CO diffusion and desorption kinetics in CO2 ices

IR Cooke, KI Öberg, EC Fayolle, Z Peeler… - The Astrophysical …, 2018 - iopscience.iop.org
IR Cooke, KI Öberg, EC Fayolle, Z Peeler, JB Bergner
The Astrophysical Journal, 2018iopscience.iop.org
The diffusion of species in icy dust grain mantles is a fundamental process that shapes the
chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are
scarce. Here we present measurements of CO diffusion into CO 2 ice at low temperatures
(T= 11–23 K) using CO 2 longitudinal optical phonon modes to monitor the level of mixing of
initially layered ices. We model the diffusion kinetics using Fick's second law and find that
the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving …
Abstract
The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO 2 ice at low temperatures (T= 11–23 K) using CO 2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick's second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300±40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO 2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO 2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240±90 K to 1410±70 K depending on the CO 2 deposition temperature and resultant ice porosity. The measured CO–CO 2 desorption barriers demonstrate that CO binds equally well to CO 2 and H 2 O ices when both are compact. The CO–CO 2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.
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