Mikael Afzelius

Thermometry in internal combustion engines via dual-broadband rotational coherent anti-Stokes Raman spectroscopy

Rotational coherent anti-Stokes Raman spectroscopy (CARS) has since the beginning of the 1980s been developed as a non-intrusive tool for temperature measurements in combustion. Since the introduction of the dual-broadband concept in 1986, the quality of the technique has been much improved, and application to practical combustion situations facilitated. Since the first demonstration of its use in spark-ignition engines in 1993, several measurement campaigns in engines have been accomplished. These campaigns concerned temperature measurements in the unburned gas mixture before combustion as part of a larger project with the aim of improving the knowledge on the phenomenon of engine knock. In this paper, the results of this work are reviewed with a focus on the characteristics of the technique and the quality of the evaluated temperatures. Re-evaluations of data using an improved theoretical model are presented and compared with previous results. Moreover, the treatment of large data sets on single shots from spatial regions with conditions varying from unburned to burned gas is discussed. It is demonstrated that dual-broadband rotational CARS probing nitrogen and oxygen has a high potential for thermometry at the conditions in the unburned gas mixture. Merits and limitations of the technique are discussed and the issues treated are, among others, experimental problems, data evaluation, and single-shot temperature accuracy.

Semiclassical calculations of collision line broadening in Raman spectra of N2 and CO mixtures.

We present a detailed theoretical study of pressure-broadened Raman line shapes in binary mixtures of nitrogen and carbon monoxide. The semiclassical Robert-Bonamy theory was used to calculate self-broadened Q-branch linewidths of N(2) and CO, and Lennard-Jones (LJ) potential energy surface parameters were fixed by comparing our results with extensive experimental linewidth data. For the case of N(2), the ab initio PES8 potential energy surface was investigated, however, the anisotropic repulsive part had to be reduced to ensure a good agreement with experimental linewidths. The agreement between calculations and experiments was remarkably good, both for self-broadened N(2) and CO Q-branch linewidths. Yet, our calculations were not able to predict the experimentally observed difference between Q- and S-branch linewidths of self-broadened N(2). The central results of this work are the Q-branch linewidths of N(2)-CO and CO-N(2), which have been calculated through an extrapolation of the parameters of the potential energy surfaces used for self-broadened linewidths by common combination rules.

Pure rotational coherent anti-Stokes Raman spectroscopy in mixtures of CO and N 2

We present a model for quantitative measurements in binary mixtures of nitrogen and carbon monoxide by the use of dual-broadband rotational coherent anti-Stokes Raman spectroscopy. The model has been compared with experimental rotational coherent anti-Stokes Raman scattering spectra recorded within the temperature range of 294-702 K. Temperatures and concentrations were evaluated by spectral fits using libraries of theoretically calculated spectra. The relative error of the temperature measurements was 1-2%, and the absolute error of the CO concentration measurements was <0.5% for temperatures < or =600 K. For higher temperatures, the gas composition was not chemically stable, and we observed a conversion of CO to CO2. The influence of important spectroscopic parameters such as the anisotropic polarizability and Raman line-broadening coefficients are discussed in terms of concentration measurements. In particular, it is shown that the CO concentration measurement was more accurate if N2-CO and CO-N2 line-broadening coefficients were included in the calculation. The applicability of the model for quantitative flame measurements is demonstrated by measuring CO concentrations in ethylene/air flames.

Development of multipoint vibrational coherent anti-Stokes Raman spectroscopy for flame applications

A novel technique for coherent anti-Stokes Raman spectroscopy (CARS) measurements in multiple points is presented. In a multipass cavity the pump and Stokes laser beams are multiply reflected and refocused into a measurement volume with an adjustable number of separated points along a line. This optical arrangement was used in a vibrational CARS setup with planar BOXCARS phase-matching configuration. The CARS spectra from spatially separated points were recorded at different heights on a CCD camera. Measurements of temperature profiles were carried out in the burned gas zone of a premixed one-dimensional flame to demonstrate the applicability of this method for temperature measurements in high-temperature regions. The ability to measure in flames with strong density gradients was demonstrated by simultaneous measurements of Q-branch spectra of N2 and CO in a Wolfhard-Parker burner flame. Interference phenomena found in multipoint spectra are discussed, and possible solutions are proposed. Merits and limitations of the technique are discussed.

Exact treatment of classical trajectories governed by an isotropic potential for linewidth computations

Two models for exact classical trajectories in the field of an isotropic potential are investigated for the purpose of semiclassical linebroadening calculations. The first directly uses the exact solution of the classical equation of motion. The second starts from the equation of motion and computes the trajectory by numerical solution of the differential equations. In the framework of both models, all the computations are performed numerically, thus allowing the use of refined ab initio potential energy surfaces. For the example of the linebroadening of pure nitrogen and carbon monoxide, it is shown that, owing to the dominant short-range forces in these self-perturbed molecular systems, the limiting case corresponding to traditional parabolic trajectories can be used without any important loss of precision.