弱结合分子Kr-HF结构与相关效应

采用二阶、三阶MollerPlesset微扰理论方法(MP2,MP3),组态相互作用方法(QCISD)在不同的基组下对弱结合分子体系KrHF进行了abinitio计算,得到了KrHF体系的两个不同的线型平衡几何结构:KrHF和KrFH.对于KrHF分子,在MP2/6311++G水平上得到Kr与HF分子中心的间距为037787nm,离解能为61480eV,谐振频率分别为ν1(σ)=41879638cm-1,ν2(π)=1622953cm-1,ν3(σ)=418689cm-1.并计算得到了这两个分子构型的热力 关键词：     

三元杂多酸-甲基紫超分子化合物的合成及光谱研究

在水溶液条件下合成了一系列具有Keggin结构的PWxV12 -x MV(x =2 ,4 ,6 ,8,10 )超分子化合物 (PWxV12 -x为具有不同配比的磷钨矾三元杂多酸 ,MV为甲基紫 ) ,并对其紫外光谱 ,红外光谱和荧光光谱进行了研究。结果表明 ,杂多酸阴离子上的端氧与甲基紫阳离子上的N 间通过配合作用相互连结而形成超分子化合物。超分子化合物中仍保持有杂多阴离子的Keggin结构以及甲基紫的基本结构。且随着V的含量增加 ,杂多阴离子的氧化能力增强 ,阴离子PWxV12 -x和阳离子MV的相互作用增强 ,νas(M =Ot) ,νas(M Ob M )和νas(M Oc M )的FTIR吸收峰分别从 96 6 ,886和 80 4cm-1变化至 95 5 ,875和 786cm-1;紫外吸收峰也从 5 19nm移至 5 0 6nm ;用 5 30nm的光激发的荧光发射峰也从 6 92移至 6 4 4nm ,与PWxV12 -x和MV间配合作用的强弱呈现了很好的对应关系。     

LiC分子基态及其低电子激发态的多参考组态相互作用方法研究

采用包含Davidson修正的多参考组态相互作用(MRCI+Q)方法结合6-311++G(3df,3pd)基组计算了LiC分子基态(X4Σ-)以及五个低电子激发态(a2Π,b2Δ,c2Σ-,d2Σ+,A4Π)的势能曲线.将得到的势能曲线拟合到Murrell-Sorbie解析势能函数形式,确定了对应态的平衡结构Re、谐振频率ωe和离解能De等光谱数据,计算值与仅有的几个其他结果进行了比较.通过求解核运动的薛定谔方程首次报道了LiC分子几个低电子态在J=0下的振动能级、转动惯量和六个离心畸变常数(Dν,Hν,Lν,Mν,Nν和Oν).     

InCl分子C1Π1态光谱研究

采用激光诱导荧光技术对InCl分子C1Π1→X1Σ+荧光光谱进行了分析和归属, 在发射谱中探测到ν′=1向下的跃迁, 证明C态预离解只能发生在ν′=1之上。 并对C1Π1→X1Σ+的荧光衰变曲线进行了观测, 得到InCl分子C1Π1(ν′=1)态的无碰撞辐射寿命τ0≈11 ns及电子跃迁矩|Re|2≈5.95D2。     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法, 分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组,对BH2和AlH2分子的结构进行了优化计算,得到BH2分子的稳态结构为C2v构型,电子态为2A1、平衡核间距RBH=0.1187nm、键角∠HBH=128.791°、离解能De=3.65eV、基态振动频率ν1(a1)=1020.103cm-1,ν2(a1)=2598.144cm-1,ν3(b2)=2759.304cm-1 .AlH2分子的稳态结构也为C2v构型,电子态为2A1、平衡核间距RAlH=0.1592nm、键角∠HAlH=118.095°、离解能De=2.27eV、基态振动频率ν1(a1)=780.81cm-1,ν2(a1)=1880.81cm-1,ν3(b2)=1910.46cm-1 .采用多体项展式理论推导了基态BH2和AlH2分子的解析势能函数,其等值势能图准确再现了BH2和AlH2分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH2反应中存在鞍点,活化能为150.204kJ/mol;AlH+H→AlH2反应中也存在鞍点,活化能为54.8064kJ/mol.     

分子轨道法（PPP—CI）计算芳烃化合物的荧光光谱及激发态结构

应用分子轨道法（ＰＰＰ－ＣＩ）计算了２５种芳烃化合物的基太和第一激发单重态的π电荷分布，偶极矩，键级，以及各分子轨道的能级分布的变化。计算得到的分子吸收光谱波长与实验值非常一致。发现计算得到的荧光辐射能△Ｅｆｌ与荧光光谱波数νｆｌ；计算得到的分子激发过程中的平均键级变化△Ｐ与荧光量子产率△存在如下关系：νｆＬ＝７．０５６０△ＥｆＬ＋２３．３８２０（Ｋｃｍ＾－＾１）ｒ＝０．９８８１ ｌｎФ＝－０．８     

团簇分子[Zn-(CH_3CH_2OH)_n]~(2+)的荧光光谱研究及理论光谱验证

通过荧光光谱实验和理论计算对金属离子在乙醇溶液中的微团簇结构进行了研究。荧光光谱实验发现在275~330 nm范围存在较强的乙醇分子荧光峰,当加入盐离子(Zn~(2+))后该处荧光强度逐渐变弱,说明盐的加入对乙醇体系的荧光效率产生了影响,破坏了原有乙醇分子之间的作用,使得其刚性结构发生改变,荧光效率降低,同时Zn~(2+)与乙醇分子通过溶剂化作用形成了新的微团簇,在350~380 nm之间出现了新峰。通过对团簇结构[Zn-(H_2O)_n]~(2+)(n=1~3)进行优化比较,得到了相对精确及运算成本较低的密度泛函理论B3LYP方法,并应用于Zn~(2+)在乙醇溶液中团簇结构计算。结果表明体系的第一溶剂化层存在着n=1~6的微团簇分子,且最多为6。比较理论计算荧光光谱与实验荧光光谱,进一步说明了Zn~(2+)与乙醇形成了新的微团簇及计算方法的可行性。     

NiH2分子的结构及其势能函数

应用群论及原子分子反应静力学方法推导了NiH2分子基态的电子态及其离解极限,在MP2/6-311G水平上,优化出NiH2(3Δg)分子稳定构型为D∞h,其平衡核间距Re=0.157 3 nm、∠HNiH=180.00°,同时计算出振动频率:对称伸缩振动频率ν1=2 000 cm-1,弯曲振动频率ν2=721 cm-1和反对称伸缩振动频率ν3=1 875 cm-1.在此基础上,使用多体项展式理论方法,导出了基态NiH2分子的全空间解析势能函数,该势能函数准确地再现了NiH2(D∞h)平衡结构.     

紫外光区S_2分子激光诱导荧光光谱

利用真空脉冲放电超声射流气体束(H_2S/Ar~3%混合气体)的方法产生了气相S_2分子,并研究了30 400~34 400cm~(-1)范围内S_2分子的时间分辨和基态振动频率分辨的激光诱导荧光光谱,获得了184支谱带的高分辨率(0.1cm~(-1))和低分辨率(0.3cm~(-1))转动光谱。实验观测并归属了S_2分子B_u~(Σ-)-X~3Σ_g~-和B″~3Π_u-X~3Σ_g~-共84支振动跃迁,分析得到了激发态B~3Σ_u~-态ν=0~9和B″~3Π_u态ν=2~12的分子常数以及B~3Σ_u~-态的基态平衡分子构型。由于S_2分子B~3Σ_u~-与B″~3Π_u态之间存在微扰,这两个电子激发态的振动能级间隔、自旋分裂常数和自旋-轨道分裂常数变化不规律,转动跃迁强度和跃迁选择定则存在异常,利用~3Σ-~3Π的齐次微扰哈密顿量定性地对这些异常光谱进行了解释,进一步丰富了S_2分子紫外区低能电子激发态的信息。     

低能电子与H_2分子碰撞振动激发动量迁移散射截面的研究

采用振动密耦合方法及基于量子力学从头计算的静电势、交换势和相关极化势,研究了低能电子与H2分子碰撞振动激发的动量迁移散射截面.通过包含18个振动波函数、8个分波和16个分子对称性,得到了收敛性很好的ν=0→ν′=0,1,2,3,4等几个振动跃迁通道的动量迁移散射截面值,并在入射电子能量1eVE≤10eV时给出了比以前的理论研究更为合理的总的动量迁移散射截面.     

硅油作为压力计的拉曼光谱研究

在金刚石压腔中,硅油作为传压介质,红宅石作为压标,在298.1 K,0.1～5 140.2 MPa下对硅油C-H伸缩振动圪v2906和v2967进行了拉曼光谱的原位测量.实验结果表明:在实验压力范同内,硅油v2906和v2967的拉曼位移与压力具有良好的线性关系.此外,探讨了在实验条件内利用压力介质硅油v2906和v2967的拉曼位移作为压力计的可行性,并且得到了硅油在298.1 K下的压力标定公式:p=0.14[(△vP)2906]2+81.92(△vP)2906+92.01,R2=0.99和P=-0.05[(△vP)v2967]2+73.07(△vP)2967+91.54,R2=0.98(0.1～5 140.2 MPa).     

High efficiency dye laser with low fluorescence yield pyrromethene dyes: experimental and theoretical studies

A combined experimental and theoretical study of the photo-physical, laser properties and molecular structures of three relatively recent Pyrromethene (PM) class dyes, PM597, PM580 and PM567, have been carried out. Laser characteristics of these three PM dyes were compared with three other widely used Rhodamine (RH) class dyes, RH6G, RHB and KRS, using a narrow-band dye laser setup, transversely pumped by the second harmonic (532 nm) of a Q-switched Nd-YAG laser. In addition to generating comparative data of these dyes for optimal use in dye lasers, we observed that unlike the RH dyes, the PM dyes show high efficiencies and wide tunability, despite the low fluorescence yield and high rate of non-radiative decay. Particularly, PM597 dye, in spite of a very low quantum yield of fluorescence (Φ=0.42), high non-radiative decay rate, and a large distortion from planarity in its excited state, when used in a laser cavity it exhibited similar laser efficiency and a beneficially wider tuning curve in comparison to other two PM dyes. Theoretical studies were carried out applying density functional theory and time-dependent density functional theory (DFT/TDDFT) to obtain new information on ground and the first excited state geometrical parameters of the PM dyes. Good correlation between calculated molecular properties and experimental results was observed for the evolution of the longest wavelength absorption maximum.     

The pH Probe CypHer™5E is Effectively Quenched by FM Dyes

Concurrent imaging of spectrally distinct fluorescence probes has become an important method for live-cell microscopy experiments in many biological disciplines. The technique enables the identification of a multitude of causal relationships. However, interactions between fluorescent dyes beyond an obvious overlap of their fluorescent spectra are often neglected. Here we present the effects of the well-established fluorescent dyes FM®2-10 or FM®1-43 on the recently introduced pH-dependent probe CypHer?5E. Spectrophotometry as well as live-cell fluorescence microscopy revealed that both FM dyes are effective quenchers of CypHer?5E. Control experiments indicated that this effect is reversible and not due to bleaching. We conclude that, in general, parallel measurements of both dyes are possible, with low FM dye concentrations. Nevertheless, our results implicate that special care has to be taken in such dual colour experiments especially when analysing dynamic CypHer?5E signals in live-cell microscopy.     

基于三维荧光光谱的克百威农药含量的检测方法

农药的广泛使用是防治病虫害的一种必要手段,在保证农业增产增收的同时,也给人们健康带来了威胁,寻求更加灵敏的农药残留检测方法至关重要。三维荧光光谱分析法选择性好、灵敏度高、快捷、取样少,可用于农药残留的分析与检测中。以自制标准浓度的克百威农药溶液作为测试样本,乙腈为溶剂,利用荧光光谱仪对样本进行测量,将实验获得的三维数据用MATLAB进行处理获得其三维荧光光谱图。实验发现乙腈作为溶剂对实验影响不大且荧光光谱的强度与克百威溶液浓度呈现良好的线性关系,相关系数r=0.997 4,接近于1。因此三维荧光光谱分析法可以检测出克百威溶液的浓度以及农药的含量。     

四氯化碳费米共振的拉曼光谱研究

费米共振现象是一种广泛存在于分子振动光谱中的现象,特别是结构比较复杂的多原子分子.在多原子分子中当振动倍频或组合频位于某一基频附近,由于发生振动耦合,会出现两个新峰,峰的位置向两侧发生移动,二者谱线强度发生变化,把这种现象称为费米共振.费米共振现象不仅存在于红外光谱中,也存在于拉曼光谱中.文章中测量了CCl4的拉曼光谱,利用所得到的谱线峰位和用Originpro7.5软件程序获得积分强度,用费米共振的相关理论计算了C-Cl的a1对称伸缩振动频率v1与C-Cl2的f对称弯曲振动频率v4的组合频(v1 v4)与(某一未知基频)C-Cl的f对称伸缩振动频率v03的费米共振特征参数,进而计算出了耦合系数W和这一未知基频v03.该文对理解费米共振,了解分子振动频率,研究分子结构有很重要的参考价值.     

Measurement of the K(L) charge asymmetry

We present a measurement of the charge asymmetry delta(L) in the mode K(L)-->pi(+/-)e(-/+)nu based on 298 x 10(6) analyzed decays. We measure a value of delta(L) = [3322+/-58(stat)+/-47(syst)]x10(-6), in good agreement with previous measurements and 2.4 times more precise than the current best published result. The result is used to place more stringent limits on CPT and DeltaS = DeltaQ violation in the neutral kaon system.     

Increased gain through identification and alleviation of dye self absorption in laser pumped dye lasers

The effect of overlapping absorption and emission spectra is to shift the gain curve of a dye to the red side of its fluorescence curve and reduce its gain. It is shown how simple binary mixtures of “adjacent” dyes can be used to produce a new gain maximum in the regions between the gain maximum of the single dyes.     

Absolute Intensities of the 10-µm Bands of (16)O(3)

Two hundred ninety experimental absolute intensities of nu(1) and nu(3) transitions of ozone have been measured, with good accuracy (<2%). They are used to derive the transition-moment parameters for these bands. The agreement between our observed and calculated line intensities is satisfactory. This work shows that the intensities of these two bands are on average 4% smaller than those used in the literature. In addition, 20 intensities of the nu(2) + nu(3) - nu(2) band confirm this value. Also, 42 line intensities of the 2nu(1)-nu(3) band are reported. Copyright 2001 Academic Press.     

Synthesis of Novel Carbazole based Styryl: Rational Approach for Photophysical Properties and TD-DFT

The synthesis and solvatochromic behavior of four novel carbazole based fluorescent styryl dyes were explained. In chlorinated solvents such as DCM and chloroform, these dyes show bathochromic shift in their absorption as well as emission. The styryl dyes 6b and 6c show solid state yellow fluorescence. DFT and TD-DFT computations were performed to study structural, molecular, electronic and photophysical properties of these dyes. The computed absorption and emission wavelength values are found to be in good agreement with the experimental results. The photophysical properties of these 1-styryl carbazole dyes are also compared with the recently reported 3-styrl carbazole dyes. The unique behavior of dye 6d is well explained by its optimized geometry found in the excited state. Ratio of ground to excited state dipole moment of the synthesized novel styryl compounds were calculated by Bakhshiev and Bilot-Kawski correlations.     

Random walks on a ( 2+1)-dimensional deformable medium

A model of random walks on a deformable medium is proposed in 2+1 dimensions. The behavior of the walk is characterized by the stability parameter beta and the stiffness exponent alpha. The average square end-to-end distance l approximately equals (2nu) and the average number of visited sites approximately equals (k) are calculated. As beta increases, for each alpha there exists a critical transition point beta(c) from purely random walks ( nu = 1/2 and k approximate to 1) to compact growth ( nu = 1/3 and k = 2/3). The relationship between beta(c) and alpha can be expressed as beta(c) = e(alpha). The landscape generated by a walk is also investigated by means of the visit-number distribution N(n)(beta). There exists a scaling relationship of the form N(n)(beta)approximately n(-2)f(n/beta(z)).