高氯酸锂在有机溶剂中离子溶剂化和离子缔合的红外光谱研究

利用红外光谱技术研究了LiClO4在碳酸丙烯酸,γ－丁内酯和碳酸二乙酯中的离子缔合和离子溶剂化。溶剂分子谱带的变化证明,锂离子与溶剂分子的相互作用主要是通过羰基氧原子进行的,醚氧也可能参与了相互作用,高氯酸锂的v1和v4谱带变化则证明了溶液中离子对的存在,而离子对的种类与溶剂分子的特性有关。     

高氯酸根及其离子对光谱指认的量子化学研究

利用红外和拉曼光谱研究了不同浓度下高氯酸锂在N,N-二甲基甲酰胺、乙腈、四氢呋喃、丙酮、二甲亚砜、乙酸甲酯等有机溶剂中的缔合情况,分析了高氯酸根v1谱带的变化,指认了溶液中光谱自由离子、直接接触离子对和离子对二聚体.使用量子化学方法计算了不同结构直接接触离子对和离子对二聚体的稳定构型和光谱行为,并和实验值进行了比较,考察了溶剂化模型、溶剂分子对直接接触离子对或离子对二聚体结构的影响,探讨了量子化学方法指认离子对的可能性和正确性.     

氟羟磷灰石通道离子的FTIR研究

以傅立叶变换红外光谱为表征手段,对合成的氟羟磷灰石通道离子进行研究。结果发现:F-离子替换羟基后,羟基在3573和634 cm-1的振动吸收带强度减弱,而在3542、678、715和736 cm-1左右出现新的振动谱带,且随F-离子含量不同出现规律性变化。新出现的谱带数目与群论推测的结果相符,表明该谱带属于羟基基团;羟基振动吸收带的变化,表明F-离子替换羟基的位置,形成[OH…F]氢键,使羟基的伸缩振动向低频偏移,弯曲振动向高频偏移。另外,通过3542-3573cm-1和715-736cm-1左右的谱带相对面积比与F-含量的关系,可为F-离子替换羟基行为提供一些依据。     

M+AsF6-(M=Li,Na,K,Rb和Cs)离子对的结构和振动光谱

利用abinitio计算方法研究了AsF6-阴离子和M AsF6-(M =Li ,Na ,K ,Rb 和Cs )直接接触离子对的结构和光谱行为。结果表明,具有C3V结构三齿相互作用的M AsF6-最稳定,二齿配位的结构只有在特定条件下才可能稳定存在。当形成离子对后,阳离子与AsF6-的相互作用将改变AsF6-的结构,这其中Li 的影响最大。另外,AsF6-光谱的变化可用来指认溶液中离子的缔合和离子对的种类。     

酸碱染料离子的缔合及等色化

本文阐述了等色染料离子对形成的实验方法,等色染料离子对的缔全机理及其形式,用吸收光谱的能级图,从电子理论角度论述了等色染料离子对的缔合效应等色化,溶剂效应等以化机理。列表示出等色染料离子对的高灵敏度,从而证明了等色染料离子对的萃取光度,浮选光度及萃取荧光光度法是高灵敏度和超灵敏度的新体系,为金属痕量和超痕量分析开辟了更为宽广的前景。     

借助功能阳离子实现敏化发光的铕配合物的溶剂效应的研究

在离子缔合型铕配合物Eu(tta)4.DEASPI中,借助功能阳离子DEASPI的电荷转移激发态可以实现对铕离子的单光子与双光子的敏化发光,其能量传递遵循Frster机制。将Eu(tta)4.DEASPI溶解于多种有机溶剂中(丙酮、DMF、乙醇和乙腈),发现溶剂效应对于该能量传递体系的影响非常显著。借助光谱测量,发现在乙腈溶液中能量传递效率远高于其他三种溶剂。本文对造成溶剂效应的多种因素进行了详细的分析。     

酮类有机物放电离子淌度谱研究

离子淌度谱是一种快速检测痕量挥发性有机物的高灵敏方法.在放电离子源离子淌度谱装置上,研究了八种酮类有机物的离子淌度谱.实验测量了各种离子的约化迁移率,其中丙酮、正丁酮、1-甲基-2-吡咯烷酮、环己酮、苯乙酮的实验结果与前人63Ni放射源离子淌度谱相一致,而甲基异丙基酮、4-甲基-2-戊酮、环戊酮单体和二聚体离子的约化迁移率则是首次报道.实验测量的约化迁移率与离子质量线性相关,获得的对酮类有机物检测灵敏度在ng·L-1量级.     

第三族金属氧化物离子对二氧化碳转化的红外光谱研究（英文）

木文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制.研究表明,对于[ScO(CO_2)_n]~+体系,在n≤4时,形成了溶剂化结构;在n=5时,形成了碳酸盐结构,实现了二氧化碳的转化.对于[YO(CO_2)_n]~+体系,需要4个二氧化碳分子就可以实现二氧化碳的转化.而在[YO(CO_2)_n]~+体系中,只发现了溶剂化结构,没有观察到碳酸盐结构.理论计算表明,[YO(CO_2)_n]~+体系拥有最小的溶剂化结构向碳酸盐结构转化能垒,[LaO(CO_2)_n]~+体系拥有最大的溶剂化结构向碳酸盐结构转化能垒.本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律.     

槲皮素作为荧光探针对氟离子的识别作用

槲皮素为天然黄酮类化合物,广泛存在于植物的根、茎、叶、花和果实中。槲皮素作为荧光探针检测氟离子不仅具有较好的选择性和灵敏度,而且与合成的荧光探针比,还具有来源广、环保、无毒等优点。实验将不同阴离子(F~-,Cl~-,Br~-,I~-,ClO_4~-,H_2PO_4~-)分别加入到槲皮素的二甲基亚砜(DMSO)溶液中,考查槲皮素溶液的荧光强度变化。实验发现当加入氟离子后,槲皮素在500nm处的荧光发射峰的强度降低,发生荧光猝灭,且其猝灭程度随着氟离子浓度的增大而改变,即荧光强度随着氟离子浓度的增大而减小,并呈线性变化。而其他阴离子的加入对槲皮素和槲皮素-氟离子体系的荧光发射强度影响不大,说明其他阴离子不影响槲皮素对氟离子的识别,显示了槲皮素对氟离子具有较好的选择性。由荧光滴定光谱和荧光滴定曲线得到槲皮素对氟离子的滴定方程为:y=-13.36x+173.4,线性关系为R2=0.991,线性范围为1.0×10~(-6)~8.0×10~(-6)mol·L~(-1),最低检测限为1.0×10-7 mol·L~(-1),表明槲皮素对氟离子的识别具有较高的灵敏度。进一步实验表明槲皮素识别氟离子的机理可能是氟离子的加入破坏了溶液体系的氢键,改变了槲皮素分子的共轭状态,发生分子内电荷转移,促使槲皮素荧光猝灭。用该法成功检测了样品中微量氟离子,回收率为100.67%~102.44%,精确度较好,测定结果稳定。     

低能离子对酪氨酸溶液损伤作用的光谱研究初报

利用气体我放电产生低能离子,其在放电间隙的电场加速下撞击水溶液样品。了低能离子作用后酪氨酸溶液的紫外及红外吸收光谱的变化。结果表明,气体放电产生的离子对Ｔｙｒ造成了多种损伤。不仅使化学键断裂,分子解体,而且外来的活性离子会与溶液中的元素形成新的化学基团,妆在受损伤分子碎片上组成新的损伤物质,充分体现了低能离子与物质相互作用的“离子沉积”效应。     

二氯苯3种同分异构体及其阳离子的红外光谱研究

用从头算理论,在B3LYP/6-31G（d）基组水平上对二氯苯3种同分异构体及其阳离子进行了优化计算,得到其稳定构型,从而得到它们的红外振动光谱;计算结果显示,二氯苯的3种同分异构体的电离是对二氯苯中氯原子的电离。通过对所得红外光谱的分析得到,二氯苯3种同分异构体及其阳离子的红外振动谱有很大的差别,氯的位置的不同对偶极矩变化的大小有很大的影响;而且,分子的电离对振动偶极矩的变化产生了较大的影响。     

原子吸收法间接测定水中可溶性PO4^3—的研究

研究并建立了测定水中PO4^3-的方法,用草酸钙将PO4^3-转化为磷酸钙,加醋酸溶解磷酸钙,离心沉降未反应的试剂,用AAS法测定清液中的Ca^2 ,即可间接测定PO4^3-的含量。     

Charge-induced fragmentation of sodium clusters

The fission of highly charged sodium clusters with fissilities X>1 is studied by ab initio molecular dynamics. Na4+24 is found to undergo predominantly sequential Na+3 emission on a time scale of 1 ps, while Na(Q+)(24) ( 5< or =Q< or =8) undergoes multifragmentation on a time scale > or =0.1 ps, with Na+ increasingly the dominant fragment as Q increases. All singly charged fragments Na(+)(n) up to size n = 6 are observed. The observed fragment spectrum is, within statistical error, independent of the temperature T of the parent cluster for T< or =1500 K. These findings are consistent with and explain recent trends observed experimentally.     

Salt permeation and exclusion in hydroxylated and functionalized silica pores

We use combined ab initio molecular dynamics (AIMD), grand canonical Monte Carlo, and molecular dynamics techniques to study the effect of pore surface chemistry and confinement on the permeation of salt into silica nanopore arrays filled with water. AIMD shows that 11.6 A diameter hydroxylated silica pores are relatively stable in water, whereas amine groups on functionalized pore surfaces abstract silanol protons, turning into NH3+. Free energy calculations using an ab initio parametrized force field show that the hydroxylated pores strongly attract Na+ and repel Cl- ions. Pores lined with NH3+ have the reverse surface charge polarity. Finally, studies of ions in carbon nanotubes suggest that hydration of Cl- is more strongly frustrated by pure confinement effects than Na+.     

Spectroscopic studies of triflate ion association in polymer gel electrolytes and their constituents

Raman and NMR spectroscopy have been used to investigate the state of ion association in systems comprising salt, polymer and/or solvent. The dissolved salt in each case was lithium triflate (lithium trifluoromethane sulphonate). Five systems were studied, comprising polymer gel electrolytes or constituents of such electrolytes. These were: salted (a) N,N'-dimethyl formamide (DMF), (b) tetraethylene glycol dimethylether (tetraglyme), (c) polyethylene glycol (PEG), (d) end-esterified PEG and (e) poly(vinylidene fluoride) (PVDF) gels containing either DMF or tetraglyme. Raman results give a broad indication of the significance of end-group, solvent and polymer choice in triflate-salted systems. In all cases, anion association rises with temperature, often with a significant increase in ion aggregation. The reliability of these results is supported by an analysis of systematic errors incident in this technique for ion association measurements. A limited comparison performed on the system having the highest concentration of ion aggregates (end-esterified PEG) suggests that Raman and NMR spectroscopy provide different information concerning ion association. Reasons for the difference are discussed, concluding that complementary information is obtained owing to the different time constants relevant to the two techniques and to the dependence of the Raman results on molecular proximity.     

Ion storage in Kingdon trap

Abstract

The characteristics of stored ions in a Kingdon trap have been investigated. The charge distribution of stored ions was measured by a time of flight (TOF) mass spectrometer. Storage of Ar^q+ (q = 1, 2, 3, 4) produced by electron beam irradiation has been confirmed. The dependences of Ar ion yields on the trapping potential and storage time have been systematically studied.

Applying a voltage to end plates is very important for the storage of ions. Remarkable oscillations of the ion yields are found in the decay curves as a function of storage time for Ar⁺, Ar²⁺ and Ar³⁺ indicating periodical motion of each ion group about the central wire. The three dimensional orbits of ions in the trap are analysed by a computer calculation to understand the experimental results.     

Dynamics for Reactions of Ion Pairs in Aqueous Solution: Reactivity of Tosylate Anion Ion Paired with the Highly Destabilized 1-(4-Methylphenyl)-2,2,2-Trifluoroethyl Carbocation

The sum of the rate constants for solvolysis and scrambling of carbon bridging and nonbridging oxygen-18 at 4-MeC(6)H(4)CH(CF(3))OS((18)O(2))Tos in 50/50 (v/v) trifluoroethanol/water, (k(solv) + k(iso)) = 5.4 × 10(-6) s(-1), is 50% larger than k(solv) = 3.6 × 10(-6) for the simple solvolysis reaction of the sulfonate ester. This shows that the ion pair intermediate of solvolysis undergoes significant internal return to form reactant. These data give a value of k(-1) = 1.7 × 10(10) s(-1) for internal return of the carbocation-anion pair to the substrate. This rate constant is larger than the value of k(-1) = 7 × 10(9) s(-1) reported for internal return of an ion pair between the 1-(4-methylphenyl)ethyl carbocation and pentafluorobenzoate anion to the neutral ester (4-MeC(6)H(4)CH(CH(3))O(2)CC(6)F(5)) in the same solvent. The partitioning of ion pairs to the 1-(4-methylphenyl)ethyl carbocation and to the highly destabilized 1-(4-methylphenyl)2,2,2-trifluoroethyl carbocation is compared and contrasted.     

Sodium trimer ordering on a NaxCoO2 surface

Sodium ion ordering on an in situ cleaved NaxCoO2 (x=0.84) surface has been studied by ultrahigh vacuum scanning tunneling microscopy at room temperature. Three main phases, with p(3 x 3), ( radical7 x radical7), and (2 radical3 x 2 radical3) hexagonal unit cells and a surface Na concentration of 1/3, 3/7, 1/2, respectively, were identified. One surprising finding is that Na trimers act as the basic building blocks that order in long range. The stability of Na trimers is attributed to the increased Na coordination with oxygen as indicated by ab initio calculations, and possibly at finite temperature by configuration entropy.