相干反斯托克斯拉曼及相干反斯托克斯超拉曼光谱微观极化率张量元的简化方案-C∞v对称性

相干反斯托克斯拉曼光谱(CARS)和四阶相干反斯托克斯超拉曼光谱(CAHRS)广泛应用于分子界面和生物膜表面的研究。然而,高阶非线性光学过程中分子微观极化率张量元数量众多,关系复杂,使研究者对CARS和CAHRS很难进行定量分析。采取以下方案对属于C_∞v对称性的分子基团的CARS和CAHRS的微观极化率张量元进行简化。首先将CARS微观极化率张量元β_{i′j′k′l′}表示成拉曼微观极化率张量元微分α′_i′j′的乘积,CAHRS微观极化率张量元β_{i′j′k′l′m′}表示成超拉曼微观极化率张量元微分β′_i′j′k′和拉曼微观极化率张量元微分α′_i′j′的乘积,再利用α′_i′j′之间的比值及β′_i′j′k′之间的比值得到β_{i′j′k′l′}和β_{i′j′k′l′m′}之间的比值。使用这些CARS和CAHRS微观极化率张量元之间的关系,能够得到CARS和CAHRS光谱的广义取向泛函及其广义取向参数,进而对界面分子取向信息进行定量分析。     

相干反斯托克斯拉曼及相干反斯托克斯超拉曼光谱微观极化率张量元的简化方案-C_(3v)对称性

相干反斯托克斯拉曼光谱(CARS)和四阶相干反斯托克斯超拉曼光谱(CAHRS)已经广泛应用于分子的光谱特性、肿瘤细胞的结构及分子反应动力学等问题的研究。对这种复杂的高阶非线性光谱进行定量分析所面临的主要难题是高阶非线性光学过程中分子微观极化率张量元数量众多,关系复杂。在前期报道的C_(∞v)对称性分子基团的CARS和CAHRS的微观极化率张量元简化方案的基础上,对分子对称性更加复杂的C_(3v)对称性的分子基团的CARS和CAHRS的微观极化率张量元进行简化,为定量分析C_(3v)对称性分子基团的CARS和CAHRS光谱信息提供必要的理论基础。首先将CARS微观极化率张量元β_(i′j′k′l′)表示为拉曼微观极化率张量元微分α′_(i′j′)的乘积, CAHRS微观极化率张量元β_(i′j′k′l′m′)表示为超拉曼微观极化率张量元微分β′_(i′j′k′)和拉曼微观极化率张量元微分α′_(i′j′)的乘积。用α′_(i′j′)和β′_(i′j′k′)之间的比值关系简化β_(i′j′k′l′)和β_(i′j′k′l′m′)之间比值。对于C_(3v)对称类型分子基团的对称振动模式A_1, 9个非零且3个独立的CARS微观极化率张量元可以用α′_(i′j′)之间的1个比值参数R■进行描述, 21个非零且6个独立的CAHRS微观极化率张量元可以用α′_(i′j′)之间及β′_(i′j′k′)之间的3个比值参数R■, R■和R■进行描述。然后利用键极化加和模型方法,通过计算C_(3v)对称性分子基团中的各个单键与单键之间的耦合关系,得到C_(3v)对称性分子基团的对称伸缩振动模式A_1所对应的所有超拉曼微观极化率张量元微分β′_(i′j′k′)分量的比值,结合文献中给出的拉曼微观极化率张量元微分α′_(i′j′)分量的比值,进一步简化C_(3v)对称性分子基团CARS和CAHRS微观极化率张量元之间的关系。从这些简化了的CARS和CAHRS微观极化率张量元之间的关系,可以进一步简化CARS和CAHRS信号及广义取向泛函R_(IJK)(θ)的表达式,得到R_(IJK)(θ)随界面分子基团取向角度θ的变化规律。此外,也详细推导了C_(3v)对称性分子基团对射式实验构型CAHRS过程的强度因子d_(IJK)、广义取向泛函R_(IJK)(θ)及广义取向参数c_2和c_4的表达式,为定量分析界面分子取向信息奠定了理论基础。     

可能的原子核形状及硬度演化性质:基于能量面计算的系统分析(英文)

基于（β₂,γ,β₄）形变空间下对-形变自洽的原子核能量面计算方法,系统研究分析了50 < Z < 82区偶偶核的形状及硬度演化特征。计算的平衡形变与其它理论预言及存在的实验值进行了对比。从相应的形变势能曲线提取了与β₂及γ相关的硬度参数C_β,C_γ,这与实验观测到的低位β及γ振动带信息相符。还简要讨论了转动情况下的硬度演化,例如基于蜈蚣型E-GOS曲线,表明存在不可忽略的振动效应。Nuclear shape and stiffness evolutions in even-even nuclei with 50 < Z < 82 are systematically analyzed in terms of the pairing-deformation self-consistent nuclear-energy-surface calculation in (β₂,γ,β₄) deformation space. Calculated equilibrium deformations are presented and compared with other theoretical predictions and available experimental data. The stiffness parameters C_β and C_γ respectively related to quadrupole deformations β₂ and γ are determined from the deformation energy curves, which are consistent with the observed low-lying β and/or γ bands. The stiffness evolution under rotation along the yrast line is briefly discussed, e.g., on the basis of the centipidelike E-GOS curves, showing an unnegligible vibration effect.     

手性分子2, 3-丁二醇的旋光拉曼光谱研究

本文从拉曼峰和旋光拉曼峰出发,通过键极化率和微分键极化率分析研究(2R, 3R)-2, 3-丁二醇. 通过分子C₁和C₂两种点群的优化结构,获得不依赖于这两种结构的结果 和有关这个手性系统物理图像的丰富信息.对分子拉曼键极化率分析,得出在拉曼弛豫过程中, 电荷主要从外围流向骨架结构.对分子微分键极化率的分析,显示在不对称C原子和与其相联系的H原子 两侧化学键, C-O和C-CH₃的微分键极化率的符号正好相反,意味着这个分子具有相当好的手性 不对称性质.对比对称和反对称的键极化率、微分键极化率,本文得到这样的结论: 对于(特别是键伸缩的)键极化率,(大体上是)对称的大于反对称的; 而对于微分键极化率则是反对称的大于对称的. 关键词： 旋光拉曼 键极化率 微分键极化率 2,3-丁二醇     

CO分子振转光谱的理论研究

采用从头算的多参考组态相互作用(MRCI)方法并结合基组aug-cc-pCVQZ计算了CO分子基态(X1Σ+)的势能曲线和偶极矩曲线,得到的势能曲线、偶极矩曲线分别与RKR势、文献的偶极矩曲线吻合较好。利用所得的势能,求解双原子分子核运动的Schrdinger方程找到了CO分子X1Σ+态转动量子数J=0时的70个振动态,对于每一振动态,分别计算了其振动能级G(v)、转动惯性常数B_v和离心畸变常数D_v,并把计算结果与已知的42个实验值做了详细比较,结果表明,计算的振动能级G(v)、转动惯性常数B_v、离心畸变常数D_v与实验值符合较好。利用G(v),B_v导出的光谱常数[谐振频率ω_e(2 160.1 cm-1)、非谐振频率ω_eχ_e(13.1 cm-1)、转动常数B_e(1.918 cm-1)、振转耦合常数α_e(0.017 3 cm-1)]也与实验值的光谱常数[ω_e(2 169.8 cm-1),ω_eχ_e(13.3 cm-1),B_e(1.931 cm-1),α_e(0.017 5 cm-1)]较为符合,这在一定程度上证明了方法MRCI/Aug-cc-pCVQZ对CO分子基态性质的计算是合适而可靠的。利用乘积近似方法计算了CO分子在常温、中温、高温时的配分函数,在此基础上,计算了CO分子在T=296 K时的1-0跃迁带的谱线强度,通过比较发现,计算所得的线强度与HITRAN数据库符合较好。进一步计算的CO分子X1Σ+态1-0,2-0,3-0,4-0,2-1,3-1和4-1跃迁带的带强度也与实验值较为吻合,同时首次计算了CO分子X1Σ+态3-2跃迁带、4-2跃迁带的线强度及带强度。     

Na2CO3的高压拉曼光谱研究

碳酸盐是碳在地球内部的重要载体之一,其在地幔高温高压条件下的晶体化学是理解地球深部碳的赋存状态和循环过程的关键,而结构稳定性和相变是晶体化学最基本的研究内容。碳酸钠（Na₂CO₃）是一种常见的碱性碳酸盐矿物,在产自地幔过渡带-下地幔的金刚石中已发现含钠的碳酸盐矿物包裹体,这成为碳酸钠能够俯冲进入地幔深部的直接矿物学证据。前人利用拉曼光谱技术研究了Na₂CO₃在常温常压下的晶格振动模式,但其在高压下的稳定性和结构变化却鲜有报道。利用金刚石压腔装置结合先进的共聚焦拉曼光谱技术,以硅油作为传压介质,在准静水压力条件下,在0.001～27.53 GPa压力区间对Na₂CO₃粉末在600~1 200 cm-1波段的振动特征进行了细致地分析。本次实验重点分析了[CO₃]2-基团振动模式在升压和卸压过程中的行为。结果表明,在0.001～11.88 GPa压力范围内,[CO₃]2-基团对称伸缩振动γ₁（1 088.06和1 070.76 cm-1）、反对称伸缩振动γ₃（865.10和797.50 cm-1）和面内弯曲振动γ₄（720.10和696.71 cm-1）都出现了振动峰的分裂。随着压力增加,所有振动峰都向高频率漂移,半高宽也逐渐增加。在13.40 GPa时,Na₂CO₃发生结构相变,具体表现为690.08 cm-1处出现1条新的拉曼峰,并且随着压力升高该峰的强度逐渐增大。同时反对称伸缩振动峰γ₃以及面内弯曲振动峰γ₄的强度持续减弱,半高宽也继续变大。这些现象表明Na₂CO₃结构相变源于[CO₃]2-内部晶格变化。当压力卸载到4.18 GPa时,[CO₃]2-的振动模式与常温常压下的完全吻合,相变出现的新峰也已经消失,表明该相变是由[CO₃]2-基团畸变引起的并且具有可逆性。继续升压至27.53 GPa,拉曼光谱继续蓝移,Na₂CO₃的拉曼谱线再没有变化,说明高压相在这一压强范围内保持稳定。在整个加压过程中,反对称伸缩振动γ₃和面内弯曲振动γ₄处的拉曼峰出现强度减弱现象。同时也计算了各个峰频率对压力的依赖系数dγ/dP,结果显示[CO₃]2-基团内各个振动模式对压力的响应是不同的,这很可能与Ｃ-Ｏ键的键长有关。最后,对比发现,对称伸缩振动γ₁峰的强度比反对称伸缩振动γ₃和面内弯曲振动γ₄峰的强度大,并且[CO₃]2-基团对称伸缩振动γ₁受压力影响相对较小,可以用来区别不同种类的碳酸盐矿物。     

基于群论的PAHs分子偏振拉曼去噪

利用群论理论研究16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)分子振动规律,并对PAHs指纹区特征拉曼峰进行偏振去噪,减少非特征拉曼峰对特征拉曼峰的干扰,增强16种PAHs之间的拉曼辨识度。群论分析发现16种PAHs分别属于C_s,C_2v,C_2h,D_2h点群,四个点群中的A′,A₁,A_g,A_g类对称振动属于全对称振动,其余对称振动为非全对称振动,其中全对称振动均具有拉曼活性。Gaussian 09杂化密度泛函理论计算与群论分析相结合,发现16种PAHs全对称振动分布拉曼位移全区域,涵盖16种PAHs基团振动模式;全对称振动产生的波动性小,具有一定的抗外部环境干扰能力,稳定性相对较高,并且其产生的拉曼峰更强。根据全对称振动具有代表性、稳定性、显著性的特征,本文将16种PAHs的全对称振动作为特征拉曼振动。此外,研究发现,拉曼偏振效应与振动模对称性直接相关,拉曼光谱的偏振效应具有增强PAHs特征拉曼峰、降低PAHs非特征峰强度的作用。16种PAHs通过拉曼光谱的偏振效应选择性调节作用后,PAHs特征拉曼峰信噪比可提高6.52%~182%,说明利用拉曼偏振效应去除非特征拉曼峰的作用显著,可有效降低特征峰的噪声干扰。因此,所建立的基于群论的PAHs分子拉曼偏振去噪方法可以改善其拉曼光谱信号质量,提高PAHs同步拉曼光谱分析效率,为实现16种PAHs同步拉曼光谱检测提供了理论依据。     

铼的弹性剪切参数C44对温度与压力响应的原位拉曼光谱研究

铼具有高体积弹性模量、高熔点、优良的抗蠕变性能,是一种重要科学研究与工程应用材料。铼的弹性剪切系数C₄₄对温度和压力的响应特性对铼及其合金材料的设计与工程应用具有重要意义。激光拉曼散射技术在研究不同温度和压力条件下六方密堆积结构(hcp)金属的弹性剪切系数C₄₄上具有独特的优势。但由于金属的强反射作用和浅的穿透深度,hcp金属的低波数拉曼散射信号往往很难获取,在一定的温度和压力加载下拉曼信号的获取尤为困难。利用侧向激发拉曼散射技术,有效降低了金属强反射对拉曼光谱采集的影响,成功测量到多晶铼在不同压力与温度条件下的E_2g拉曼振动模,获得铼在常温常压条件的弹性剪切系数(C₄₄=133 GPa)以及其弹性剪切系数C₄₄对温度和压力的响应特性。研究结果表明,多晶铼的弹性剪切系数C₄₄模量随压强的增加而增大,随温度的增加而减小。这也为用光散射方法研究金属材料剪切模量提供了良好研究方法。     

基于分数阶微分算法的大豆冠层氮素含量估测研究

氮素与作物的生长发育、产量和品质密切相关。作物冠层氮素含量的快速、准确、无损检测对于作物营养诊断和长势评估具有重要意义。传统的氮素检测方法检测周期长、操作复杂,同时具有破坏性,无法实现作物氮素含量在时间和空间上的连续动态监测。基于光谱遥感技术快速、无损地获取作物氮素含量是近年来作物组分快速检测研究的热点。当前的研究大多基于原始光谱或整数阶微分(一阶、二阶)预处理后的光谱进行氮素含量预测,原始光谱或整数阶微分预处理后的光谱会忽略光谱曲线间的渐变信息,影响氮素含量的预测准确度。与原始光谱和整数阶微分方法相比,分数阶微分算法在背景噪声去除、有效信息提取等方面较有优势。为研究分数阶微分预处理算法在作物氮素检测中的应用,本文以不同施肥处理下的盆栽大豆作物为研究对象,获取大豆苗期、花期、结荚期和鼓粒期四个生育期共256组冠层高光谱及对应的大豆冠层氮素含量(CNC)数据,运用分数阶微分算法对光谱数据进行0～2阶微分预处理,微分间隔为0.1,分别采用归一化光谱植被指数NDSI、比值光谱指数RSI对预处理后的光谱数据和大豆冠层氮素含量数据进行相关性分析,得到各阶微分预处理下NDSIα(α代表分数阶微分阶数)与大豆CNC,RSIα与大豆CNC相关系数绝对值的最大值及其对应的波段组合--最优波段组合NDSIα(opt)和RSIα(opt),采用线性回归方法,建立各阶微分下NDSIα(opt)与CNC,RSIα(opt)与CNC的预测模型,并与常用植被指数(VOGII, MTCI, DCNI, NDRE)建立的氮素含量预测模型进行比较,研究分数阶微分算法对大豆作物冠层氮素含量预测模型的效果。结果表明：(1)在0～2阶微分范围内,最优波段组合NDSIα(opt),RSIα(opt)与大豆CNC的相关系数随阶数增加呈现先升高后下降趋势。其中,0.8阶微分下NDSI_0.8(R₇₂₅, R₇₆₉)与大豆CNC的相关系数最大,为0.875 9;0.7阶微分下RSI_0.7(R₅₄₈, R₇₆₇)与大豆CNC的相关系数最大,为0.865 1;(2)分数阶微分预处理能够细化光谱数据中的有效信息,增强光谱数据对冠层氮素含量的敏感性,尤其是增强红边平台波段与氮素含量的正相关性及绿波段与氮含量的负相关性;(3)与整数阶微分、常用植被指数相比,分数阶微分能够提高大豆CNC预测模型的准确性。其中,基于0.7阶微分RSI_0.7(R₅₄₈, R₇₆₇)建立的大豆CNC预测模型与0阶微分RSI₀(R₇₂₅, R₇₆₉)相比建模集决定系数(R2_C)和预测集决定系数(R2_P)分别提高了0.061 9和0.016 6,建模集均方根误差(RMSEC)和预测集均方根误差(RMSEP)分别降低了0.552 5和0.180 9,预测相对偏差(RPD)提高了0.110 4。基于0.7阶微分RSI_0.7(R₅₄₈, R₇₆₇)建立的大豆CNC预测模型与VOG II相比R2_C和R2_P分别提高了0.086 6和0.025 5,RMSEC和RMSEP分别降低了0.757 5和0.248 3,RPD提高了0.146 88;(4)基于0.7阶微分比值光谱指数RSI(R₅₄₈, R₇₆₇)建立的大豆LNC预测模型较优,其R2_C为0.748 4,R2_P为0.800 3,RMSEC为4.752 9,RMSEP为3.511 1,RPD为2.253 7,能够较好的估测大豆冠层氮素含量。研究表明分数阶微分算法在大豆冠层氮素含量的定量预测中具有一定的优势,为光谱遥感技术在作物氮营养检测中的应用开拓了新的思路。     

厦漳地区原水DOM的3-DEEM-FRI表征与分析研究

采用三维荧光光谱结合荧光区域积分分析法（3DEEM-FRI）研究了厦漳地区江东泵站、北溪水闸、汀溪水库、莲花水库、坂头水库以及石兜水库原水中溶解性有机物（DOM）的荧光特性、污染特征及其他水质指标与各荧光区域积分体积之间的相关性。结果表明,三种荧光组分-荧光类蛋白质组分（组分Ⅰ,C1）、荧光类蛋白质组分（组分Ⅱ,C2）以及类富里酸组分（组分Ⅲ,C3）在所调查水样中均有显著检出,而溶解性微生物代谢产物组分（组分Ⅳ,C4）在莲花、坂头以及石兜水样中有检出,类腐殖酸组分（组分Ⅴ,C5）在所调查水样中检出不明显;不同水体中同一组分的相对含量差别不大,其中荧光类蛋白质组分占比（P_{1, n}+P_{2, n}）均在60%以上,组分Ⅲ（P_{3, n}）与组分Ⅳ占比（P_{4, n}）均在10%～20%之间,组分Ⅴ占比（P_{5, n}）小于6%;荧光特征参数（1.28β∶α<0.97）显示水体中DOM具有典型的陆源与自生源混合输入的污染特征,组分Ⅰ、组分Ⅱ与组分Ⅳ之间具有同源性特征;TOC与总标准荧光积分体积（Ф_T,n）之间具显著的相关性（R2=0.979 34）,NH+₄-N与组分Ⅳ的标准荧光积分体积（Ф_4,n）之间相关性较好（R2=0.827 98）,而类腐殖质的相对含量（P_{3, n}+P_{5, n}）与SUVA之间的R2为0.703 25。研究表明,3DEEM-FRI分析法可用于识别江湖水库型原水DOM的组成及污染来源,同时还可以实现对TOC含量、NH+₄-N含量以及水体腐殖化程度的有效追踪和指示。     

Shot-by-shot frequency calibration of CARS spectra: Application to the measurement of the collisional line shift in oxygen

A technique using a Fabry-Perot interferometer has been developed to calibrate high-resolution spectra obtained by Coherent Anti-Stokes Raman Spectroscopy (CARS). This technique was used to measure simultaneously the Raman frequency and the Raman signal at each laser shot. We demonstrate the accuracy of the method by measuring theQ(15) line shifts of molecular oxygen due to collisions with oxygen and water vapour.     

Oxygen concentration and temperature measurements in N2–O2 mixtures using rotational coherent anti-Stokes Raman spectroscopy

The accuracy and precision of oxygen concentration and temperature measured by dual-broadband rotational Coherent Anti-Stokes Raman Spectroscopy (CARS) were investigated in nitrogen-oxygen mixtures at atmospheric pressure and temperatures between 290 and 1410 K. The relative standard deviation of temperatures evaluated from pure oxygen rotational CARS spectra was found to be around 5%, and the mean temperature was the same as for nitrogen CARS spectra, except for temperatures above 1000 K, where the temperature was 120 K below the correct value. The in situ calibrated oxygen concentrations were within 10% of the correct value, with a standard deviation of around 1.2% for the mixtures of 12 and 20% oxygen in nitrogen. For the lowest oxygen concentrations considered in this study (2 and 4%), the systematic errors in the evaluated concentrations were very large, and the standard deviation of repeated single-shot measurements was above 2%. However, employing weighting in the spectral fitting routine reduced the errors in the concentration and the single-shot standard deviation was lowered to 0.5%. Finally, it was shown that spectral interference (from oxygen) in a rotational CARS spectrum of nitrogen generally had little impact on the temperature evaluated from fitting the spectra to theoretical nitrogen spectra.     

Cars measurement of vibrational temperatures in electric discharges

The measurement of vibrational and rotational temperatures of D₂ at the center of an electrical discharge has been demonstrated by a new diagnostic technique: Coherent Anti-Stokes Raman Spectroscopy (CARS). On the assumption of equilibration among vibrational levels, T_v was estimated to be approximately 1050 K, whereas T_r was determined to be near ambient (?400 K).     

Ultrabroadband single-pulse CARS of liquids using a spatially dispersive Stokes beam

A double-channel spectrometer, which enables to acquire ultrabroadband single-pulse spectra of liquids by Coherent Anti-Stokes Raman Spectroscopy (CARS), is described. The method used to fulfill the phase-matching condition is based on the fact that the CARS efficiency in dispersive media is the largest when the interactive waves cross each other under frequency-determined angles. The dependence of the spatial separation between the pump and Stokes beam, in front of the crossing CARS lens, due to their frequency difference is analysed. It is shown that the different spectral components of an ultrabroadband Stokes source have phase-matched the CARS process when they are laterally shifted by a conjugated prism pair and focused into the sample. The method is tested in the spectral region 2800–3800 cm^–1 of a non-resonant medium (CCl₄) using an ultrabroadband dye laser (1000 cm^–1 FWHM). The influence of the Stokes beam spatial dispersion on the width of CARS generation is demonstrated. By this method, 1060 cm^–1 wide single-pulse spectra of the OH stretching vibration of liquid water are obtained for the first time. The ratio between the resonant and non-resonant part of the third-order susceptibility in water and methanol is determined.     

CARS thermometry in a transversely heated graphite-tube atomizer used in atomic absorption spectrometry

An experimental setup for gas-temperature diagnostics using Coherent Anti-Stokes Raman Scattering (CARS) in very small sample volumes with great spatial and temporal temperature variations is presented. Studies have been started of a newly designed transversely heated graphite-tube atomizer for atomic absorption spectrometry (Perkin-Elmer, 4100 ZL). For the investigations, high spatial resolution and precise time synchronization of the measurements and also automatic control of the time-dependent intensity of the anti-Stokes signal were realized. The graphite-tube atomizer also offers the possibility of high-temperature-gas spectroscopy. A high-temperature CARS spectrum of CO₂, recorded in the graphite tube at 2300 K, is shown for the first time. A number of hot-band transitions in the spectral region of the Fermi doublet at a Raman shift from 1230 to 1450cm^–1 was observed and assigned, making possible the use of CO₂ as spectroscopic thermometer gas, similar to N₂.     

Determination of temperature and concentration of molecular nitrogen,oxygen and methane with coherent anti-stokes raman scattering

Temperature and concentration measurements by Coherent Anti-Stokes Raman Scattering (CARS) of molecular nitrogen, oxygen and methane were carried out. A comparison of corrected thermocouple and CARS temperature measurements in a high-temperature furnace up to 2000 K is presented. The temperature dependent CARS spectra of N₂ and O₂ are evaluated by a simulation program. Agreement between CARS and thermocouple temperatures is obtained within 40 K for N₂ and 80 K for O₂. Good agreement is found between measurements and calculations of the decrease of CARS intensity with temperature. Various quick-fit methods for N₂-and O₂-temperature measurements from temperature sensitive spectral parameters were tested. Temperature dependent CARS spectra of thev ₁-fundamental of methane are recorded and the methane CARS intensity as function of temperature is measured.     

Temperature and concentration measurements of molecular hydrogen in a filamentary discharge by coherent anti-stokes raman spectroscopy (CARS)

Coherent anti-Stokes Raman Spectroscopy (CARS) is applied to a filamentary discharge in H₂. Temperature and density profiles of molecular hydrogen are determined. The maximum temperature observed on the discharge axis is 5685 K. Vibrational and rotational transitions are analyzed and a difference in the evaluated temperatures is found which increases with pressure. In addition, the reactive thermal conductivity associated with dissociation is determined and compared with earlier work.     

The line shape of Coherent Antistokes Raman Scattering excited under resonance conditions

If Coherent Antistokes Raman Scattering (CARS) is excited by a biharmonic pump in resonance with one photon molecular transition, the Raman line shape is significantly changed compared to the case of nonresonant excitation. This is due to an essential alteration of the 3rd order susceptibility responsible for CARS. Aside from a considerable enhancement of the Raman signal (which makes it possible to detect dissolved molecules in concentration lower than 10^-4 mole/l) the most marked effects are a reversal of the spectral sequence of the Raman maximum and minimum in the CARS-spectrum and for a specially chosen concentration an enhanced contrast of the signal. The factors determining the CARS line shape are discussed theoretically and preliminary experimental results concerning resonance CARS spectra are reported.     

Dispersion of the third-order susceptibility of a cyanine dye measured by coherent anti-Stokes Raman scattering

The dispersion of the third-order susceptibility of the cyanine dye bis-(dimethylamino)-heptamethinium chloride was measured by Coherent Anti-Stokes Raman Scattering (CARS) over a wide wavelength range from 530 to 830 nm. Large negative values of the real part of the second-order hyperpolarizability are observed. The data are analyzed with the help of theoretical calculations based on a perturbative approach for the nonlinearities. The dispersion behavior of the third-order susceptibility is governed by the resonant enhancement due to vibrational transitions of the first excited electronic state and, to lesser extent, by an electronic two-photon resonance around 600 nm.