RESUMO
The CO(2)(010)-O((3)P) vibrational energy transfer (VET) efficiency is a key input to aeronomical models of the energy budget of the upper atmospheres of Earth, Venus, and Mars. This work addresses the physical mechanisms responsible for the high efficiency of the VET process at the thermal energies existing in the terrestrial upper atmosphere (150 K=T=550 K). We present a quantum-mechanical study of the process within a reduced-dimensionality approach. In this model, all the particles remain along a plane and the O((3)P) atom collides along the C(2v) symmetry axis of CO(2), which can present bending oscillations around the linear arrangement, while the stretching C-O coordinates are kept fixed at their equilibrium values. Two kinds of scattering calculations are performed on high-quality ab initio potential energy surfaces (PESs). In the first approach, the calculations are carried out separately for each one of the three PESs correlating to O((3)P). In the second approach, nonadiabatic effects induced by spin-orbit couplings (SOC) are also accounted for. The results presented here provide an explanation to some of the questions raised by the experiments and aeronomical observations. At thermal energies, nonadiabatic transitions induced by SOC play a key role in causing large VET efficiencies, the process being highly sensitive to the initial fine-structure level of oxygen. At higher energies, the two above-mentioned approaches tend to coincide towards an impulsive Landau-Teller mechanism of the vibrational to translational (V-T) energy transfer.
RESUMO
For data analysis of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) atmospheric limb emission spectroscopic experiment on Environmental Satellite microwindows, i.e., small spectral regions for data analysis, have been defined and optimized. A novel optimization scheme has been developed for this purpose that adjusts microwindow boundaries such that the total retrieval error with respect to measurement noise, parameter uncertainties, and systematic errors is minimized. Dedicated databases that contain optimized microwindows for retrieval of vertical profiles of pressure and temperature, H2O, O3, HNO3, CH4, N2O, and NO2 have been generated. Furthermore, a tool for optimal selection of subsets of predefined microwindows for specific retrieval situations has been provided. This tool can be used further for estimating total retrieval errors for a selected microwindow subset. It has been shown by use of this tool that an altitude-dependent definition of microwindows is superior to an altitude-independent definition. For computational efficiency a dedicated microwindow-related list of spectral lines has been defined that contains only those spectral lines that are of relevance for MIPAS limb sounding observations.