We use experimental mid-infrared optical constants and extended effective medium approximations to determine the porosity and the band strengths of multi-phase composite ices grown at 30 K. A set of porous H₂O:CH₄ ices are taken as a prototypical example. As a benchmark and proof of concept, the stoichiometry of the ice constituents is retreived with good accuracy from the refractive indices and the extinction coefficients of the reference binary ice mixtures with known compositions. Accurate band strengths are then calculated from experimental mid-infrared spectra of complex ices. We notice that the presence of pores has only a small effect on the overall band strengths, whereas a water dilution can considerably alter them. Different levels of porosity are observed depending on the abundance of methane used as a gas contaminant premixed with water prior to background deposition. The absorption profiles are also found to vary with deposition rate. To explain this, we use Monte Carlo simulations and we observe that the deposition rate strongly affects the pore size distribution as well as the ice morphology through reorganization processes. Extrapolated to genuine interstellar ices, the methodology presented in this paper can be used to evaluate the porosity and to quantify the relative abundances from observational data.

The level of porosity of interstellar ices, largely comprised of amorphous solid water (ASW), contains clues about the trapping capacity of other volatile species and determines the surface accessibility that is needed for solid-state reactions to take place. Aims. Our goal is to simulate the growth of amorphous water ice at low temperature (10 K) and to characterise the evolution of the porosity (and the specific surface area) as a function of temperature (from 10 to 120 K). Methods. Kinetic Monte Carlo simulations are used to mimic the formation and the thermal evolution of pores in amorphous water ice. We follow the accretion of gas-phase water molecules as well as their migration on surfaces with different grid sizes, both at the top growing layer and within the bulk. Results. We show that the porosity characteristics change substantially in water ice as the temperature increases. The total surface of the pores decreases to a great extend while the total volume decreases only slightly for higher temperatures. This will decrease the overall reaction efficiency, but in parallel, small pores connect and merge, which allows trapped molecules to meet and react within the pores network and provides a pathway to increase the reaction efficiency. We introduce pore coalescence as a new solid-state process that may boost the solid-state formation of new molecules in space, and which has not been considered so far.

Aims. This article aims to provide an alternative method of measuring the porosity of multi-phase composite ices from their refractive indices and of characterising how the abundance of a premixed contaminant (e.g., CO ₂) affects the porosity of water-rich ice mixtures during omni-directional deposition. Methods. We combine optical laser interference and extended effective medium approximations (EMAs) to measure the porosity of three astrophysically relevant ice mixtures: H₂O:CO₂ = 10:1, 4:1, and 2:1. Infrared spectroscopy is used as a benchmarking test of this new laboratory-based method. Results. By independently monitoring the O-H dangling modes of the different water-rich ice mixtures, we confirm the porosities predicted by the extended EMAs. We also demonstrate that CO₂ premixed with water in the gas phase does not significantly affect the ice morphology during omni-directional deposition, as long as the physical conditions favourable to segregation are not reached. We propose a mechanism in which CO₂ molecules diffuse on the surface of the growing ice sample prior to being incorporated into the bulk and then fill the pores partly or completely, depending on the relative abundance and the growth temperature.