Density dependence of measured line intensities for O2 transitions

Abstract

We report predictions and measurements of O2 absorption spectra that exhibit line intensity depletion with increasing gas density. This effect, which is attributed to the finite duration of collisions, alters the line shape by redistributing a portion of the intensity from a relatively narrow spectrum that can be described by an impact-approximation-based profile to a broad pedestal with a width that is inversely related to the collision duration. Using classical molecular dynamics simulations (CMDS), we predicted details regarding this mechanism for O2 with four collision partners: O2, N2, Ar, and He at a temperature of 296 K. These simulations were validated by comparisons with experimental intensity depletion coefficients obtained from absorption spectra of the 1.27 μm band of O2 in air; Ar and He acquired over a wide pressure range up to 120 kPa. All experimental spectra were recorded using high-precision cavity ring-down spectroscopy (CRDS) apparatuses at NIST (United States of America) and LIPhy (France). For air-broadened O2, more specifically, a mean depletion value of ∼0.3% amagat−1 was observed, with almost no resolvable rotational dependence. The temperature dependence of the intensity depletion in this system was also investigated by CMDS at 250 and 296 K and by CRDS spectra of air at 250, 275, and 296 K. The theoretical results suggest a nearly 1/T2 temperature dependence of the intensity-weighted depletion coefficient, which over the limited temperature range considered, was only slightly greater than the measurement precision. Finally, simulations of atmospheric solar absorption spectra were implemented to quantify the impact of neglecting this depletion effect on the retrieved surface pressure, resulting in a negatively biased measurement of ∼0.14%, with a spread of ∼0.02% caused by seasonal variations in gas temperature.