Space-Resolved OH Vibrational Spectra of the Hydration Shell around CO2

The CO2 molecule is weakly bound in water. Here we analyze the influence of a dissolved CO2 molecule on the structure and OH vibrational spectra of the surrounding water. From the analysis of ab initio molecular dynamics simulations (BLYP-D3) we present static (structure, coordination, H-bonding, tetrahedrality) and dynamical (OH vibrational spectra) properties of the water molecules as a function of distance from the solute. We find a weakly oscillatory variation (“ABBA”) in the ‘solution minus bulk water’ spectrum. The origin of these features can largely be traced back to solvent–solute hard-core interactions which lead to variations in density and tetrahedrality when moving from the solute’s vicinity out to the bulk region. The high-frequency peak in the solute-affected spectra is specifically analyzed and found to originate from both water OH groups that fulfill the geometric H-bond criteria, and from those that do not (dangling ones). Effectively, neither is hydrogen-bonded.