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O2−O2 and O2−N2 collision-induced absorption mechanisms unravelled

A Publisher Correction to this article was published on 13 April 2018

This article has been updated


Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2−O2 and O2−N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2−O2 and O2−N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

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Fig. 1: Experimental and theoretical collision-induced absorption spectra for the \({X}^{3}{\Sigma }_{g}^{-}(v^{\prime\prime} =0)\to {a}^{1}{\Delta }_{g}(v^{\prime} )\) bands of O2−O2 and O2−N2.
Fig. 2: Experimental and theoretical collision-induced absorption spectra for the \({X}^{3}{{\rm{\Sigma }}}_{g}^{-}(v^{\prime\prime} =0)\to {b}^{1}{{\rm{\Sigma }}}_{g}^{+}(v^{\prime} )\) bands of O2−O2 and O2−N2.
Fig. 3: Translational profiles for the \({X}^{3}{\Sigma }_{g}^{-}\to {a}^{1}{{\rm{\Delta }}}_{g}\) transition for both exchange and spin–orbit mechanisms.
Fig. 4: Collision-induced absorption spectra for the \({X}^{3}{{\rm{\Sigma }}}_{g}^{-}(v^{\prime\prime} =0)\to {b}^{1}{{\rm{\Sigma }}}_{g}^{+}(v^{\prime} =0)\) band in air, normalized to the product of O2 and air number densities.
Fig. 5: Collision-induced absorption spectra for the \({X}^{3}{\Sigma }_{g}^{-}\to {a}^{1}{\Delta }_{g}\) and \({b}^{1}{{\rm{\Sigma }}}_{g}^{+}\) transitions in O2−O2 and experimental results.

Change history

  • 13 April 2018

    In the version of this Article originally published, Figures 3 and 4 were erroneously swapped, this has been corrected in all versions of the Article.


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This work was funded by the Netherlands Organisation for Scientific Research (NWO; grant 022.003.048). T.K. acknowledges additional support by the EU COST Action MOLIM (CM1405) and a pre-doctoral fellowship of the Smithsonian Astrophysical Observatory. A.B. and D.H.P. acknowledge EU H2020 ITN-EID project ‘PUFF’ (grant no. 642820) for support. I.E.G. is supported by NASA AURA program grant NNX14AI55G.

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The theory was developed by T.K., A.v.d.A. and G.C.G. Cavity ring-down experiments were performed M.A.J.K., A.B., D.H.P. and W.J.v.d.Z. I.E.G. contributed to the comparison between experiment and theory.

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Correspondence to Gerrit C. Groenenboom.

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Supplementary information

Supplementary Information

Supplementary Figure 1, Supplementary Tables 1–3, Supplementary calculations, modelling, methods and analysis

Supplementary Data Set 1

Experimental results for the a1Δg(v′=1) band for O2–N2 and O2–O2

Supplementary Data Set 2

Theoretical collision-induced absorption spectra for O2-N2

Supplementary Data Set 3

Theoretical collision-induced absorption spectra for O2-O2

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Karman, T., Koenis, M.A.J., Banerjee, A. et al. O2−O2 and O2−N2 collision-induced absorption mechanisms unravelled. Nature Chem 10, 549–554 (2018).

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