Simulations and spectra of water in CO matrices

Abstract

Models for the inclusion of water molecules in carbon monoxide matrices are developed using density functional theory applied to amorphous solid systems. The models cover a large range of systems for smaller or larger CO matrices with different water content, consisting of either individual H₂O molecules or small clusters linked by H-bonds. The vibrational spectra of the samples are predicted at the minimum of their potential energy surface. The spectra allow instances where the water molecules remain isolated or form aggregates to be discerned, and they also provide an indication of the strength of the H-bonding, when present. The calculations support recent experimental observations that linked IR bands at 3707 cm⁻¹ and 3617 cm⁻¹ to the presence of unbound water molecules in water-poor CO/H₂O mixed ices. Assignment of some observed bands to water dimers or trimers is suggested as well. The residual static pressure in fixed-volume simulation cells is also calculated.