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用傅立叶红外光谱(FTIR)中差示光谱技术研究了具有特殊相行为的羧化聚苯醚(CPPO)和聚苯乙烯(PS)共混体系特征红外吸收谱带随相区的转变而发生的变化.发现当核化度为8.0mol%时,CPPO/PS共混体系的红外特征吸收峰的频率位移速率随温度的变化与该体系的特殊相行为(即同时具有UCST和LCST)有相互对应关系.研究了随温度变化,共混体系中分子间特殊相互作用的变化.探讨了此共混体系相容和相分离的机理. 相似文献
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本文综述了在DNA测序方面分析化学的最新进展,包括电泳,毛细管电泳(CE),质谱(MS),电喷雾电离-质谱(ESI-MS),荧光光谱、共振离子谱(RIS)和单分子测定,同时还叙述了两维技术和多段测序方法的进展。 相似文献
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采用硫脲做为表面修饰剂,合成了硫脲表面修饰的掺杂Cd^2+的ZnS纳米晶(ZnS:CA/SC(NH2)2),用X射线粉末衍射、透射电子显微镜、红外光谱以及荧光光谱等手段进行了表征.实验结果表明,CA抖掺入了ZnS纳米晶中,硫脲分子中的S原子与该纳米晶表面的金属离子存在配位作用,ZnS:CA/SC(NH2)2纳米晶为分散性较好、平均粒径7nm的球形粒子且具有良好的荧光性质. 相似文献
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苯基荧光酮—TritonX—100荧光熄灭法测定微量钼研究 总被引:2,自引:0,他引:2
本文用荧光熄灭法研究了苯基荧光酮-TritonX-100-Mo(Ⅵ)体系的测定方法及条件。在pH1.0-3.0的盐酸介质中,Mo(Ⅵ)检测限为0.2μg/25mL范围内具有线性关系。本法灵敏度高,选择性好,用于检测球墨铸铁中的微量钼,结果满意。 相似文献
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飞秒受激拉曼光谱(femtosecond stimulated raman spectroscopy,FSRS)是一种新型的非线性振动光谱技术.它使用两束重叠的窄带拉曼泵浦和宽带探测脉冲激光束,利用外差式检波方法在探测光方向上进行信号探测.FSRS既可以用来探测分子电子基态的振动动力学,也可以用来探测分子电子激发态的振动动力学,比如同质异构类反应.即使荧光背景很强的分子,也可以用FSRS来研究.FSRS可以用三阶微扰的波包图像来描绘.单从相位匹配条件出发,共有48项对应于FSRS过程,但是其中只有8项满足共振条件.可以用3种方法来描述这8项:双时间线拉曼图、封闭时间路径环路图和四波混频的能级图.进一步分析表明,这8项可以分成4类,即SRS(I),SRS(II),IRS(I)和IRS(II),其中SRS代表受激拉曼散射,IRS代表反转拉曼散射.SRS(I)可以用来解释自发拉曼散射,但是其余的SRS(II)、IRS(I)和IRS(II)三项只在受激拉曼光谱中存在.FSRS光谱中SRS(I)过程产生的是斯托克斯拉曼谱线,而IRS(I)过程则产生的是反斯托克斯谱线.其余的两项SRS(II)和IRS(II)只是产生很宽的背景基线,基本和我们感兴趣的观测量不相关.使用简谐振动模型,我们可以得到三阶微扰极化率的四时间相关函数的解析表达式.我们讨论了FSRS光谱之所以能够得到高时间分辨率和高频率分辨率的物理原理.在文章中,我们还就以下研究做了计算与实验结果的比较:(a)荧光性罗丹明6G的共振FSRS谱和(b)CDCl3分子非共振脉冲泵浦光制备的相干振动态的二维FSRS谱.计算得到的结果与实验十分吻合,同时在理论上证明了CDCl3二维FSRS光谱中级联效应是占主导作用的. 相似文献
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在流动余辉装置上, 研究了活性氮与SO2和SOCl2之间的反应过程. 在280~500 nm, 观察到了SO2( A1A2,B1B1→X1A1 )和SO2(a3B1→X1A1)的发射光谱. 对比由Ar(3P0,2)与N2碰撞反应产生的纯N2(A3Σu+)与SO2、SOCl2之间反应的实验结果, 可以说明, N2(A3Σu+)在活性氮与SO2的反应中是主要的能量载体, 它与SO2的直接能量转移反应形成了激发态的SO2(A1A2, B1B1); 在活性氮与SOCl2的反应中观测到的激发态SO2(a3B1), 则可能主要是通过N(4S)与SOCl2反应生成的N2O(X1Σ+)和N2(A3Σu+)与SOCl2反应生成的SO(X3Σ-)之间的化学反应过程产生. 相似文献
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Wang W Wang S Liu F Zheng W Wang D 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(2):477-482
In this study, the emission spectra of OH (A2sigma --> X2pi, 0-0) emitted from the high-voltage pulsed corona discharge (HVPCD) of N2 and H2O mixture gas and humid air in a wire-plate reactor were successfully recorded against a severe electromagnetic interference coming from HVPCD at one atmosphere. The relative vibrational populations and the vibrational temperature of N2 (C, v') were determined. The emission spectra of the deltaupsilon = +1 (1-0, 2-1, 3-2, 4-3) vibration transition band of N2 (C3pi(u) --> B3pi(g)) is simulated through gauss distribution. The emission intensity of OH (A2sigma --> X2pi, 0-0) has been exactly gotten by subtracting the emission intensity of the deltaupsilon = +1 vibration transition band of N2 (C3pi(u) --> B3pi(g)) from the overlapping spectra. The relative population of OH (A2sigma) has been obtained by the emission intensity of OH (A2sigma --> X2pi, 0-0) and Einstein's transition probability. The influences of pulsed peak voltage and pulse repetition rate on the relative population of OH (A2sigma) radicals in N2 and H2O mixture gas and humid air are investigated separately. It is found that the relative population of OH (A2sigma) rises linearly with increasing the applied peak voltage and the pulse repetition rate. When the oxygen is added in N2 and H2O mixture gas, the relative population of OH (A2sigma) radicals decreases exponentially with increasing the added oxygen. The main involved physicochemical processes have also been discussed. 相似文献
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Liu F Wang W Zheng W Wang Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,69(3):776-781
Optical emission spectroscopy has been applied to study the spatially resolved measurements of the emission intensities of OH (A(2)Sigma-->X(2)Pi, 0-0) and N(2)(+) (B(2)Sigma(u)(+)-->X(2)Sigma(g)(+), 0-0, 391.4 nm) produced by a high-voltage positive pulsed streamer discharge consisting of a gas mixture of N(2) and H(2)O in a wire-plate reactor under severe electromagnetic interference at atmospheric pressure. The effects of pulse peak voltage, pulse repetition rate, and the added O(2) flow rate on the spatial distributions of the emission intensity of OH (A(2)Sigma-->X(2)Pi, 0-0) and N(2)(+) (B(2)Sigma(u)(+)-->X(2)Sigma(g)(+), 0-0, 391.4 nm) in the lengthwise direction (direction from wire to plate) are investigated. It has been found that the emission intensities of OH (A(2)Sigma-->X(2)Pi, 0-0) and N(2)(+) (B(2)Sigma(u)(+)-->X(2)Sigma(g)(+), 0-0, 391.4 nm) rise with an increase in both pulse peak voltage and pulse repetition rate and decrease with an increase in oxygen flows added in an N(2) and H(2)O gas mixture. The emission intensity of OH (A(2)Sigma-->X(2)Pi, 0-0) decreases with increasing the distance from the wire electrode. The emission intensity of N(2)(+) (B(2)Sigma(u)(+)-->X(2)Sigma(g)(+), 0-0, 391.4 nm) is nearly constant at 0-4mm from wire electrode, and sharply increases near the ground electrode. The vibrational temperature of N(2) (C) increases with increasing O(2) flows and keeps almost constant in the lengthwise direction under the present experimental conditions. The main physicochemical processes involved are also discussed in this paper. 相似文献
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在超声分子束条件下,利用380.85 nm的电离激光使SO2分子经由[3+1]共振增强多光子电离(REMPI)产生纯净的SO2+(X 2A1)分子离子,用另一束解离激光在可见光波长区(563~660 nm)扫描获得了光解碎片SO+的激发(PHOFEX)谱.从563~660 nm波长区SO+的无结构连续谱以及SO2+解离的效率随波长增加而减少的实验事实,提供了SO2+(E,D,C)电子态附近存在α2A2对称性排斥态的证据,分析了产生SO+的[1+1]光解机理:(1)SO2+(X2A1)首先经由单光子激发到达B2B2中间态的密集能级区;(2)吸收另一个光子到达SO2+(E,D,C)电子态附近的α2A2排斥态,经由α2A2排斥态产生了到SO+(X2∏)+O(3Pg)的直接解离. 相似文献
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The two-photon resonance-enhanced multiphoton ionization spectrum between 285 and 288.5 nm of the 5pπE2Πr(v’=1)←X2Πr(v’’=0) band of CF radical is reported. The band is rotationally analyzed, and the spectroscopic constants of the state are first derived: σ0 = 69566.38±0.52 cm-1, A'v= 46.4±0.3 cm-1, B'v= 2.565±0.017 cm-1, D' v = (8.6±1.2)×10-6cm-1. 相似文献
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通过四波混频差频的方法产生高分辨的真空紫外激光,用以测量143.6至146.9 nm范围内的射流冷却N2O分子吸收光谱,对应于C1Π←X1Σ+的吸收跃迁.谱图显示出三个分立的振动谱峰叠加在宽吸收背景上,谱峰间隔分别是521和482 cm-1.前人的高精度量子化学计算表明C1Π态在N—O键长方向表现为无势垒的排斥态,而在N—N键伸缩及N2O弯曲振动方向则表现为束缚态,因此观测到的振动谱峰被归属为激发态的Feshbach共振.通过反Fourier变换可以得到Feshbach共振对应的非稳定周期轨道的特征周期为61 fs,相应的振动频率为546 cm-1.鉴于这一频率与弯曲振动频率非常接近,非稳定周期轨道被认为是由C1Π态的弯曲振动与解离运动相互作用而形成的,N—N伸缩振动没有参与形成非稳定周期轨道.由此,N2O分子C1Π态光激发-解离过程得以清晰地阐述. 相似文献
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Ruthenium(II) Phthalocyanines: Preparation and Properties of Di(halo)phthalocyaninatoruthenate(II) [Ru(Py)2Pc2?] reacts with molten (nBu4N)X forming stable, green (nBu4N)2[Ru(X)2Pc2?] (X = Cl, Br). The cyclovoltammogram shows a quasireversible redoxprocess for the metal oxidation at E1/2(I) = ?0.02 V (X = Cl) resp. 0.05 V (X = Br) and for the first ringoxidation at E1/2(II) = 0.70 V. The typical π-π*-transitions (B < Q < N) of the phthalocyanine dianion (Pc2?) are observed in the uv-vis spectrum. With respect to RuIII phthalocyanines B is shifted significantly to higher, Q, N to lower energy. The strong extra-band at 24.2 kK is diagnostic for these RuII phthalocyanines. The vibrational spectra are typical for the Pc2? ligand with D4h symmetry, too, and bands at 513, 909, 1 171 und 1 329 cm?1 in the m.i.r. spectrum are specific for hexa-coordinated low spin RuII. In the Raman spectrum with excitation at ~480 nm the intensity of the totally symmetrical Ru? X stretching vibration at 266 cm?1 (X = Cl) resp. 168 cm?1 (X = Br) together with a progression of up to three overtones is selectively resonance Raman enhanced. The asymmetrical Ru? X stretching vibration is observed in the f.i.r. spectrum at 272 cm?1 (X = Cl) resp. 215 cm?1 (X = Br). 相似文献
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利用脉冲分子束技术, 在305-322 nm范围内研究了1-萘酚(1NP)的共振双光子电离(R2PI)光谱. 1NP分子存在cis和trans两种旋转异构体, 但实验中仅观测到trans异构体的电子振动跃迁光谱, 其S1←S0跃迁的(0-0)带头出现在317.90 nm(即31456 cm-1)位置. 利用光谱选律及ab initio和密度泛函(DFT)计算, 对trans异构体在S1态的振动模进行标识, 得出主要对应于对称性为a'的平面内振动模. 计算显示, cis异构体在电子基态S0的能量较trans异构体高出439 cm-1, 而第一激发能却比trans异构体的低1216 cm-1, 与之相应的实验值分别是220和274 cm-1. 计算数值与实验结果在能量变化趋势上完全一致. 共振双光子电离谱中没有观测到cis异构体的光谱信号, 其原因可归结为分子束的有效冷却效应使得处于基态的cis异构体的布居数密度相对trans异构体极低, 导致cis光谱信号太小而未能被探测到. 相似文献