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 N_{2}, 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.