Constrained multispectrum analysis of CO2-Ar broadening at 6227 and 6348 cm-1

We report the first extensive experimental measurements of Ar-broadened half-width and pressure-induced shift coefficients, speed dependence parameters, and line mixing coefficients for the 30013 <- 00001 and 30012 <- 00001 bands of (OCO)-O-16-C-12-O-16 centered near 6227 and 6348 cm(-1), respectively. These parameters were determined from 15 self-broadened and six Ar-broadened CO2 spectra recorded at room temperature with long absorption path lengths (25 to 121 m) using the McMath-Pierce Fourier transform spectrometer (FTS) at the National Solar Observatory. All 21 spectra were fit simultaneously using a multispectrum nonlinear least-squares technique. The line positions and line intensities were constrained to quantum mechanical expressions to obtain maximum accuracies in the retrieved parameters. Speed-dependent line shapes with line mixing (via the relaxation matrix formalism) were required to remove systematic errors in the fit residuals using only the Voigt profile. Remaining fit residuals were minimized by adjusting the half-width and pressure-induced shift coefficients of the overlapping 31113 <- 01101 and 31112 <- 01101 hot bands. We compare the Ar-broadening parameters with those recently determined for self-and air-broadening in the 30012 <- 00001 and 30013/ 00001 bands and also with other Ar-broadening values from the literature, as appropriate.