Effect of Non-Markovian Collisions on Measured Integrated Line Shapes of CO

Using cavity ring-down spectroscopy to probe R-branch transitions of CO in N2, we show that the spectral core of the line shapes associated with the first few rotational quantum numbers, J, can be accurately modeled using a sophisticated line profile, provided that a pressure-dependent line area is introduced. This correction vanishes as J increases and is always negligible in CO-He mixtures. The results are supported by molecular dynamics simulations attributing the effect to non-Markovian behavior of collisions at short times. This work has large implications because corrections must be considered for accurate determinations of integrated line intensities, and for spectroscopic databases and radiative transfer codes used for climate predictions and remote sensing.