NASA - National Aeronautics and Space Administration

CO2-rich planetary atmospheres such as those of Mars and Venus require accurate knowledge of CO2 broadened HDO half-width coefficients and their temperature dependence exponents for reliable abundance determination. Although a few calculated line lists have recently been published on HDO–CO2 line shapes and their temperature dependences, laboratory measurements of those parameters are thus far non-existent. In this work, we report the first measurements of CO2-broadened half-width and pressure-shift coefficients and their temperature dependences for over 220 transitions in the ν2 band. First measurements of self-broadened half-width and self-shift coefficients at room temperature are also obtained for majority of these transitions. In addition, the first experimental determination of collisional line mixing has been reported for 11 transition pairs for HDO–CO2 and HDO–HDO systems. These results were obtained by analyzing ten high-resolution spectra of HDO and HDO–CO2 mixtures at various sample temperatures and pressures recorded with the Bruker IFS-125HR Fourier transform spectrometer at the Jet Propulsion Laboratory (JPL). Two coolable absorption cells with path lengths of 20.38 cm and 20.941 m were used to record the spectra. The various line parameters were retrieved by fitting all ten spectra simultaneously using a multispectrum nonlinear least squares fitting algorithm.

The HDO transitions in the 1100–4100 cm
1 range were extracted from the HITRAN2012 database. For the ν2 and 2ν2 -ν2 bands there were 2245 and 435 transitions, respectively. Modified Complex Robert–Bonamy formalism (MCRB) calculations were made for the half-width coefficients, their temperature dependence and the pressure shift coefficients for the HDO–CO2 and HDO–HDO collision systems. MCRB calculations are compared with the measured values.