Review of Fluorescence Suppression Techniques in Raman Spectroscopy

Abstract

Raman spectroscopy is an important and powerful technique for analyzing the chemical composition of biological or nonbiological samples in many fields. A serious challenge frequently encountered in Raman measurements arises from the existence of the concurrent fluorescence background. The fluorescence intensity is normally several orders of magnitude larger than the Raman scattering signal, especially in biological samples. Such fluorescence background must be suppressed in order to obtain accurate Raman spectra. Several different techniques have been explored for this purpose. These techniques could be generally grouped into time-domain, frequency-domain, wavelength-domain, and computational methods in addition to various Raman enhancement techniques and other unconventional methods. This review briefly describes the fundamental principles of each group of methods, reports the most recent advances, and makes comparison across those major categories of techniques in terms of cost and performance in a hope to guide interested readers to select proper methods for specific applications.     

甲醇分子(CH3OH)光谱性质的理论计算

研究了气相甲醇分子(CH3OH)基态和激发态性质。在对不同方法基组所得计算结果和实验结果进行比较之后,选用MP2(full)/6-311++G(2d,2p)理论方法进行计算,得到甲醇分子(CH3OH)基态和三重激发态的几何结构、能量以及频率信息;频率计算显示基态和三重态都为稳定构型。从三重态的结构出发,解释了三重态势能面为排斥型势能面的合理性。计算了甲醇分子单重激发态的垂直激发能,比较不同方法不同基组计算的甲醇分子单重激发态的垂直激发能,发现用TDDFT 中的b3p86方法使用6-311++G**基组的计算值和实验值符合得最好。计算得到的甲醇分子在MP2(full)/6-311++G(2d,2p)的绝热电离能和垂直电离能分别为11.18eV和11.32eV;计算得到的绝热电子亲和势与垂直电子亲和势分别为0.888eV和0.893eV。计算结果对实验研究有指导意义。     

V+20离子的能量和偶极振子强度

用全实加关联方法计算了类锂V+20离子 1s2nl(l=s,p, d;n≤9) 态的电离势和精细结构.依据单通道量子亏损理论, 确定了这三个Rydberg系列的量子数亏损.用这些作为能量的缓变函数的量子亏损,可以实现对任意高激发态(n≥10)的能量的可靠预言.用在计算能量过程中确定的波函数,计算了V+20离子1s22s-1s2np及1s22p-1s2nd (n≤9)跃迁的振子强度.将这些分立态振子强度与单通道量子亏损理论相结合,得到在电离域附近束缚态间的偶极跃迁振子强度以及束缚态-连续态跃迁的振子强度密度,从而将V+20离子的这一重要光谱特性的理论预言外推到整个能域.     

双色激光场中激光强度和脉宽对线性多原子分子离子电离的影响

 利用强激光场电离和离解分子来研究分子激发态的波包结构是强场物理的重要研究方向。利用短时指数传播子对称分割法和快速傅里叶变换技术，数值求解了一维含时Schr-dinger方程，探讨了双色激光场中激光的基波和谐波强度之间的不同配比以及脉宽对线性多原子分子离子电离的影响。理论计算结果表明：基波和谐波的相对相位为π时，尽管随着激光的基波和谐波强度之间配比的变化，电离几率随原子间距变化的趋势基本保持不变，但在一定的激光基波强度下（1.2×10¹³~1.2×10¹⁵ W/cm²)，激光基波强度的变化可以明显改变电离几率随原子间距变化的趋势。另外，激光脉冲的持续作用可以增强分子的电离，取原子个数为5，基频光波长为800 nm，基波与谐波的强度配比为4，频率配比为2，当其作用时间达到75 fs时，电离基本接近饱和。采用外静电场电离模型能够合理地解释这些现象。     

分子拓扑学方法估算多环芳香烃类化合物的电离能

在构建多环芳烃类化合物分子的邻接矩阵主对角元时,结合烷基极化效应指数考虑分子图顶点的性质,以分子碎片C、CH、CH2、CH3等的相对能量作主元,用分子拓扑学方法构建了多环芳香烃类化合物新的邻接矩阵.研究结果发现,新的邻接矩阵特征根与多环芳香烃类化合物的电离能有良好的相关性Ipi=4.756+2.870OMOi,R=0.9853,s=0.1765,n=446.用这种新方法估算多环芳香烃类化合物的电离能,所用参数少且为分子结构性参数,稳定可靠,计算简便,结果较满意.     

Energy levels and spectral lines of Ne VIII

All experimental data on the valence-shell-excited and core-excited spectra of Li-like neon, including previously unpublished beam-foil spectroscopy data, have been compiled and critically evaluated. Seventeen spectral lines have been newly identified. Sets of recommended energy levels have been derived from the total list of observed lines and from selected results of theoretical and semi-empirical calculations. An accurate value of the ionization potential has been derived from existing theoretical calculations. Electronic supplementary material Online Material     

Energy levels and spectral lines of Ne VII

All experimental data on Ne VII, including previously unpublished beam-foil spectroscopy data, have been compiled and critically evaluated. More than a hundred spectral lines have been newly identified. For 40 transitions, the previous identifications have been revised. These revisions resolved all existing contradictions between previously published interpretations of the spectrum. An optimized level scheme has been derived from the total list of observed lines. About a hundred new energy levels have been found, including several highly excited hydrogenic levels. Based on these newly determined levels, as well as on the analysis of theoretical data, the ionization potential has been newly determined with improved confidence. Electronic supplementary material Online Material     

Dual channel detection–diode array and mass spectroscopy (El or Cl)–in HPLC

Simultaneous recording of UV and mass spectra (electron impact or chemical Ionization) in conventional HPLC is described. The LC eluent is divided into two parts; one is directed into a diode array detector and the other is introduced into the mass spectrometer via a particle beam interface. The analysis of the steroid esters of a pharmaceutical formulation illustrates the possibilities of dual channel (DAD-MS) HPLC detection.     

Optical mm-wave generation by using external modulator based on optical carrier suppression

In this paper, we have theoretically investigated the transmission performance of the optical millimeter (mm)-wave generated by using an external modulator based on optical carrier suppression for the first time. According to our theory, the data signals carried by the optical mm-wave are transmitted in the dispersion fiber without fading but are degraded greatly because of the time shift of the code edges, which still limits the transmission distance. The experimental results agree well with our theory.