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1.
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
2.
运用密度泛函理论(DFT)在ωB97XD/gen (O、H元素Aug-cc-PVDZ; Rb元素Lanl2DZ)基组水平上研究了[Rb(H_2O)_n]~+(n=1～12)水合团簇的结构和光谱学性质。研究结果表明,通过分析气相和液相中的稳定能以及水合团簇可知,稳定构型出现在8配位的团簇中。第一配位层水分子数为8时形成Rb~+第一近似饱和水合层。此外,拉曼光谱显示[Rb(H_2O)_n]~+(n=1～12)水合团簇中O-H伸缩振动峰随着水分子数增加发生移动和加宽,Rb~+发生水合时,O-H对称和非对称伸缩振动发生红移,随着水合数的增多,频率蓝移。此外,文中对拉曼光谱中O-H振动的频率位置结合团簇结构进行了说明。 相似文献
3.
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
4.
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
5.
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
6.
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
7.
报道由硫酸钠水溶液实验径向分布函数通过理论模型计算,解析溶液结构参数的方法。其中包括建立理论结构模型的基本依据,专用KURLVR程序使用和结构参数最小二乘精修,以及高斯多峰拟合等实用方法,最终给出能够阐述溶液本质的微观结构参数。结果表明,硫酸钠溶液中水合Na+有2个水合层,第一水合层Na+-OH2(I)距离为0.243 nm,配位数6.0;第二水合层距离为0.448 nm,配位数为13.3;SO2-4存在第一水合层,SO2-4-H2O距离为0.374 nm,配位数为9.1;水合硫酸根原子团中氧原子与水分子的作用距离和配位数按OS-W(1)、OS-W(2)、OS-W(3)、OS-W(4),距离依次为0.283、0.322、0.375和0.486 nm,配位数除OS-W(2)为12.9,其余都在8左右;除此之外溶液中还存在NaOSO-3接触离子对,Na-S距离为0.348 nm,配位数0.20,与晶体结构比较证实SO2-4以单齿形式配位到Na+;水共享离子对Na+-W-SO2-4中Na-S距离精修为0.491 nm,配位数0.62。精修的R因子为0.16,表明获得了很好的精修结果。 相似文献
8.
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
9.
采用分子动力学(MD)模拟研究了5.55 mol·kg~(-1)氯化钙溶液的微观结构特征,尤其是溶液中高配位Ca-Cl离子团簇的结构与性质,探究了温度对于高配位Ca-Cl离子团簇的影响。结果显示,5.55 mol·kg~(-1)氯化钙溶液中,除形成[CaCl]~+、[CaCl_2]~0离子对外,还存在一些高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇。高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇在5.55 mol·kg~(-1)氯化钙溶液中介稳存在,易解离或进一步缔合形成更大Ca-Cl离子团簇,这可能与溶液中大量未完全水合Ca~(2+)对高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇水壳层的扰动破坏有关。温度升高,氯化钙溶液中Ca-Cl离子缔合增强,但高配位Ca-Cl离子团簇的平均存在时间(t_(av))减小,这表示高温下溶液中Ca-Cl离子团簇频繁地解离与缔合,离子团聚趋势更为显著。本工作观测到的高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇可能是浓氯化钙溶液Ca-Cl离子缔合过程中一种热力学不稳定结构,但这些高配位Ca-Cl离子团簇的形成可能对溶液结晶及相关化学过程产生不利影响。 相似文献
10.
利用精密量热仪测定了MgCl_2、MgCl_2·2H_2O、MgCl_2·4H_2O和MgCl_2·6H_2O在298.15°K溶于水的积分溶解热,并利用Pitzer电解质溶液的。~ΦL方程,计算了溶质的相对表观摩尔热焓,从而得到标准溶解焓分别为(KJ·mol~(-1))—155.86±0.17、—79.45±O.17,—41.78±O.18和—14.58±0.16;晶格能分别为—2490.36,—3158.37,—3772.70和—4376.56。二、四、六水合物的标准生成焓分别为—1289.39,—1898.72和—2497.58;水合焓分别为—76.41,—114.08和—141.28。 相似文献
11.
四川盆地雷口坡组大量钻井资料揭示中三叠统雷口坡组主要成盐期分别为雷三2期和雷四2期。岩性组合特征、沉积环境研究表明,在川中的平昌—南充—遂宁一带发育雷三2期浓缩盐膏质蒸发泻湖微相,在川中-川西地区的南部—盐亭—成都—邛崃地区发育雷四2期盐膏湖盆微相。两期盐岩差异主要表现是,雷三2期时,盆地处于频繁的海进、海退过程中,沉积环境变化较快,成盐环境相对开放,盐盆往往多次蒸发浓缩、补给、淡化,海水表现出接近或者达到盐岩沉积浓度,其间往往夹杂石膏和云质团块沉积。雷四2期时,四川盆地处于持续的海退蒸发期,蒸发量远远大于补给量,海水以蒸发浓缩为主,海水表现为超过石盐沉积浓度,沉积石盐中夹杂卤石,局部地区钾含量极高。 相似文献
12.
We have measured the distribution coefficient (Kd) of210Po and210Pb in laboratory systems and in natural freshwater systems. In the laboratory systems, an inverse relationship was observed between the particle concentration of sand or lake sediment, and the distribution coefficients of210Po and210Pb. The slope of the log-linearK
d
vs particle concentration relation is consistent with existingK
d-particle concentration theories. These laboratory observations are consistent with similar measurements in two lakes. TheK
d values of Po and Pb for the bottom sediment-pore water system with a high particle concentration were 10 to 100 times lower than those for dilute concentrations of particles suspended in the lake water. TheK
d of210Pb in the sediments was >104 so that the diffusive transport of210Pb has only a small influence on the interpretation of210Pb concentration-depth profiles and the210Pb dating of these sediments.This is the second of a series of papers to be published by this journal following the 20th anniversary of the first application of210Pb dating of lake sediments. Dr P. G. Appleby is guest editing. 相似文献
13.
14.
Jörn Parplies Andreas Lücke Heinz Vos Jens Mingram Martina Stebich Ulrich Radtke Jingtai Han Gerhard H. Schleser 《Journal of Paleolimnology》2008,40(1):471-487
Total organic carbon (TOC) content, total nitrogen (TN) content, stable nitrogen isotope (δ15N) and stable organic carbon isotope (δ13Corg) ratios were continuously analysed on a high resolution sediment profile from Lake Sihailongwan (SHL), covering the time
span between 16,500 and 9,500 years BP. Strong variations of the investigated proxy parameters are attributed to great climatic
fluctuations during the investigated time period. Variations in organic carbon isotope ratios and the ratio of TOC/TN (C/N
ratio) are discussed with respect to changing proportions of different organic matter (OM) sources to bulk sedimentary OM.
Phases of high TOC content, high TN content, depleted δ13Corg values and high δ15N values are interpreted as times with increased productivity of lacustrine algae in relation to input of terrigenous organic
matter. Two distinct phases of enriched nitrogen isotope ratios from 14,200 to 13,700 and 11,550 to 11,050 years BP point
towards a reduced phytoplankton discrimination against 15N due to a diminished dissolved inorganic nitrogen pool. The combination of geochemical (TOC, TN, C/N ratio) and isotopic
(δ13Corg, δ15N) proxy parameters points to a division of climate development into four stages. A cold and dry stage before 14,200 years
BP, a warm optimum stage with high phytoplankton productivity from 14,200 to 12,450 BP, a colder and drier stage from 12,450
to 11,600 BP and a stage of climatic amelioration with high variability in TOC and TN contents after 11,600 BP. These results
are discussed in relation to monsoon variability and Northern Hemisphere climate development of the late glacial. 相似文献
15.
I. D. L. Foster T. M. Mighall H. Proffitt D. E. Walling P. N. Owens 《Journal of Paleolimnology》2006,35(4):881-895
We present 137Cs profiles for three low lying coastal lagoons in Southwest England that show a decline in activity with sediment depth.
137Cs inventories are lower than expected by comparison with local reference inventories despite the fact that sampling was undertaken
in the deep-water zone of each lake where sediment and 137Cs focusing would be expected. At all three locations, lake sediment 7Be and unsupported 210Pb (210Pbun) inventories are not significantly lower than the local reference inventory. 137Cs inventories in the study cores range from 38 to 95% of local reference inventories. The standing water level and mud: water
interface at two sites are below maximum tide level and, at all three sites, salinity increases significantly in the water
columns between low and high tide and in the pore waters of the underlying sediments. We suggest that the difference in hydrostatic
pressure between sea level and standing water levels in the lagoons forces salt water up through the sediment column and that
monovalent cations (especially Na+ and K+) replace 137Cs on exchange sites leading to the upward migration and loss of 137Cs. Rising sea levels may therefore contribute to remobilisation and release of 137Cs to the aquatic environment from the sediments of coastal lagoons. 相似文献
16.
Human disturbance and trophic status changes in Crystal Lake, McHenry County, Illinois, USA 总被引：6，自引：0，他引：6
The paleolimnology (sediment chemistry, 210Pb dating, pollen, and diatoms) of Crystal Lake, McHenry County, Illinois, USA was studied to investigate the impact of European settlement on lake trophic status. Pollen clearly indicates a vegetational shift from Quercus dominance to Ambrosia. 210Pb dating suggests that the Ambrosia rise likely occurs around the 1840's, which is consistent with historical records on the European settlement in this area. Coincident with the vegetational shifts, several diatom species, Cyclotella meneghiniana, Fragilaria crotenensis, Asterionella formosa and Tabellaria fenestrata, all increase while C. comta decreases after the settlement. However, C. comta and Aulacoseira ambigua, two dominant species, remain abundant throughout the entire core. Their relative abundances at the surface sediments reach presettlement levels. It is hypothesized that Crystal Lake, a glacial lake rich in CaCO3, may have been able to assimilate increases of phosphorus by coprecipitating phosphorus with CaCO3. Such a 'buffering mechanism may be responsible for the lake's resistance to trophic changes or recovery following disturbance. 相似文献
17.
Claire L. Schelske Arthur Peplow Mark Brenner Craig N. Spencer 《Journal of Paleolimnology》1994,10(2):115-128
Sediment cores from three lakes were dated with210Pb using a constant rate of supply (CRS) model. We used low-background gamma counting to measure naturally occurring levels of210Pb,226Ra, and137Cs in sediment samples because sample preparation is simple and non-destructive,226Ra activity provides a direct measure of supported210Pb activity for each sample analyzed, and137Cs activity may provide an independent age marker for the 1962–1963 peak in atmospheric fallout of this radionuclide. In one core supported210Pb activity was estimated equally well from226Ra activity of each sampling interval or from the mean total210Pb activity of constant activity samples at depth. Supported210Pb activity was constant with depth in this core. In a short freeze core, determining226Ra activity of every sample proved advantageous in estimating supported210Pb activity because supported210Pb activity could be estimated from210Pb measurements only at the deepest sampling interval. Supported210Pb activity estimated from226Ra activity also yielded more precise estimates of highly variable sedimentation rates. In the third core226Ra activity exceeded210Pb activity at the top of the core and varied 20 fold with depth. This high input of226Ra in disequilibrium with210Pb is attributed to recent erosion of radium-bearing materials in the drainage basin. These data invalidate the assumption that supported210Pb activity is constant in sediment cores and can be estimated from the mean total210Pb activity at depths where210Pb activity is constant. We recommend using gamma counting or another independent assay of226Ra to validate the assumption of constant supported210Pb activity in sediment cores if there is reason to expect that226Ra activity varies with depth.This is the fourth of a series of papers to be published by this journal following the 20
th
anniversary of the first application of210Pb dating of lake sediments. Dr. P.G. Appleby is guest editing this series. 相似文献
18.
Pierre Giresse Makaya Mvoubou Jean Maley Alfred Ngomanda 《Journal of Paleolimnology》2009,41(2):369-392
Seven vibro-cores were collected from three shallow lakes of the Gabon (Kamalété, Nguène, Maridor) along a 300-km west–east
transect close to the Equator. These lakes are located in very distinct landscapes: coastal forest-savanna mosaic, rain forest
and savanna with colonising forest, respectively. Core chronologies were established by radiocarbon dating. Study of these
lacustrine archives (textural variables, clay minerals, organic matter components, δ13C, pollen) allowed comparison of late Holocene environmental changes recorded at each site and with results from other studies.
Lake Kamalété indicates minor climatic deterioration (increased drying and greater seasonality) between 1,410 and 500 cal.
years BP, which is also recognised in southern Cameroon and east-central Africa. Lake Nguène was surrounded by dense moist
forest throughout the last 4,110 years, but shows significant deterioration from ~2,800 cal. years BP, a phenomenon seen at
nearby sites. Lake Maridor shows a decline of forest initiated a little after 3,800 cal. years BP, which indicates timing
that is distinct from the two other sites. This was probably a response to local conditions (i.e. outlet damming). Although
the three lakes display generally parallel climatic trends perhaps linked to SST oscillations, there is not perfect coherence
between these three sites. Differences among the three basins may be attributable to local factors like groundwater hydrology
and slope instabilities of such shallow lake systems in this equatorial region. 相似文献
19.
P.G. Appleby 《Journal of Paleolimnology》2004,31(4):433-443
Sediment cores collected from eight lakes along the western coast of Svalbard as part of a project investigating atmospheric pollution and environmental change in Arctic regions were dated radiometrically using natural (210Pb) and artificial (137Cs and 241Am) fallout radionuclides. At four sites the sedimentation rates were relatively uniform, and in consequence the 210Pb dates were relatively unambiguous. At the remaining sites there were irregularities in the 210Pb activity versus depth profiles, indicating significant variations in the net sediment accumulation rate during the past 120 years. At these sites, there were significant differences between 210Pb dates calculated using the two standard simple dating models, constant rate of supply (CRS) and constant initial concentration (CIC). In most cases, stratigraphic dates based on the 137Cs and 241Am records supported use of the CRS model, though at one site (Ossian Sarsfjellet) the CIC model appeared more appropriate. The irregularities in the 210Pb records were mainly caused by episodes of accelerated sedimentation due, for example, to inwash or slump events, though at some sites there appears to have been a systematic increase in sediment accumulation rates in recent decades. Sediment accumulation rates were generally lower at the northern sites, and higher at the more southerly locations. Mean sediment accumulation rates varied by an order of magnitude, ranging from 0.002 to 0.050 g cm−2 y−1 (0.02–0.10 cm y−1). 210Pb fluxes measured from the core inventories were mostly in the range 34–80 Bq m−2 y−1 typical of Arctic sites. Much higher values, recorded at two sites (Birgervatnet and Daltjørna), may be due to significant inputs from the catchments during spring thaw. 相似文献
20.
210Pb and 137Cs dating methods in lakes: A retrospective study 总被引：1，自引：0，他引：1
210Pb has been used for more than two decades to provide the geochronology of annually deposited sediments and to construct pollution histories. Evidence from some lakes suggests that this radionuclide may be adequately mobile to compromise dating reliability. This study provides one test of that possibility by comparing recent measurements of 210Pb and trace metals to ones carried out more than 20 yrs in the past. 137Cs dating is used to confirm sediment accumulation rates in the recent cores. In the three Connecticut, USA, lakes studied, sediment accumulation rates changed abruptly to higher values between 40-50 yrs ago (increasing by factors of 2.2, 2.9, and 3.0). In all three lakes, rates calculated from 210Pb distributions both above and below this horizon agreed, within measurement uncertainty, in recent and older cores. Furthermore, when the older data were corrected for 20 yrs of burial, the changes in slope in 210Pb distributions occurred at the same depth in each pair of cores. The depth of sharp peaks in concentrations of trace metals also matched. In general, this evidence supports the idea that sediments in these lakes have simply been buried, without significant diagenetic remobilization of 210Pb and trace metals . Nevertheless, some important differences were also observed. For two of the three lakes, there was a significant difference in average sediment accumulation rate during the past 33 yrs as calculated from 137Cs and 210Pb in the recent cores. Most potential causes for this difference can be ruled out, and it appears that one of the two nuclides is remobilized compared to the other. There were also significant differences in the total inventories of both 210Pb and trace metals (both up to 2 ×) between recent and older cores in some cases. This may be due to dissimilar sediment focusing, since it is not known for certain whether the new cores were collected at exactly the same sites as in the past. 相似文献