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Since January 2004, the planetary Fourier spectrometer (PFS) onboard the Mars Express satellite has been recording near-infrared limbspectra of high quality up to the tangent altitudes ≈ 150 km, withpotential information on density and thermal structure of the upper Martianatmosphere. We present first results of our modeling of the PFS shortwavelength channel (SWC) daytime limb spectra for the altitude region above90 km. We applied a ro-vibrational non-LTE model based on the stellarastrophysics technique of accelerated lambda iteration (ALI) to solve themulti-species and multi-level CO2 problem in the Martian atmosphere. Weshow that the long-standing discrepancy between observed and calculatedspectra in the cores and wings of 4.3 µm region is explained by thenon-thermal rotational distribution of molecules in the upper vibrationalstates 10011 and 10012 of the CO2 main isotope second hot (SH) bandsabove 90 km altitude. The redistribution of SH band intensities from bandbranch cores into their wings is caused (a) by intensive production of theCO2 molecules in rotational states with j > 30 due to the absorption ofsolar radiation in optically thin wings of 2.7 µm bands and (b) by ashort radiative lifetime of excited molecules, which is insufficient ataltitudes above 90 km for collisions to maintain rotation of excitedmolecules thermalized. Implications for developing operational algorithms formassive processing of PFS and other instrument limb observations arediscussed

Evidence of a significant rotational non-LTE effect in the CO&lt;sub&gt;2&lt;/sub&gt; 4.3 µm PFS-MEX limb spectra

Evidence of a significant rotational non-LTE effect in the CO<sub>2</sub> 4.3 µm PFS-MEX limb spectra