Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering （CARS） suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump （or Stokes） spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump （or Stokes） spectrum with the π spectral phase step.

Selective excitation of molecular mode in a mixture by femtosecond resonance-enhanced coherent anti-Stokes Raman scattering spectroscopy

Femtosecond time-resolved coherent anti-Stokes Raman scattering （CARS） spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this broad spectroscopy. However, it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible. Using an electronically resonance-enhanced effect, iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm （corresponding to a saturation iodine vapour as low as about 35 Pa）. The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies （vacuum, heated and pure iodine） in the femtoseeond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.

Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

In broadband coherent anti-Stokes Raman scattering （CARS） spectroscopy with supercontinuum （SC）, the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.

High-resolution imaging of graphene by tip-enhanced coherent anti-Stokes Raman scattering

Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.

Coherent coupling between vibrational modes of C-H bonds at different positions studied by femtosecond time-resolved coherent anti-Stokes Raman scattering

We performed femtosecond time-resolved coherent anti-Stokes Raman scattering （fs-CARS） measurements on liquid toluene and PVK film. For both samples, we selectively excited the CH stretching vibrational modes and observed the expected quantum beat signals. The frequency of the well-defined beats is in good agreement with the energy difference between the two simultaneously excited modes, which demonstrates that a coherent coupling between the vibrational modes of the C H chemical bonds exists at the different positions of the molecules. The dephasing times of the excited modes are obtained simultaneously.

COHERENT ANTI-STOKES RAMAN SCATTERING MICROSCOPY TO MONITOR DRUG DISSOLUTION IN DIFFERENT ORAL PHARMACEUTICAL TABLETS

Coherent anti-Stokes Raman scattering(CARS)microscopy is used to visualize the release of a model drug(theophylline)from a lipid(tripalmitin)based tablet during dissolution.The effects of transformation and dissolution of the drug are imaged in real time.This study reveals that the manufacturing process causes significant differences in the release process:tablets prepared from powder show formation of theophylline monohydrate on the surface which prevents a controlled drug release,whereas solid lipid extrudates did not show formation of monohydrate.This visualization technique can aid future tablet design.

Theoretical and experimental investigations of coherent phonon dynamics in sapphire crystal using femto-second time-resolved coherent anti-Stokes Raman scattering

We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering （fs-CARS） technique. The temporal chirped white-light continuum （WLC） is used for the Stokes pulse, therefore we can perform the selective excitation of the phonon modes without using a complicated laser system. The expected quantum beat phenomenon is clearly observed. The theoretical formulas consist very well with the experimental results. The dephasing times of the excited phonon modes, the wavenumber difference, and the phase shift between the simultaneously excited modes are obtained and discussed. This work opens up a way to study directly high-frequency coherent phonon dynamics in bulk crystals on a femtosecond time scale and is especially helpful for understanding the nature of coherent phonons.

Analysis of detection limit to time-resolved coherent anti-Stokes Raman scattering nanoscopy

In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume can be detected. Here reported is a theoretical analysis of detection limit （DL） to time-resolved CARS （T-CARS） nanoscopy based on our proposed additional probe-beam-induced phonon depletion （APIPD） method for the low concentration samples. In order to acquire a detailed shot-noise limited signal-to-noise （SNR） and the involved parameters to evaluate DL, the T-CARS process is described with full quantum theory to estimate the extreme power density levels of the pump and Stokes beams determined by saturation behavior of coherent phonons, which are both actually on the order of ~ 109 W/cm2. When the pump and Stokes intensities reach such values and the total intensity of the excitation beams arrives at a maximum tolerable by most biological samples in a certain suppressed focal volume （40-nm suppressed focal scale in APIPD method）, the DL correspondingly varies with exposure time, for example, DL values are 103 and 102 when exposure times are 20 ms and 200 ms respectively.

Selective Excitation of Two-pulse Femtosecond Coherent Anti-Stokes Raman Scattering in a Mixture

In this paper, we experimentally study the selective excitation of two-pulse femtosecond coherent anti-Stokes Raman scattering (CARS) in a mixture of dibromomethane (CH2Br2) and chloroform (CHCl3) by adaptive pulse shaping based on genetic algorithm. Second harmonic generation frequency-resolved optical gating (SHG-FROG) traces indicate that the spectral amplitude and phase of the optimal pulse are both modulated. Finally, we discuss the physical mechanism for the selective excitation of femtosecond CARS based on the retrieved information from SHG-FROG traces.

基于anti-Stokes Raman散射温度效应的温度解调理论研究

激光脉冲进入光纤中,与光纤分子相互作用,产生Raman散射和Raylei曲散射。由于Raman散射具有温度效应,其散射光强度受温度调制,可作为温度信息的载体,用于温度解调及测温系统设计。本文提出了可行的温度解调方法及理论推导,并推导出单通道和双通道条件下的测温关系,设计出两种条件下的传感器系统。

Simultons in Nonstationary CARS by Polaritons: Energy and Velocity

This paper is the continuation of our previous research in which we studied such aspects of CARS spectroscopy in dipole-active crystals by polaritons as the regimes of coherent simultaneous propagation of three waves (anti-Stokes, Stokes, and the pump field) to increase the efficiency of CARS as a spectroscopic method. In our previous research, we have shown the possibility of the existence of simultons at all frequencies of interacting waves. All interacting waves were supposed to be linearly polarised and plane, the medium was assumed to be nonmagnetic, and the medium was transparent at frequencies of anti-Stokes, Stokes, and the pump field (laser). The purpose of the present paper is to consider the energy carried by electromagnetic waves and its relationship with the gain factor and velocity of the simultons.

相干反Stokes Raman效应的微分强度

以量子电动力学的基本理论为依据,从最一般的四光子过程入手,给出了相干反Stokes Raman效应的量子解积.

Stimulated Raman scattering microscopy for rapid brain tumor histology

Rapid histology of brain tissues with sufficient diagnostic information has the great potential to aid neurosurgons during operations.Stimulated Raman Scattering(SRS)microscopy is an emerging label-free imaging technique,with the intrinsic chemical resolutions to delineate brain tumors from normal tissues without the nood of time-consuming tissue processing.Growing number of studies have shown SRS as a“virtual histology"tool for rapid diagnosis of various types of brain tumors.In this review,we focus on the basic principles and current developments of SRS microscopy,as well as its applications for brain tumor imaging.

用于CARS成像的波长可调谐光纤激光器

相干反斯托克斯拉曼散射(CARS)显微成像在快速病理学分析、药代动力学等领域展现了极大的应用潜力,然而在成像时产生的非共振背景噪声信号会影响CARS信号的探测。通过调谐波长,可实现在拉曼共振、非共振噪声共存处产生信号,也可实现在仅有非共振噪声处产生信号,两信号相消可以在一定程度上消除非共振背景噪声的影响。文章搭建了基于分离脉冲放大及晶体倍频的波长可调谐掺铒光纤激光系统,通过控制两级放大器的泵浦功率实现了779.1~784.5 nm,777.5~786.1 nm,784.5~790.5 nm的波长调谐,获得了110.8 mW,136 fs的脉冲输出。通过与掺镱激光系统被动同步,可用于CARS成像。

Improvement in the calculation of anti-Stokes energy transfer and experimental justification based on Er_(0.01)Yb_xY_(1 0.01 x)VO_4 crystal

The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering theory as compared with the classical Raman theory is introduced to successfully describe the anti-Stokes energy transfer. The theoretical formula for the improvement on the calculation of anti-Stokes energy transfer rate is derived for the first time in this study. The correctness of introducing coefficient exp{△E/kT} from well-known Raman scatter theory is demonstrated also. Moreover, the experimental lifetime measurement in Er0.01YbxY1-0.01-xVO4 crystal is performed to justify the validity of our important improvement in the original phonon-assisted energy transfer theory for the first time.

飞秒相干反斯托克斯拉曼散射光谱测温研究进展

当今世界大约90%的能量供应都是由燃烧生成的。在燃烧场中,火焰的温度影响着场中各种组分链式反应的途径和浓度,获取燃烧场温度信息可以为提高燃料燃烧效率,改进燃烧装置的设计提供重要的支撑依据。随着我国在航空、航天和航海这类高端制造业领域的不断发展,各种大型燃气轮机和超声速发动机的研发进入加速期,此类燃烧装置产生的火焰具有高温、高压、湍流超声速和持续时间短等特点。传统的接触式测温法难以对这类湍流燃烧场进行温度测量,近年以激光光谱法为代表的非接触式测温技术逐渐走向成熟,并获得了广泛地应用。与超短脉冲相结合的飞秒相干反斯托克斯拉曼散射光谱测温技术凭借可提供高时间分辨率(每秒可提供上千个测温数据)、高测温精度和高测温灵敏度等优势而被应用到各种高温、湍流等复杂燃烧场景温度诊断中。文章概述了飞秒相干反斯托克斯拉曼散射测温技术的基本原理,综述了该技术在稳态火焰、加热气体、模拟燃气轮机等燃烧环境中测温工作的研究进展,简要介绍了飞秒时间分辨相干反斯托克斯拉曼光谱的研究和应用,着重介绍了可以实现毫秒量级时间分辨率的飞秒啁啾探测脉冲相干反斯托克斯拉曼散射测温技术和混合飞秒/皮秒相干反斯托克斯拉曼散射测温技术的基本原理和应用进展。指出了三种测温技术的优缺点,并提出飞秒相干反斯托克斯拉曼散射测温技术目前需要关注并解决的技术问题,主要为在高温高压湍流燃烧等极端条件下实现高精度CARS光谱高保真反演出温度信息,以及高温高压湍流燃烧场极端条件下如何获得高信噪比CARS信号的问题。展望了今后的发展趋势:通过高时间分辨的测量,获得湍流火焰中温度的瞬时演化规律,并建立各种复杂火焰的温度演化信息数据库,为研究各种发动机机理提供支撑。

非平衡等离子体流场相干反斯托克斯拉曼散射光谱计算及振转温度测量

高温非平衡问题是高超声速流动中最基本的科学问题之一,而热力学非平衡特性的准确表征是理解高温非平衡问题和高超声速空气动力学的基础,如何准确可靠地表征流场的热力学非平衡特性是解决高超声速飞行器在稀薄流域高温非平衡问题的关键.本文基于相干反斯托克斯拉曼散射基本原理,开发了面向非平衡流场的振转温度反演算法,并在宽温度范围静态环境开展验证.搭建了非平衡等离子体流场相干反斯托克斯拉曼散射测温实验平台并开展实验验证,结果表明微波等离子体处于热力学非平衡状态,并且振动温度和转动温度与微波功率成正比,而热力学非平衡度与微波功率成反比,当微波功率从80W增加至180 W时,等离子体电子数密度增加,中性粒子通过与电子碰撞获得能量使振动温度从(2201±43)K增加至(2452±56)K、转动温度从(382±20)K增加至(535±49)K;而处于振动激发态的分子通过振动-平动弛豫过程(对于N2分子弛豫速率与温度成正比)将部分振动能转化为平动能,导致振动温度与转动温度的差异降低,等离子体热力学非平衡度从0.83降低至0.78.

CARS技术及其在火炸药燃烧诊断中的应用

介绍了推进剂燃烧火焰的特点和CARS(CoherentAnti StokesRamanScattering)检测技术在推进剂燃烧诊断 (温度、浓度和燃烧机理研究 )中的应用。根据研究结果 ,论述了CARS技术在推进剂燃烧诊断应用中的几个关键问题 :准确度。

阻尼最小二乘算法CARS光谱温度拟合

为了解决相干反斯托克斯喇曼散射(CARS)光谱CARSFT计算程序在温度拟合过程中,对初值依赖大、测量光谱信噪比差、不易收敛的问题,通过分析非线性迭代算法,采用了阻尼最小二乘算法对氮气CARS光谱进行温度拟合。针对CARS理论光谱计算公式较为复杂的特点,采用数值差分的方式来获得迭代计算时所需要的设计矩阵。分析了横向偏移、纵向偏移和温度三个主要参量对拟合残差的影响,发现纵向偏移的初值设置对温度拟合影响较大。拟合温度2000K时的标准理论CARS光谱,设置偏离较大的初始值,采用阻尼最小二乘法获得了较好的结果。迭代计算167步后,温度拟合为2 005.6K,残差为0.027 463。拟合光谱信噪比较差的CARS光谱,阻尼最小二乘法也能稳定收敛。结果验证了阻尼最小二乘法对初值的依赖不大,并且当拟合谱信噪比较差时也能收敛,可用于在恶劣环境下CARS测量光谱的拟合。

一种新的USED CARS相位匹配实现技术

相位匹配是相干反斯托克斯拉曼散射(CARS)测温的关键技术之一,针对现有非稳腔空间增强探测(USED)相位匹配方式中存在的背景辐射大、光路调试不灵活以及斯托克斯光利用率低的不足,提出了一种新的USED CARS相位匹配实现方案:即设计一个与斯托克斯光斑大小相当、呈45°斜角的斜反镜,用于反射全部斯托克斯光,并以斜反镜代替传统USED CARS中的环反镜,让泵浦光从斜反镜后方射入,从而形成USED相位匹配方式。新的USED CARS相位匹配方案中:由于斜反镜面积相对于环反镜大为减小,使得因反射而进入光路的背景辐射大幅降低;斜反镜本身可作为光路调节元件,因而增加了光路调试灵活度;斯托克斯光被斜反镜全部反射用于产生CARS信号,提高了其利用效率。基于平面火焰炉稳态火焰开展的测温实验结果表明:新的USED CARS相位匹配方案不但克服了传统USED CARS中存在的不足,而且具有更小的标准差,是一种更为有效的相位匹配方法。