Coherent Anti-Stokes Raman Spectrocopy Technique for Combustion Analysis or CARS

Introduction:
CARS is a relatively new kind of spectroscopic technique which is used for various purposes like bacterial analyses, chemical fluid analyses and combustion analyses. It is based on a non-linear conversion of two laser beams i-e i.e. the scattered signal is not linearly related to the input laser intensity, into a coherent, laser like Raman beam of high intensity in the anti-Stokes region. This method is very useful for obtaining Raman spectra of fluorescing samples, gases in discharge, plasmas, combustion and atmospheric chemistry. The coherent and nonlinear nature of the process leads to an enormous increase of scattering intensity compared to conventional linear Raman scattering. The price to be paid is a reduction to 0-D spatial resolution, a single point is measured at a time. The nonlinear dependence of the signal on almost everything render quantitative measurements of concentrations difficult or impossible. Nevertheless experimental spectral multiplexing methods allow for temperature measurement, within a single laser shot. So at least it is easily possible to gather statistical information on temperature at a rate of the pulse repetition capability of the laser system. 3-D space, on the other hand, has to be scanned geometrically.

How it works:By the CRAS technique two relatively high powered, typically pulsed, laser beams at angular frequencies 1 and 2 are focused together along with a dye laser beam in a sample. As a result of mixing the two lasers, a coherent beam resembling a low intensity laser beam at frequency, 3 = 21 2, is generated in the medium. The efficiency of the conversion to frequency 3 depends critically upon the presence of molecular resonances at a frequency 1 2, the laser intensities, the resonance line width, and the number density. Typically (os is varied to obtain a spectrum. As 1 2 is swept over the molecular resonance, the intensity of the beam at 3 changes. Recording this intensity as a function of 21 2 constitutes a CARS spectrum.

As can be seen from above figure the three incoming laser beams, usually two green beams of a Nd:YAG laser and a red beam of a dye laser, have to overlap in a volume of about 0.05 mm in diameter and 0.5 mm in length. Only in that overlap volume the interaction with the molecules takes place, so the actual measurement is confined to a very small place. By changing the frequency difference (1- 2) to a particular Raman resonance, various molecules can be probed.

Figure: Energy level diagram for resonant CARS. Real and virtual states are indicated by solid and dashed lines respectively The energy of the scattered light depends quadratically on the number of molecules and hence a measurement of the molecular density can be obtained. In addition, the frequency of the signal depends on the Boltzmann relationship,

which means that an analysis of the frequency content allows the measurement of temperature.

CARS Combustion diagnostic setup (above) Most often nitrogen is used as a thermometer molecule" since these molecules are stable, they are less likely to be involved in combustion reactions. The nitrogen molecules interact with the incoming beams and produce a signal with a high "laser like" directionality and thus are used as a good indicator of temperature.

Types of CARS:
Depending on the nature of the flow, either broadband CARS or narrow band CARS can be used

Narrowband CARS:
Narrow-band CARS is based on the use of a narrow-band laser, and therefore a fine wavelength tuning has to be performed in order to match an excitation wavelength and obtain sufficiently strong output signal. In this case, the sensitivity of this technique is considerably enhanced, and the detection limit can reach several ppm.

Broadband CARS:
Broadband CARS is achieved by using a broadband laser that does not need to be tuned to a specific excitation peak. The accuracy of broadband CARS thermometry is therefore lower than with the narrow-band method, but its main advantage lies in its ability to perform rapid measurements.

Advantages of CARS:
The high laser-like directionality of signal emitted by interacting N2 molecules is a dramatic advantage over linear Raman scattering, where the signal is emitted in all directions. The directionality allows for large distances between "emitter" and "receiver". This method can have errors less than 5% for temperatures, which is more satisfactory than most LIF results. Unlike LIF, the measurements are limited to specific points and quantitative measurements require in-depth understanding of the instrumentation and spectroscopic factors. The reason why CARS might be preferred to LIF is because of its ability to provide accurate temperature and species concentration measurements in extremely hostile environments.