Rotational CARS for simultaneous measurements of temperature and concentrations of N2, O2, CO, and CO2 demonstrated in a CO/air diffusion flame

Rotational coherent anti-Stokes Raman spectroscopy (CARS) has over the years demonstrated its strong potential to measure temperature and relative concentrations of major species in combustion. A recent work is the development and experimental validation of a CO₂ model for thermometry, in addition to our previous rotational CARS models for other molecules. In the present work, additional calibration measurements for relative CO₂/N₂ concentrations have been made in the temperature range 294-1246 K in standardized CO₂/N₂ mixtures. Following these calibration measurements, rotational CARS measurements were performed in a laminar CO/air diffusion flame stabilized on a Wolfhard-Parker burner. High-quality spectra were recorded from the fuel-rich region to the surrounding hot air in a lateral cross section of the flame. The spectra were evaluated to obtain simultaneous profiles of temperature and concentrations of all major species; N₂, O₂, CO, and CO₂. The potential for rotational CARS as a multi-species detection technique is discussed in relation to corresponding strategies for vibrational CARS.     

High‐resolution narrowband CARS spectroscopy in the spectral fingerprint region

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy is an important technique for spectroscopy and chemically selective microscopy, but wider implementation requires dedicated versatile tunable sources. We describe an optical parametric oscillator (OPO) based on a magnesium oxide‐doped periodically poled lithium niobate crystal, with a novel variable output coupler, used as a tunable coherent light source. The OPO's signal wavelength ranges from 880 to 1040 nm and its idler wavelength from 1090 to 1350 nm. We use this OPO to demonstrate high‐resolution narrowband CARS spectroscopy on bulk polystyrene from 900 to 3600 cm⁻¹, covering a large part of the molecular fingerprint region. Recording vibrational spectra using narrowband CARS spectroscopy has several advantages over spontaneous Raman spectroscopy, which we discuss. We isolate the resonant part of the CARS spectrum and compare it to the spontaneous Raman spectrum of polystyrene using the maximum entropy method of phase retrieval; we find them to be in extremely good agreement. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical modeling of single-laser-shot, chirped-probe-pulse femtosecond coherent anti-Stokes Raman scattering thermometry

Chirped-probe-pulse (CPP) femtosecond (fs) coherent anti-Stokes Raman scattering (CARS) spectroscopy for single-laser-shot temperature measurements in flames is discussed. In CPP fs CARS, a giant Raman coherence is created in the medium by impulsive pump-Stokes excitation, and the temperature-dependent temporal decay of this initial coherence is mapped into the frequency of the CARS signal using a CPP. The theory of the CPP fs CARS technique is presented. A computer code has been developed to calculate theoretical CPP fs CARS spectra. The input parameters for the calculation of the theoretical spectra include the temperature, probe time delay, ratio of the resonant and nonresonant susceptibilities, and parameters for characterizing the pump, Stokes and probe pulses. The parameters for characterizing the pump, Stokes and probe pulses are determined from the best fit of theoretical spectra to experimental spectra acquired from calibration flames at a known temperature. For spectra acquired in subsequent measurements, these laser parameters are fixed and temperature is determined as one of the fit parameters from the best fit of theoretical spectra to experimental spectra. For single-laser-shot CPP fs CARS temperature measurements performed in steady, near-adiabatic flames, the best-fit temperature distribution width is typically less than 1.5% of the mean temperature. The mean temperature is accurate to within approximately 3% with respect to the adiabatic flame temperature. The most significant limitation on temperature measurement accuracy is associated with the evaluation of the theoretical laser parameters. Significant improvements in the temperature measurement accuracy are expected once monitoring equipment capable of characterizing the spectrum and phase of each laser pulse is incorporated in the experiments.     

Temperature and concentration measurements in acetylene-nitrogen mixtures in the range 300–600 K using dual-broadband rotational CARS

Pure rotational coherent anti-Stokes Raman scattering (CARS) experiments have been performed in acetylene for temperatures ranging from 294 to 582 K, and in mixtures of acetylene and nitrogen in the mole fraction range of 0.06–0.32 for acetylene at room temperature. The experimental spectra are evaluated by a least-square fitting to libraries of theoretically calculated spectra using two different Raman linewidth models, one with and one without dependence on the rotational quantum number J. It is found that a J-dependent model is favourable, both regarding temperature measurements in pure acetylene, and simultaneous acetylene concentration and temperature measurements in different mixtures of acetylene and nitrogen. For the temperature measurements performed in pure acetylene the temperature inaccuracy is generally less than 2% when the J-dependent model for the Raman linewidths is used. It is found that fitting the value of the non-resonant susceptibility significantly improves the quality of the spectral fits and is a requirement for high temperature accuracy with the present model. The evaluated concentrations show a maximum error of 13% on a relative scale. Potential sources of systematical errors both regarding measured temperatures and acetylene concentrations are discussed. Received: 8 June 1999 / Revised version: 3 Spetember 1999 / Published online: 3 November 1999     

CARS difference spectroscopy. II—Determination of small frequency shifts and band width changes in binary mixtures

The experimental verification of CARS difference spectroscopy (CARS-DS) is presented and its application to binary mixtures is shown. The experimental set-up allows the simultaneous measurement of CARS spectra of two different samples under identical conditions. It is shown how the method can be used for the accurate determination of small frequency shifts and band width changes in liquid mixtures. The experimental spectra obtained were analysed by their numerical simulation using a least-squares fitting routine. As examples, experimental results for chloroform–deuterochloroform isotopic mixtures and binary mixtures of benzene and toluene of different concentrations are presented. In both cases frequency shifts and changes in the band width were observed which exhibit an almost linear dependence on the mole fraction of the probe species.     

Dual-pump coherent anti-Stokes Raman scattering thermometry in a sooting turbulent pool fire

We present a dual-pump coherent anti-Stokes Raman scattering (CARS) instrument, which has been constructed for the probing of temperature fluctuations in turbulent pool fires of meter-scale. The measurements were performed at the Fire Laboratory for Accreditation of Models and Experiments (FLAME) facility at Sandia National Laboratories, which provides a canonical fire plume in quiescent wind conditions, with well-characterized boundary conditions and access for modern laser-diagnostic probes. The details of the dual-pump CARS experimental facility for the fire-science application are presented, and single-laser-shot CARS spectra containing information from in-fire N₂, O₂, H₂, and CO₂ are provided. Single-shot temperatures are obtained from spectral fitting of the Raman Q-branch signature of N₂, from which histograms that estimate the pdf of the enthalpy-averaged temperature fluctuations at the center of the fire plume are presented. Results from two different sooting fire experiments reveal excellent test-to-test repeatability of the fire plume provided by FLAME, as well as the CARS-measured temperatures. The accuracy and precision of the CARS temperatures is assessed from measurements in furnace-heated air, where the temperature can be accurately determined by a thermocouple. At temperatures in excess of 500 K, the furnace results show that the CARS measurements are accurate to within 2-3% and precise to within ±3-5% of the measured absolute temperature.     

Narrow-band BoxCARS applied to CO2 laser discharges

Summary CARS (Coherent Anti-Stokes Raman Scattering) has developed into a powerful tool for studying molecular systems. One of its possibilities is to derive vibrational and rotational temperatures as well as concentrations of molecules from measurements of the energy level population differences. A very good spatial resolution of CARS technique is one of its important advantages. This feature has been utilized for making spatially resolved measurements of the vibrational and rotational temperatures of N₂ in a d.c.-excited transverse-flow CO₂ laser discharge. Apart from that also spectra of CO₂, CO and O₂ in the discharge have been taken, which allowed us to evaluate the spatial distributions of those components in the discharge. Additionally first investigations of a microwave-excited CO₂ laser module have been performed for comparison. Paper presented at the ?XI European CARS Workshop?, Florence, Italy, 23–25 March, 1992.     

Resonance CARS in solids

Summary Solid-state resonance CARS spectroscopy is applied to investigate the vibronic properties of polydiacetylene chains and of the permanganate ion. Results are presented for single crystals of the symmetrically substituted diacetylene FBS where few polymer chains are embedded in the host lattice built by the monomers and for the permanganate ion doped in potassium perchlorate single crystals. Particularly, spectra of the C=C and the C≡C stretching vibrations of the polymer chains and of the fully symmetric ν₁-breathing mode of the permanganate ion, recorded for different pump laser frequencies, have been investigated. For the polydiacetylenes a theoretical model is introduced which describes the excitation and line profiles. The model is based on a crude Born-Oppenheimer approximation. The electronic wave functions are calculated by means of an LCAO-MO method in the Hückel approach. The Franck-Condon integrals are calculated under the assumption of harmonic potential functions. The simulation of the CARS spectra is based on results of calculations of absorption and resonance Raman spectra obtained from the diacetylene single crystals. Paper presented at the “XI European CARS Workshop?, Florence, Italy, 23–25 March, 1992.     

Heterodyne interferometric polarization coherent anti‐Stokes Raman scattering (HIP‐CARS) spectroscopy

We demonstrate a new technique that combines polarization sensitivity of the coherent anti‐Stokes Raman scattering (CARS) response with heterodyne amplification for background‐free detection of CARS signals. In this heterodyne interferometric polarization CARS (HIP‐CARS), the major drawbacks of polarization and heterodyne CARS are rectified. Using a home‐built picosecond optical parametric oscillator, we are able to address vibrational stretches between 600 and 1650 cm⁻¹ and record continuous high‐resolution Raman equivalent HIP‐CARS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Development of rotational CARS for combustion diagnostics using a polarization approach

Rotational Coherent anti-Stokes Raman spectroscopy (CARS) has the last decades been developed into a useful tool for thermometry and concentration measurements in combustion. In this paper, we present a novel polarization approach of the technique, which will enhance its potential and widen the range of conditions at which it can be utilized. The theory of the polarization approach is described in detail. It is shown that by specific arrangement of the polarizations of the laser beams, total suppression of the non-resonant background signal can be obtained, and thus by probing only the resonant CARS signal the diagnostic utility of the technique increases. The main benefit of the approach is in situations where the non-resonant background signal is relatively high in comparison with the resonant signal. The high potential of polarization rotational CARS for thermometry is demonstrated in some illustrative examples, for example, nitrogen thermometry on the fuel side of diffusion flames, and carbon monoxide thermometry in the product gas of ethylene/oxygen/argon-flames.     

Ultrafast Raman loss spectroscopy

This paper deals with a new form of nonlinear Raman spectroscopy called ‘ultrafast Raman loss spectroscopy (URLS)’. URLS is analogous to stimulated Raman spectroscopy (SRS) but is much more sensitive than SRS. The signals are background (noise) free unlike in coherent anti‐Stokes Raman spectroscopy (CARS) and it provides natural fluorescence rejection, which is a major problem in Raman spectroscopy. In addition, being a self‐phase matching process, the URLS experiment is much easier than CARS, which requires specific phase matching of the laser pulses. URLS is expected to be alternative if not competitive to CARS microscopy, which has become a popular technique in applications to materials, biology and medicine. Copyright © 2009 John Wiley & Sons, Ltd.     

Microanalytical nonlinear single-beam spectroscopy combining an unamplified femtosecond fibre laser,pulse shaping and interferometry

Nonlinear vibrational spectroscopy using a single beam of femtosecond pulses from an unamplified fibre laser oscillator is demonstrated. To achieve high spectral resolution and sensitive signal detection with the picojoule pulse energies available, pulse shaping and integrated interferometric detection is employed. The spectroscopic technique used is coherent anti-Stokes Raman scattering (CARS), which yields well-resolved spectra of molecular vibrations in the 100–350 cm^-1 domain of halomethane samples in the liquid phase. We explore the implications of phase control for the interferometric detection of weak signals. The presented combination of a fiber laser, pulse shaping and CARS microspectroscopy is a first example of simplified schemes for compact and robust nonlinear spectroscopic detection and sensing, which is demonstrated exemplarily by on-line monitoring of the chemical composition in a microfluidic flow cell. PACS 42.55.Wd; 42.62.Fi; 78.47.Fg; 42.65.Dr; 82.80.Gk; 92.20.cn     

部分临床药物的拉曼光谱研究

针对目前临床药物拉曼光谱的缺乏和药物检测领域的现状,利用拉曼光谱技术对抗生素、抗组织胺、血凝酶和止吐剂等几类常用临床药物进行了拉曼光谱的测量和研究。通过观测上述具有良好拉曼活性的药物样品拉曼光谱,不仅确定了样品拉曼峰的位移、强度和线宽,还探索了其包络的线形等光谱特性。通过分析和比较拉曼光谱图,找出各药物间的异同; 对于那些由于拉曼活性低或拉曼光谱的复杂样品,虽然暂时无法识别,但也进行了尝试性的测量或提出了测量建议。研究表明: 小分子药物的光谱特征很明显,拉曼峰分布较广, 对其进行光谱识别简单易行; 而大分子都表现出较弱的光谱特征峰, 常常伴随复杂的包络,不仅导致了对其光谱识别的困难, 也很难准确确定特征峰位置。对于不同药物,提出了用拉曼光谱测量和分析其药物成分的可行性,并通过分析其拉曼光谱的特性, 为医学工作者识别和分析药物成分提供了实验证据。不仅为建立药物的拉曼光谱数据库奠定了基础。还使业界看到了快速识别和检测药物的前景,从而促进拉曼光谱技术在药物检测上的运用。     

CARS spectral fitting with multiple resonant species using sparse libraries

The coherent anti‐Stokes Raman spectroscopy (CARS) technique is often used in the study of turbulent flames. Fast and accurate algorithms are needed for fitting CARS spectra for temperature and multiple chemical species. This paper describes the development of such an algorithm. The algorithm employs sparse libraries whose size grows more slowly with number of species than a regular library. It was demonstrated by fitting synthetic ‘experimental’ dual‐pump CARS spectra containing four resonant species (N₂, O₂, H₂ and CO₂), both with added noise and without it, and by fitting experimental spectra from a H₂ air flat flame produced by a Hencken burner. In the four‐species example, the library was nearly an order of magnitude smaller than the equivalent regular library (fitting times are correspondingly faster), and the fitting errors in the absence of added noise were negligible compared to the random errors associated with fitting noisy spectra. When fitting noisy spectra, weighted least squares fitting to signal intensity, as opposed to least squares fitting or least squares fitting to square root of intensity, minimized random and bias errors in fit parameters. Copyright © 2011 John Wiley & Sons, Ltd.     

Single-pulse CARS spectra in solid propellant combustion at atmosphere pressure

The unstable-resonator spatially enhanced detection (USED) coherent anti-stokes Raman spectroscopy (CARS) measurements of temperature and N2 concentration in the combustion of solid propellant at atmosphere pressure are reported. The USED CARS measurement system has a high spatial solution of ~ 0.1 mm in diameter and 3 mm in length, and permits instantaneous measurement at 10-Hz rate. The single-pulse N2 Q-branch CARS spectra have been obtained from the propellant combustion. The temperatures and N2 concentrations of the propellant flame at different height have been achieved by fitting the experimental data to theoretical spectra. The results indicate that the temperature is up to ~ 2500 K with N2 concentration in a range from 10% to 26%.     

Effects of laser linewidth on coherent antiStokes Raman spectroscopy

Expressions for the generated antiStokes spectral density in coherent antiStokes Raman spectroscopy (CARS) are obtained, which take into account the finite linewidths of laser sources and which may be used to analyse observed spectra. Lorentzian and gaussian laser lineshapes are taken as special cases, which enable further analytic results for single and multiline CARS spectra to be derived. Emphasis is placed on scanning and broadband (multiplex) CARS techniques, and the choice of laser sources discussed from the spectral point of view. As examples of multiline spectra an analytical account of a periodic spectrum is presented and temperature measurement from Q-branch spectra is treated.     

Multipoint temperature and oxygen-concentration measurements using rotational coherent anti-Stokes Raman spectroscopy

A novel technique for coherent anti-Stokes Raman spectroscopy (CARS) measurements in multiple points is presented. With a system of cylindrical lenses, each laser beam is split into several focused beams, yielding separate planar boxcars configurations. Spectrally resolved CARS signals are detected at different heights on the CCD chip. With dual-broadband rotational CARS the setup is demonstrated for quantitative measurements of temperature- and oxygen-concentration profiles. The technique was demonstrated for three points only, but it can be extended to more points by use of special optics; this choice must be based on a sufficient signal-to-noise ratio in all points for the actual measurement condition.     

Tracking molecular structure deformation of nitrobenzene and its torsion-vibration coupling by intense pumping CARS

The structural deformation induced by intense laser field of liquid nitrobenzene(NB) molecule,a typical molecule with restricting internal rotation,is tracked by time- and frequency-resolved coherent anti-Stokes.Raman spectroscopy(CARS) technique with an intense pump laser.The CARS spectra of liquid NB show that the NO_2 torsional mode couples with the NO_2 symmetric stretching mode,and the NB molecule undergoes ultrafast structural deformation with a relaxation time of 265 fs.The frequency of NO_2 torsional mode in liquid NB(42 cm~(-1)) at room temperature is found from the sum and difference combination bands involving the NO_2 symmetric stretching mode and torsional mode in time- and frequency-resolved CARS spectra.     

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.