)n]+水合团簇比其五配位的异构体稳定,即在水溶液中Li+易形成四配位的四面体结构。随着同时水分子数的增加,Li-O键长增大,Li+上的电荷密度减小。但是当水分子数大于4时,Li-O键长和Li+上的电荷密度变化很小。[Li(H2O)n]+水合团簇中每个水分子的结合能计算结果表明,7个水分子已足以形成Li+的近似饱和水合层。另外红外光谱显示[Li(H2O)n]+水合团簇中O-H伸缩振动随着水分子数的增加发生蓝移,而~3 600 cm-1和~3 500 cm-1处的吸收峰是第二水合层与第一水合层、第三水合层和第二水合层的水分子形成氢键引起的。 相似文献
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由密度泛函理论(DFT)和扩展X-射线吸收精细结构(EXAFS)光谱研究硫酸镍溶液的微观水合结构。对硫酸镍水合团簇[NiSO4(H2O)n]0 (n=1-12) 的结构优化和能量计算采用DFT计算中的B3LYP方法进行。对于每一个团簇尺寸尽可能考虑所有初始构型，并以此确定能量最低结构。 DFT计算结果表明，在[NiSO4(H2O)n]0团簇中六配位结构的Ni2+为稳定构型. 水合能计算结果表明，当水合团簇尺寸较小时(n≤5),六配位直接接触离子对(CIP)为稳定构型；而当6≤n≤10时, 溶剂共享离子对 (SSIP)为稳定结构。随着团簇尺寸的增加，当n≥11时，x个水分子分割离子对 (xSIP, x是Ni2+和SO42-之间的水分子数目，且x≥2)为稳定构型。对 NiSO4溶液和NiSO4?6H2O进行EXAFS实验，结果证实Ni2+第一水合层是由六个水分子形成的稳定八面体结构，且当 NiSO4溶液浓度从0.70 mol/L到2.22 mol/L(近似饱和溶液)并未发现CIP构型。Ni-O距离和配位数(CN)分别是 2.040±0.020 ? 和6.0±1.0，这些结论与[NiSO4(H2O)n]0水合团簇的DFT计算结果一致。 相似文献
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采用经典分子动力学、OPLS-AA全原子力场及TIP4P水模型,研究了300 K温度下无限稀释及1.0 mol/L的RbCl水溶液中Rb~+与Cl~-微观水合结构、水化及离子缔合特征。RbCl溶液中,水分子以氧原子去接近Rb~+,而Cl~-周围的水分子则以其中的一个氢原子去靠近。对模拟轨迹分析,获得了径向分布函数、配位数曲线、取向分布函数、水化因子等微观结构及水化信息。计算得到的Rb~+和Cl~-的第一水合层的水合距离及水合数分别为0.288、0.318 nm和7.30、7.17,对应的水化半径及水化数分别为0.270、0.290 nm和2.37、3.05。在1.0 mol/L的RbCl水溶液中,Rb~+与Cl~-之间存在直接接触和溶剂共享离子对,其Rb~+与Cl~-之间的特征距离分别为0.326和0.522 nm。采用Einstein法计算得到Rb~+和Cl~-的自扩散系数分别为(2.194±0.091 3)×10-5和(2.002±0.074 8)×10-5cm~2/s,计算得到的自扩散系数与实验值吻合很好。 相似文献
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Li2SO4溶液中离子间的缔合相互作用:基于密度泛函理论和分子动力学模拟的研究 总被引：1，自引：1，他引：0
基于密度泛函理论,使用B3LYP/aVDZ方法对[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇的结构和性质进行了系统地研究,并结合Car-Parrinello分子动力学(CPMD)模拟了不同浓度的Li_2SO_4溶液结构,目的在于理解在Li_2SO_4溶液中离子间缔合相互作用及可能存在的物种。研究发现,对于[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇,双配位单齿螯合接触离子对结构比双配位双齿螯合接触离子对结构更稳定,溶剂共享离子对结构最不稳定。同时,CPMD模拟结果表明,在3.09和3.17 mol/kg的Li_2SO_4溶液中,双配位单齿螯合接触离子对结构仍然是主要物种。以上结果表明在饱和的Li_2SO_4溶液(3.16 mol/kg)中,Li~+和SO_4~(2-)离子间的相互缔合作用主要以双配位单齿螯合接触离子对结构的物种存在,而具有双配位双齿螯合离子对结构的物种占少数,溶剂共享离子对结构几乎不存在。 相似文献
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基于密度泛函理论,采用ωB97XD方法和6-311++G(d,p)基组,系统研究了[K(H2O)n]+,[NO3(H2O)n]-和KNO3(H2O)n水合团簇的结构和性质;并结合经典分子动力学、OPLS-AA全原子力场以及SPC/E水模型模拟了不同水盐比(WSR) KNO3溶液,目的在于深入理解KNO3溶液中K+和 NO-3的微观水合结构,以及K+-NO-3离子间缔合作用特征。研究发现,对于KNO3(H2O)n (n=6,8,10和12)水合团簇,K+第一水合层稳定结构为四、五和六水合结构,其中五水合结构最稳定。K+和NO-3主要以溶剂共享离子对形式存在。随着团簇尺寸减小,直接接触离子对(CIP)物种出现。同时,分子动力学模拟证实KNO3溶液中形成了直接接触K+-NO-3离子对,且随着溶液浓度增加,CIP物种形成需越过更大能垒。以上结果表明在KNO3稀溶液中主要存在物种为水合K+和NO-3,随浓度增大,单齿直接接触离子对(MCIP)逐渐出现。在高浓溶液或过饱和溶液中,K+-NO-3离子缔合主要以单齿CIP和少量双齿CIP结构存在。 相似文献
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不同浓度的Na2SO4水溶液的拉曼光谱显示了SO42-的四个拉曼活性带:980 cm-1处的SO42-的对称伸缩振动模式v1带,1 106 cm-1处的反对称伸缩振动模式v3带,448 cm-1处的变形振动模式v2带和617 cm-1处的变形振动模式v4带。482 cm-1处的肩膀峰是由于NaSO4-离子对的形成对448 cm-1的v2带的影响而形成的SO42-的一个新的振动峰。浓Na2SO4水溶液中,水共享离子对[Na+.H2O.SO42-]-是主要的离子对物种。随着Na2SO4水溶液浓度的增加,Na+和SO42-的相互作用增强,NaSO4-离子对所占的摩尔分数增加。 相似文献
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LIU Hong-yan ZHU Fa-yan ZHOU Yong-quan WANG Guang-guo FANG Yan ZHANG Wen-qian HAN Li 《盐湖研究》2019,27(2):53-68
The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory( DFT) calculation and extended X-ray absorption fine structure( EXAFS) spectroscopy. The geometric optimization and energy calculation of nickel sulfate hydrated clusters of the molecular formula [NiSO_4( H_2 O)_n]~0( n = 1-12) were determined via DFT using the B3 LYP method. Several possible initial structures were considered for clusters of each size to locate the equilibrium geometry.Based on the DFT calculation,the favorable structure of Ni~(2+)includes the six-coordinated form of [NiSO_4( H_2 O)_n]~0 clusters. The results of hydration energy calculation suggest that the six-coordinated contact ion pair( CIP) is the stable configuration for small hydration clusters( n≤5),while the solventshared ion pair( SSIP) represents the favorable structure for medium hydration clusters( 6≤n≤10).The solvent is separated by x water molecules( xSIP,x ≥2 is the number of water molecule between Ni~(2+)and SO_4~(2-)) in larger hydration clusters( n≥11). The EXAFS analysis of the NiSO_4 aqueous solutions and NiSO_4·6 H_2 O solid established that Ni~(2+)was surrounded by six water molecules tightly forming an octahedral structure in the first hydration shell,and no CIP was found from 0. 70 mol/L to 2. 22 mol/L( near saturation). The Ni-O distance and coordinated number were 2. 040 ± 0. 020 ? and 6. 0 ± 1. 0,respectively. These results are consistent with the DFT calculations for [NiSO_4( H_2 O)_n]~0 clusters. DFT and EXAFS are powerful techniques that can be used to enhance the resolution of NiSO_4 solution microstructure. 相似文献
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采用静态试验法研究了水溶性富勒烯对U(VI)在氧化多壁碳纳米管上吸附的影响。结果表明,羟基化富勒烯(C60(OH)n)和羧基化富勒烯(C60(C(COOH)2)n)的加入对U(VI)在氧化多壁碳纳米管上的吸附量影响作用类似。在pH<3范围内,羟基化富勒烯和羧基化富勒烯对吸附几乎没有影响,在pH>3以后,二者开始抑制碳纳米管对U(VI)的吸附。较低浓度(10 mg/L)的C60(OH)n对U(VI)的吸附几乎没有影响。而等量的C60(C(COOH)2)n已呈现出明显的抑制作用。但两者的作用机理不同,前者可能是由于羟基化富勒烯和U(VI)竞争氧化多壁碳纳米管上的吸附位点造成的,后者则可能改变了氧化多壁碳纳米管的表面电荷。用双位点模型对不同固液比和U(VI)初始浓度下U(VI)的吸附率随C60(OH)n和C60(C(COOH)2)n初始浓度的变化进行了拟合得到了很好的结果。 相似文献
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当观测资料的数据量少而又存在多个相互影响或关联的变量时,常用的灰色预测模型GM（1,1）不能全面考虑多个变量。为此,采用自适应MGM（1,n）模型—多变量灰色预测模型,较好地解决了这一问题。针对一些地区气象数据较少甚至缺失的情况,以内蒙古正蓝旗的气象资料用Penman-Monteith计算的参考作物蒸散量（ET0）为研究对象,运用灰色系统理论建立MGM（1,3）模型,模拟预测参考作物蒸散量变化规律,并与GM（1,1）模型和BP神经网络模型比较,结果表明MGM（1,3）模型有较好的预测效果。 相似文献
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This paper aims to demonstrate the relationships between ENSO and rice production of Jiangxi province in order to identify the reason that ENSO might have little effect on Chinese rice production. Using a data set with measures of Jiangxi's climate and rice production,we find the reason that during 1985 and 2004 ENSO's well correlated with rainfall did not promote Chinese rice production. First,the largest effects of ENSO mostly occur in the months when there is no rice in the field. Second,there is almost ... 相似文献
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《The Professional geographer》2012,64(1):1-8
The Great Plains is the grasslands of the central United States, but precise delineation of this region has evaded agreement due to the transition between Great Plains grasslands and forests of the eastern United States. After comparing Great Plains delineations in readily available geographic information system layers, I established a northeastern boundary using evidence from historical tree surveys during the 1800s. Additionally, I described tree presence within the Great Plains over time and potential drivers of change. The definition documented here diverges from others by including most of Iowa and part of Illinois, and even small sections in Indiana and Wisconsin, but excluding Missouri due to regular tree presence overall at landscape scales of ecological subsections. In this definition, the Great Plains had an extent of 2.29 million km2 in fifteen states, including Indiana and Wisconsin, and 2.19 million km2 after removal of open forests in Oklahoma and Texas. Tree presence occurs within the Great Plains and tree encroachment is not a new process; however, tree encroachment is increasing in the Great Plains, which causes a decrease in the grasslands region. Nevertheless, clarifying the historical eastern boundary provides a solution to the problem of competing versions of the Great Plains region. Key Words: ecotone, prairie, savanna, tree encroachment. 相似文献
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This article examines the effect of high foreclosure rates on postrecession lending. Our hypothesis is that high neighborhood foreclosure rates will have a significant and positive effect on the likelihood of mortgage loan denial. In a case study on Toledo, Ohio, we explore the role of foreclosure activity, race, and racial disparities in lending practices and how they differ across neighborhoods. Our results suggest that applicants in high-foreclosure neighborhoods have a greater likelihood of loan denial (ceteris paribus). We also find that minority applicants face a higher probability of loan denial in high-foreclosure minority neighborhoods. Overall, the results depict highly variable lending practices where race seems to make a difference albeit in a small subset of neighborhoods deeply affected by the foreclosure crisis. There is also some indication of a chilling effect on minority loan applicants in Toledo during the postrecession period. Key Words: foreclosure, logistic regression, mortgage lending, neighborhood contingency, race discrimination. 相似文献
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Inequality has been the subject of intense debates in China, but inequality across cities remains less studied. This article investigates economic inequality based on prefectural-level cities during the period from 1990 to 2010. Statistical analyses indicate that interregional inequality among cities has increased, which is mostly attributable to widening intraregional inequality, especially within the western region. The high gross domestic product (GDP) per capita clusters emerged in the Pearl River Delta in the 1990s, spread to the Yangtze River Delta in the 2000s, and then reached north China in the 2010s. In contrast, the number of low GDP per capita clusters significantly increased in the central and western regions in the 2010s. In addition, the significance of national development zones and foreign direct investment indicates the greatest effect of globalization on the increasing intercity inequality. Decentralization also contributes to the intercity inequality of China. We suggest that in addition to national programs aimed at reducing the inequality between the eastern region and the rest of China, efforts are needed to reduce inequality within each region through provincial and local government policies, especially in western China. Key Words: China, cluster, decentralization, globalization, regional inequality, urban inequality. 相似文献