β-三氯锗基丙酸类化合物的拉曼光谱和红外光谱

我们合成了β-三氯锗基丙酸及其类似物并测量了该化合物的拉曼光谱和红外光谱 ,经光谱分析 ,指认了主要波数所对应的分子振动。在 A、B、C、D四种化合物的拉曼光谱中 ,Ge- Cl的振动分别出现在 397cm- 1( vs)、40 0 cm- 1( vs)、394cm- 1( vs)、385cm- 1( vs)中 ,而在红外光谱中却无法证明 Ge- Cl键的存在 ,Ge- C键的振动在 Raman光谱中分别在 594cm- 1( w)、62 6cm- 1( w)、634cm- 1( w)、641 cm- 1( w)。在红外光谱中 ,各种极性基团的振动表现的更明显 ,分别出现了 O- H、CH2 、C- O和 C=O的振动峰。     

基于脉冲石英增强光声光谱的中红外超高灵敏CO探测

发展了一种超高灵敏的CO痕量气体测量装置,该装置采用4.65μm脉冲式中红外外腔量子级联激光器作为激发光源,结合石英增强光声光谱技术,对2135~2225cm-1之间的CO基频振动光谱带R支进行连续光谱扫描。水被加入到被测气体中,以加快较慢的CO分子振动-平动弛豫率。在锁相放大器时间常数为3ms,激光器占空比和扫描速率为50%和18cm-1/s时,获得的最小探测极限为4.6×10-8(体积分数),与之对应的归一化噪声等效吸收系数为1.07×10-8 cm-1 W/Hz。     

β-三苯锗基丙酸及β-三苯锗基丁酸的拉曼及红外光谱

我们合成了有机锗化合物的一类重要中间体β-三苯锗基丙酸和β-三苯锗基丁酸 ,测量了该化合物的拉曼光谱和红外光谱 ,经光谱分析 ,指认了主要波数所对应的分子振动。在这两种化合物的拉曼光谱中 ,30 50 cm- 1( m)、1 0 2 5cm- 1( m)和 61 8cm- 1( m)分属于 Ph- H的伸缩振动、面内弯曲振动和面外扭曲振动。饱和 Ge- C键的振动分别在 594cm- 1和 587cm- 1,同时指出了 Ph- Ge的几种振动所对应的振动频率。在红外光谱中 ,C=O的振动出现在 1 70 9cm- 1( s)和 1 70 5cm- 1( s) ,与饱和碳相连接的 Ge- C振动出现在 61 7cm- 1( w)和 61 7cm- 1( w)。     

液芯光纤方法研究溶剂对分子拉曼光谱强度的影响

液芯光纤可以大幅度提高拉曼光谱强度. 本文用液芯光纤方法测量了CCl4 在CS2 和C6H5Br中不同浓度下459 cm-1,314 cm-1和218 cm-1的拉曼光谱强度,验证了一些溶剂使某些分子拉曼光谱增强的溶剂效应.     

N_2O的近红外腔增强吸收光谱技术研究

以外腔式可调谐、窄线宽近红外半导体激光为光源,以一对曲率半径r=1 000mm的宽带高反射率平凹镜(反射率R=99.97%)构成的腔长为650mm的对称高精度光学稳定腔,建立了腔增强吸收光谱系统。详细研究了纯净N2O气体、以及N2O和N2的混合气体在不同浓度和不同气压下、中心波长位于6 561.39cm-1的腔增强吸收光谱、光谱强度和谱线宽度,该腔增强吸收光谱系统的有效吸收光程可达1 460km。获得了光谱线宽与气体压强的关系曲线,导出了波数6 561.39cm-1处N2对N2O的压力展宽系数为(0.114±0.004)cm-1·atm-1。采用该腔增强吸收光谱系统,开展了N2O气体检测研究,建立可用于定量检测的N2O气体腔增强吸收光谱强度与气体浓度关系曲线,获得了2.34×10-7cm-1的检测灵敏度,多次重复测量的相对标准偏差(RSD)为1.73%,在微量N2O气体检测中具有很好的应用前景。     

基于光腔衰荡光谱技术的压力计校准方法

压强是工业生产过程中的一个重要参数,其准确测量是过程控制的关键。气体分子光谱线型和线宽取决于分子间相互作用和温度、气压等因素,利用窄线宽气体吸收光谱的压力展宽效应,可通过高分辨地测量气体吸收谱线得到压强信息,实现压力计校准。提出了一种基于光腔衰荡光谱技术和气体吸收谱线压力展宽效应的压力计校准方法。采用5.2 μm可调谐量子级联激光器,基于连续光腔衰荡光谱技术建立了压力计校准实验装置。室温下,测量水汽在1 877 cm-1附近的一吸收谱线,线宽为0.084 21 cm-1,重复性测量误差小于1.53×10-4 cm-1,对应的压强大小为98.12 kPa,检测灵敏度优于0.18 kPa,与高精度压力计读数98.14 kPa一致。利用测试谱线线宽与压强的关系得到压力展宽系数(0.087 12±0.000 965) cm-1·atm-1,与HITARN数据库参考值0.087 1 cm-1·atm-1一致。实验校准了一小量程压力计。结果表明基于光腔衰荡光谱的高分辨吸收谱线测量在压强检测和压力计校准领域具有很好的应用前景。     

利用石英增强光声光谱技术在2.0μm处实现高灵敏CO_2检测的实验研究

基于石英增强光声光谱技术,以中心波长为2.0μm的窄线宽分布反馈式半导体激光器(DFB)为激励光源,采用波长调制及二次谐波解调技术通过改变激光器工作电流实现波长扫描完成了痕量CO2气体检测系统,并通过优化实验参数确定了常压下激光最佳调制深度,实现了高灵敏CO2浓度的检测。通过改变待测气体中的水汽浓度,研究了水汽对CO2气体探测结果的影响,结果显示在水汽浓度低于0.2%范围内,CO2气体光声信号随H2O浓度的上升而明显增强,当浓度高于此值后,H2O浓度的增加对CO2光声信号的增强作用几乎维持不变。数据显示,常温常压下H2O分子通过提高分子弛豫率最多可将二氧化碳R16吸收线的光声信号幅值提高约2.1倍。优化后的装置可以很好的实现大气中CO2浓度的检测。该装置获得的最小探测灵敏度为19ppm(1σ,300ms积分时间),相应的归一化噪声等效吸收系数为4.71×10-9 cm-1·W·Hz-1/2。     

4.4 μm中红外激光外差光谱探测技术研究

在国内首次报道以窄线宽的4.4 μm外腔量子级联激光(QCL)作为本地振荡光源,黑体作为辐射光源的激光外差光谱实验装置的建立和测量工作。激光外差光谱是一种高灵敏度的光谱探测技术,并可以用于发展一种小型的光谱探测系统,进行地基或星载的地球大气或天文观测。介绍了激光外差的基本理论、装置的建立和实验测量工作。此激光外差光谱实验装置采用4.4 μm外腔量子级联激光,出光功率高达180 mW,在4.38～4.52 μm间连续可调,具有很宽的光谱调谐范围,能实现CO₂,CO和N₂O等大气重要分子的同时测量。通过开展不同压力下CO₂气体的激光外差光谱测量,对激光外差光谱实验装置的性能进行了评估。目前该激光外差系统的信噪比达到86,低于散粒噪声极限条件的理论计算值287,系统的光谱分辨率约为0.007 8 cm-1,能满足较窄线宽条件下的高分辨率激光外差光谱的测量。分析结果表明,中红外激光外差光谱系统具有很高的瞬态信噪比及光谱分辨率,在高精度测量大气温室气体的柱浓度和温室气体垂直廓线分布方面具有广阔的应用前景。     

红外光谱分辨率对气体定量分析的影响研究

利用不同分辨率(1, 2, 4, 8 cm-1)的红外光谱建立对多组分气体样本(一氧化碳、二氧化碳、一氧化氮)的定量分析模型,研究了分辨率对气体定量测量精确性的影响。研究发现：对于样本中的各气体组分,在合适的分辨率下都有其最佳的测量精确性;而对于模型的整体精确性,在高分辨率1和2 cm-1以及低分辨率8 cm-1时模型都有较好的精确性,各组分相关系数(r)均值达到0.999 5以上,校正均方根误差(RMSEC)和验证均方根误差(RMSEP)的均值分别为18.36和15.43以下,而在分辨率为4 cm-1时,模型测量精确性陡然降低,r均值降到0.989 66,RMSEC均值为90.37,RMSEP均值为64.33。实验结果表明：光谱分辨率对气体定量分析有明显的影响。为提高定量分析测量的精确性,需要针对不同的待测气体和应用场合采用合适的分辨率参数。     

苯海拉明的拉曼光谱和红外光谱研究

测量并分析了盐酸苯海拉明的红外光谱和拉曼光谱。在Raman光谱中, 1001 cm-1出现一个极强峰, 在1030 cm-1和618 cm-1各有一个中等峰,此外,在红外光谱中, 714 cm-1和757 cm-1附近出现极强的吸收峰,认定这个化合物中存在单取代苯。C-N的对称伸缩振动出现在837 cm-1, 1433 cm-1和1470 cm-1分别为CH2和CH3的变形振动, 在红外光谱中, 1020 cm-1处明显的吸收峰属于C-O-C反对称伸缩振动。此外, 测量得到含量为25 mg苯海拉明药片的拉曼光谱与纯苯海拉明的拉曼峰比较一致, 可作为无损快速检测该药物的手段。     

Application of a widely electrically tunable diode laser to chemical gas sensing with quartz-enhanced photoacoustic spectroscopy

A near-infrared diode laser with sample-grating distributed Bragg reflectors was used as a widely tunable spectroscopic source for multispecies chemical sensing. Quartz-enhanced photoacoustic spectroscopy was utilized to obtain high absorption sensitivity in a compact gas cell. CO2, H2O C2H2, and NH3 were monitored. A noise equivalent sensitivity of 8 x 10(-9) cm(-1) W(-1) Hz(-1/2)for NH3 detection was achieved, which corresponds to a NH3 mixing ratio of 4.4 parts in 10(6) by volume (ppmv) with a 1-s time constant and available 5.2-mW optical power in the gas cell.     

几种哌嗪类抗肿瘤化合物的拉曼光谱

几种哌嗪类抗肿瘤化合物的拉曼光谱刘社文１梁二军１李祥杰２（１郑州大学河南省激光应用技术重点实验室，２郑州大学化学化工学院，郑州４５００５２）ＲａｍａｎＳｐｅｃｔｒａｏｆＳｅｖｅｒａｌＡｎｔｉｔｕｍｏｒＰｉｐｅｒａｚｉｎｅｓＣｏｍｐｏｕｎｄｓＬｉｕＳｈ...     

Optical parametric oscillator based off-axis integrated cavity output spectroscopy for rapid chemical sensing

An optical parametric oscillator (OPO), pumped by a fiber-amplified diode laser, is combined with off-axis integrated cavity output spectroscopy (OA-ICOS). The cw OPO (power 1.2 W, tunability 3-4 μm, 5 cm(-1) mode-hop-free tuning) has a tuning speed of 100 THz/s, which is ideal for rapid and sensitive trace gas detection. Combined with OA-ICOS, a detection limit of 50 parts per trillion by volume (1×10(12)) of ethane (C(2)H(6)) in nitrogen was obtained in 0.25s at 2997 cm(-1), corresponding to a noise equivalent absorption sensitivity of 4.8×10(-11) cm(-1) Hz(-1/2). The system demonstrates real-time measurements of methane and water in exhaled human breath.     

Resonant optothermoacoustic detection: technique for measuring weak optical absorption by gases and micro-objects

We report a laser spectroscopy technique for detecting optical absorption in gases and micro-objects via linked thermal effects and by using a sharp mechanical resonance in a quartz crystal. The performance of this technique is studied using near-IR diode lasers and two gases, pure CO(2) and C(2)H(2) diluted in nitrogen. A 7.3 × 10(-8) cm(-1)W/(Hz)(1/2) noise equivalent sensitivity to absorption in gases is demonstrated. Based on experimental results, it was estimated that 10(-8) fractional absorption of optical radiation by a micro-object deposited on a thin transparent fiber can be detected.     

QED effects in molecules: test on rotational quantum states of H2

Quantum electrodynamic effects have been systematically tested in the progression of rotational quantum states in the X?1Σ(g)(+), v=0 vibronic ground state of molecular hydrogen. High-precision Doppler-free spectroscopy of the EF?1Σ(g)(+)-X?1Σ(g)(+) (0,0) band was performed with 0.005 cm(-1) accuracy on rotationally hot H2 (with rotational quantum states J up to 16). QED and relativistic contributions to rotational level energies as high as 0.13 cm(-1) are extracted, and are in perfect agreement with recent calculations of QED and high-order relativistic effects for the H2 ground state.     

The Rotational Spectra, Structure, Internal Dynamics, and Electric Dipole Moment of the Argon-Ketene van der Waals Complex

Pulsed-beam Fourier transform microwave spectroscopy was used to observe and assign the rotational spectra of the argon-ketene van der Waals complex. Tunneling of the hydrogen or deuterium atoms splits the a- and b-type rotational transitions of H(2)CCO-Ar, H(2)(13)CCO-Ar, H(2)C(13)CO-Ar, and D(2)CCO-Ar into two states. This internal motion appears to be quenched for HDCCO-Ar where only one state is observed. The spectra of all isotopomers were satisfactorily fit to a Watson asymmetric top Hamiltonian which gave A=10 447.9248(10) MHz, B=1918.0138(16) MHz, C=1606.7642(15) MHz, Delta(J)=16.0856(70) kHz, Delta(JK)=274.779(64) kHz, Delta(K)=-152.24(23) kHz, delta(J)=2.5313(18) kHz, delta(K)=209.85(82) kHz, and h(K)=1.562(64) kHz for the A(1) state of H(2)CCO-Ar. Electric dipole moment measurements determined &mgr;(a)=0.417(10)x10(-30) C m [0.125(3) D] and &mgr;(b)=4.566(7)x10(-30) C m [1.369(2) D] along the a and b principal axes of the A(1) state of the normal isotopomer. A least squares fit of principal moments of inertia, I(a) and I(c), of H(2)CCO-Ar, H(2)(13)CCO-Ar, and H(2)C(13)CO-Ar for the A(1) states give the argon-ketene center of mass separation, R(cm)=3.5868(3) ?, and the angle between the line connecting argon with the center of mass of ketene and the C=C=O axis, θ(cm)=96.4 degrees (2). The spectral data are consistent with a planar geometry with the argon atom tilted toward the carbonyl carbon of ketene by 6.4 degrees from a T-shaped configuration. Copyright 2001 Academic Press.     

2-噻吩乙醛酸-邻菲罗啉-铕配合物的合成、结构表征及荧光性能的研究

合成了铕与 2 噻吩乙醛酸 (HL)和邻菲罗啉 (phen)的配合物 ,用元素分析、电导率、红外光谱和核磁共振谱测定了配合物的分子式为 [EuL2 phen·(H2 O) 3 ]NO3 ;配合物中的Eu(Ⅲ )离子与 2 噻吩乙醛酸和水分子中的O原子以及邻菲罗啉中的N原子配位。在室温下测定了配合物的激发和发射光谱 ,配合物中Eu(Ⅲ )离子的5D0 7F1和5D0 7F2 跃迁分别位于 5 92和 6 18nm。该固体配合物于室温下被紫外光激发可以发出强的特征红色荧光。IR光谱中 ,2 噻吩乙醛酸的特征吸收峰νCO (1719cm-1) ,νC—O(12 32cm-1) ,δO—H(90 9cm-1)在形成配合物后消失。在配合物中出现—COO-的反对称νas(16 4 2cm-1)和对称νs(14 0 8cm-1)伸缩振动吸收峰。在1HNMR谱图中 ,2 噻吩乙醛酸环上的 3个氢原子的化学位移形成配合物后移向高场 ,邻菲罗啉环上 4种不同环境的质子峰的化学位移形成配合物后向低场移动。从TG曲线可以看出 ,此配合物在常温至 2 5 0℃以下是稳定的。     

吉林长白山硅藻土的红外光谱研究

对长白山硅藻土在 10 0～ 1330℃温度范围进行热处理并开展红外光谱研究 ,结果表明经 5 0 0℃热处理样品开始出现 374 5cm- 1 峰 ,在 90 0℃达到最大 ,12 0 0℃消失 ,此时硅藻土转变成方石英。对 374 5cm- 1 峰所反映的以孤立Si—OH形式存在的水的含量进行了半定量计算 ,表明这种OH除存在于样品表面外 ,还存在于内部的结构缺陷处 ,并推测硅藻土转变成方石英与这种孤立Si—OH的消失有关     

二正丁基锡三齿酰腙Schiff碱配合物的合成和红外光谱研究

合成了 4种三齿酰腙Schiff碱配体H2 L [H2 L1 :C6 H5C(O)NHN =CHC6 H4OH 2 ,H2 L2 :C6 H5C(O)NHN =CHC6 H3(OH) 2 2 ,4,H2 L3:NC5H4C(O)NHN =CHC6 H4OH 2 ,H2 L4:NC5H4C(O)NHN =CHC6 H3(OH) 2 2 ,4]和它们的二正丁基锡新型配合物 (n Bu) 2 SnL ,通过元素分析确定了这些配合物的组成 ,并对配合物在 4 0 0 0～ 40 0cm- 1范围内的主要红外光谱吸收峰进行了归属和讨论 ,推测出配合物可能的分子结构。     

High-frequency and -field EPR and FDMRS study of the [Fe(H2O)6]2+ ion in ferrous fluorosilicate

The complex [Fe(H2O)6]SiF6 is one of the most stable and best characterized high-spin Fe(II) salts and as such, is a paradigm for the study of this important transition metal ion. We describe high-frequency and -field electron paramagnetic resonance studies of both pure [Fe(H2O)6]SiF6 and [Zn(H2O)6]SiF6 doped with 8% of Fe(II). In addition, frequency domain magnetic resonance spectroscopy was applied to these samples. High signal-to-noise, high resolution spectra were recorded which allowed an accurate determination of spin Hamiltonian parameters for Fe(II) in each of these two, related, environments. For pure [Fe(H2O)6]SiF6, the following parameters were obtained: D=+11.95(1) cm(-1), E=0.658(4) cm(-1), g=[2.099(4),2.151(5),1.997(3)], along with fourth-order zero-field splitting parameters: B4(0)=17(1)×10(-4) cm(-1) and B4(4)=18(4)×10(-4) cm(-1), which are rarely obtainable by any technique. For the doped complex, D=+13.42(1) cm(-1), E=0.05(1) cm(-1), g=[2.25(1),2.22(1),2.23(1)]. These parameters are in good agreement with those obtained using other techniques. Ligand-field theory was used to analyze the electronic absorption data for [Fe(H2O)6]SiF6 and suggests that the ground state is 5A1, which allows successful use of a spin Hamiltonian model. Density functional theory and unrestricted Hartree-Fock calculations were performed which, in the case of latter, reproduced the spin Hamiltonian parameters very well for the doped complex.